The maximum rate of mammal evolution
Evans, Alistair R.; Jones, David; Boyer, Alison G.; Brown, James H.; Costa, Daniel P.; Ernest, S. K. Morgan; Fitzgerald, Erich M. G.; Fortelius, Mikael; Gittleman, John L.; Hamilton, Marcus J.; Harding, Larisa E.; Lintulaakso, Kari; Lyons, S. Kathleen; Okie, Jordan G.; Saarinen, Juha J.; Sibly, Richard M.; Smith, Felisa A.; Stephens, Patrick R.; Theodor, Jessica M.; Uhen, Mark D.
2012-03-01
How fast can a mammal evolve from the size of a mouse to the size of an elephant? Achieving such a large transformation calls for major biological reorganization. Thus, the speed at which this occurs has important implications for extensive faunal changes, including adaptive radiations and recovery from mass extinctions. To quantify the pace of large-scale evolution we developed a metric, clade maximum rate, which represents the maximum evolutionary rate of a trait within a clade. We applied this metric to body mass evolution in mammals over the last 70 million years, during which multiple large evolutionary transitions occurred in oceans and on continents and islands. Our computations suggest that it took a minimum of 1.6, 5.1, and 10 million generations for terrestrial mammal mass to increase 100-, and 1,000-, and 5,000-fold, respectively. Values for whales were down to half the length (i.e., 1.1, 3, and 5 million generations), perhaps due to the reduced mechanical constraints of living in an aquatic environment. When differences in generation time are considered, we find an exponential increase in maximum mammal body mass during the 35 million years following the Cretaceous-Paleogene (K-Pg) extinction event. Our results also indicate a basic asymmetry in macroevolution: very large decreases (such as extreme insular dwarfism) can happen at more than 10 times the rate of increases. Our findings allow more rigorous comparisons of microevolutionary and macroevolutionary patterns and processes.
The maximum rate of mammal evolution
Evans, Alistair R.; Jones, David; Boyer, Alison G.; Brown, James H.; Costa, Daniel P.; Ernest, S. K. Morgan; Fitzgerald, Erich M. G.; Fortelius, Mikael; Gittleman, John L.; Hamilton, Marcus J.; Harding, Larisa E.; Lintulaakso, Kari; Lyons, S. Kathleen; Okie, Jordan G.; Saarinen, Juha J.; Sibly, Richard M.; Smith, Felisa A.; Stephens, Patrick R.; Theodor, Jessica M.; Uhen, Mark D.
2012-01-01
How fast can a mammal evolve from the size of a mouse to the size of an elephant? Achieving such a large transformation calls for major biological reorganization. Thus, the speed at which this occurs has important implications for extensive faunal changes, including adaptive radiations and recovery from mass extinctions. To quantify the pace of large-scale evolution we developed a metric, clade maximum rate, which represents the maximum evolutionary rate of a trait within a clade. We applied this metric to body mass evolution in mammals over the last 70 million years, during which multiple large evolutionary transitions occurred in oceans and on continents and islands. Our computations suggest that it took a minimum of 1.6, 5.1, and 10 million generations for terrestrial mammal mass to increase 100-, and 1,000-, and 5,000-fold, respectively. Values for whales were down to half the length (i.e., 1.1, 3, and 5 million generations), perhaps due to the reduced mechanical constraints of living in an aquatic environment. When differences in generation time are considered, we find an exponential increase in maximum mammal body mass during the 35 million years following the Cretaceous–Paleogene (K–Pg) extinction event. Our results also indicate a basic asymmetry in macroevolution: very large decreases (such as extreme insular dwarfism) can happen at more than 10 times the rate of increases. Our findings allow more rigorous comparisons of microevolutionary and macroevolutionary patterns and processes. PMID:22308461
The maximum rate of mammal evolution.
Evans, Alistair R; Jones, David; Boyer, Alison G; Brown, James H; Costa, Daniel P; Ernest, S K Morgan; Fitzgerald, Erich M G; Fortelius, Mikael; Gittleman, John L; Hamilton, Marcus J; Harding, Larisa E; Lintulaakso, Kari; Lyons, S Kathleen; Okie, Jordan G; Saarinen, Juha J; Sibly, Richard M; Smith, Felisa A; Stephens, Patrick R; Theodor, Jessica M; Uhen, Mark D
2012-03-13
How fast can a mammal evolve from the size of a mouse to the size of an elephant? Achieving such a large transformation calls for major biological reorganization. Thus, the speed at which this occurs has important implications for extensive faunal changes, including adaptive radiations and recovery from mass extinctions. To quantify the pace of large-scale evolution we developed a metric, clade maximum rate, which represents the maximum evolutionary rate of a trait within a clade. We applied this metric to body mass evolution in mammals over the last 70 million years, during which multiple large evolutionary transitions occurred in oceans and on continents and islands. Our computations suggest that it took a minimum of 1.6, 5.1, and 10 million generations for terrestrial mammal mass to increase 100-, and 1,000-, and 5,000-fold, respectively. Values for whales were down to half the length (i.e., 1.1, 3, and 5 million generations), perhaps due to the reduced mechanical constraints of living in an aquatic environment. When differences in generation time are considered, we find an exponential increase in maximum mammal body mass during the 35 million years following the Cretaceous-Paleogene (K-Pg) extinction event. Our results also indicate a basic asymmetry in macroevolution: very large decreases (such as extreme insular dwarfism) can happen at more than 10 times the rate of increases. Our findings allow more rigorous comparisons of microevolutionary and macroevolutionary patterns and processes.
Maximum Principles for Discrete and Semidiscrete Reaction-Diffusion Equation
Petr Stehlík
2015-01-01
Full Text Available We study reaction-diffusion equations with a general reaction function f on one-dimensional lattices with continuous or discrete time ux′ (or Δtux=k(ux-1-2ux+ux+1+f(ux, x∈Z. We prove weak and strong maximum and minimum principles for corresponding initial-boundary value problems. Whereas the maximum principles in the semidiscrete case (continuous time exhibit similar features to those of fully continuous reaction-diffusion model, in the discrete case the weak maximum principle holds for a smaller class of functions and the strong maximum principle is valid in a weaker sense. We describe in detail how the validity of maximum principles depends on the nonlinearity and the time step. We illustrate our results on the Nagumo equation with the bistable nonlinearity.
Mean square convergence rates for maximum quasi-likelihood estimator
Arnoud V. den Boer
2015-03-01
Full Text Available In this note we study the behavior of maximum quasilikelihood estimators (MQLEs for a class of statistical models, in which only knowledge about the first two moments of the response variable is assumed. This class includes, but is not restricted to, generalized linear models with general link function. Our main results are related to guarantees on existence, strong consistency and mean square convergence rates of MQLEs. The rates are obtained from first principles and are stronger than known a.s. rates. Our results find important application in sequential decision problems with parametric uncertainty arising in dynamic pricing.
The tropical lapse rate steepened during the Last Glacial Maximum.
Loomis, Shannon E; Russell, James M; Verschuren, Dirk; Morrill, Carrie; De Cort, Gijs; Sinninghe Damsté, Jaap S; Olago, Daniel; Eggermont, Hilde; Street-Perrott, F Alayne; Kelly, Meredith A
2017-01-01
The gradient of air temperature with elevation (the temperature lapse rate) in the tropics is predicted to become less steep during the coming century as surface temperature rises, enhancing the threat of warming in high-mountain environments. However, the sensitivity of the lapse rate to climate change is uncertain because of poor constraints on high-elevation temperature during past climate states. We present a 25,000-year temperature reconstruction from Mount Kenya, East Africa, which demonstrates that cooling during the Last Glacial Maximum was amplified with elevation and hence that the lapse rate was significantly steeper than today. Comparison of our data with paleoclimate simulations indicates that state-of-the-art models underestimate this lapse-rate change. Consequently, future high-elevation tropical warming may be even greater than predicted.
The tropical lapse rate steepened during the Last Glacial Maximum
Loomis, Shannon E.; Russell, James M.; Verschuren, Dirk; Morrill, Carrie; De Cort, Gijs; Sinninghe Damsté, Jaap S.; Olago, Daniel; Eggermont, Hilde; Street-Perrott, F. Alayne; Kelly, Meredith A.
2017-01-01
The gradient of air temperature with elevation (the temperature lapse rate) in the tropics is predicted to become less steep during the coming century as surface temperature rises, enhancing the threat of warming in high-mountain environments. However, the sensitivity of the lapse rate to climate change is uncertain because of poor constraints on high-elevation temperature during past climate states. We present a 25,000-year temperature reconstruction from Mount Kenya, East Africa, which demonstrates that cooling during the Last Glacial Maximum was amplified with elevation and hence that the lapse rate was significantly steeper than today. Comparison of our data with paleoclimate simulations indicates that state-of-the-art models underestimate this lapse-rate change. Consequently, future high-elevation tropical warming may be even greater than predicted. PMID:28138544
Maximum orbit plane change with heat-transfer-rate considerations
Lee, J. Y.; Hull, D. G.
1990-01-01
Two aerodynamic maneuvers are considered for maximizing the plane change of a circular orbit: gliding flight with a maximum thrust segment to regain lost energy (aeroglide) and constant altitude cruise with the thrust being used to cancel the drag and maintain a high energy level (aerocruise). In both cases, the stagnation heating rate is limited. For aeroglide, the controls are the angle of attack, the bank angle, the time at which the burn begins, and the length of the burn. For aerocruise, the maneuver is divided into three segments: descent, cruise, and ascent. During descent the thrust is zero, and the controls are the angle of attack and the bank angle. During cruise, the only control is the assumed-constant angle of attack. During ascent, a maximum thrust segment is used to restore lost energy, and the controls are the angle of attack and bank angle. The optimization problems are solved with a nonlinear programming code known as GRG2. Numerical results for the Maneuverable Re-entry Research Vehicle with a heating-rate limit of 100 Btu/ft(2)-s show that aerocruise gives a maximum plane change of 2 deg, which is only 1 deg larger than that of aeroglide. On the other hand, even though aerocruise requires two thrust levels, the cruise characteristics of constant altitude, velocity, thrust, and angle of attack are easy to control.
Maximum, minimum, and optimal mutation rates in dynamic environments
Ancliff, Mark; Park, Jeong-Man
2009-12-01
We analyze the dynamics of the parallel mutation-selection quasispecies model with a changing environment. For an environment with the sharp-peak fitness function in which the most fit sequence changes by k spin flips every period T , we find analytical expressions for the minimum and maximum mutation rates for which a quasispecies can survive, valid in the limit of large sequence size. We find an asymptotic solution in which the quasispecies population changes periodically according to the periodic environmental change. In this state we compute the mutation rate that gives the optimal mean fitness over a period. We find that the optimal mutation rate per genome, k/T , is independent of genome size, a relationship which is observed across broad groups of real organisms.
Predicting the solar maximum with the rising rate
Du, Z L
2011-01-01
The growth rate of solar activity in the early phase of a solar cycle has been known to be well correlated with the subsequent amplitude (solar maximum). It provides very useful information for a new solar cycle as its variation reflects the temporal evolution of the dynamic process of solar magnetic activities from the initial phase to the peak phase of the cycle. The correlation coefficient between the solar maximum (Rmax) and the rising rate ({\\beta}a) at {\\Delta}m months after the solar minimum (Rmin) is studied and shown to increase as the cycle progresses with an inflection point (r = 0.83) at about {\\Delta}m = 20 months. The prediction error of Rmax based on {\\beta}a is found within estimation at the 90% level of confidence and the relative prediction error will be less than 20% when {\\Delta}m \\geq 20. From the above relationship, the current cycle (24) is preliminarily predicted to peak around October 2013 with a size of Rmax =84 \\pm 33 at the 90% level of confidence.
Measurement and relevance of maximum metabolic rate in fishes.
Norin, T; Clark, T D
2016-01-01
Maximum (aerobic) metabolic rate (MMR) is defined here as the maximum rate of oxygen consumption (M˙O2max ) that a fish can achieve at a given temperature under any ecologically relevant circumstance. Different techniques exist for eliciting MMR of fishes, of which swim-flume respirometry (critical swimming speed tests and burst-swimming protocols) and exhaustive chases are the most common. Available data suggest that the most suitable method for eliciting MMR varies with species and ecotype, and depends on the propensity of the fish to sustain swimming for extended durations as well as its capacity to simultaneously exercise and digest food. MMR varies substantially (>10 fold) between species with different lifestyles (i.e. interspecific variation), and to a lesser extent (aerobic scope, interest in measuring this trait has spread across disciplines in attempts to predict effects of climate change on fish populations. Here, various techniques used to elicit and measure MMR in different fish species with contrasting lifestyles are outlined and the relevance of MMR to the ecology, fitness and climate change resilience of fishes is discussed.
Reaction Order Ambiguity in Integrated Rate Plots
Lee, Joe
2008-01-01
Integrated rate plots are frequently used in reaction kinetics to determine orders of reactions. It is often emphasised, when using this methodology in practice, that it is necessary to monitor the reaction to a substantial fraction of completion for these plots to yield unambiguous orders. The present article gives a theoretical and statistical…
Reaction rates for reaction-diffusion kinetics on unstructured meshes
Hellander, Stefan; Petzold, Linda
2017-02-01
The reaction-diffusion master equation is a stochastic model often utilized in the study of biochemical reaction networks in living cells. It is applied when the spatial distribution of molecules is important to the dynamics of the system. A viable approach to resolve the complex geometry of cells accurately is to discretize space with an unstructured mesh. Diffusion is modeled as discrete jumps between nodes on the mesh, and the diffusion jump rates can be obtained through a discretization of the diffusion equation on the mesh. Reactions can occur when molecules occupy the same voxel. In this paper, we develop a method for computing accurate reaction rates between molecules occupying the same voxel in an unstructured mesh. For large voxels, these rates are known to be well approximated by the reaction rates derived by Collins and Kimball, but as the mesh is refined, no analytical expression for the rates exists. We reduce the problem of computing accurate reaction rates to a pure preprocessing step, depending only on the mesh and not on the model parameters, and we devise an efficient numerical scheme to estimate them to high accuracy. We show in several numerical examples that as we refine the mesh, the results obtained with the reaction-diffusion master equation approach those of a more fine-grained Smoluchowski particle-tracking model.
Maximum entropy analysis of flow and reaction networks
Niven, Robert K.; Abel, Markus; Schlegel, Michael; Waldrip, Steven H.
2015-01-01
We present a generalised MaxEnt method to infer the stationary state of a flow network, subject to "observable" constraints on expectations of various parameters, as well as "physical" constraints arising from frictional properties (resistance functions) and conservation laws (Kirchhoff laws). The method invokes an entropy defined over all uncertainties in the system, in this case the internal and external flow rates and potential differences. The proposed MaxEnt framework is readily extendable to the analysis of networks with uncertainty in the network structure itself.
Resonances and the thermonuclear reaction rate
Hussein, M S; Sargeant, A J; Pato, M P
2003-01-01
We present an approximate analytic expression for thermonuclear reaction rate of charged particles when the cross section contains a single narrow or wide resonance described by a Breit-Wigner shape. The resulting expression is uniformly valid as the effective energy and resonance energy coalesce. We use our expressions to calculate the reaction rate for $^{12}$C(p,$\\gamma$)$^{13}$N.
Screened Thermonuclear Reaction Rates on Magnetar Surfaces
LIU Hong-Lin; LUO Zhi-Quan; LIU Jing-Jing; LAI Xiang-Jun
2008-01-01
Improving Salpeter's method, we discuss the effect of superstrong magnetic fields (such as those of magnetars) on thermonuclear reaction rates. These most interesting reactions, including the hydrogen burning by the CNO cycle and the helium burning by the triple alpha reaction, are investigated as examples on the magnetar surfaces. The obtained result shows that the superstrong magnetic fields can increase the thermonuclear reaction rates by many orders of magnitude. The enhancement may have significant influence for further study research of the magnetars, especially for the x-ray luminosity observation and the evolution of magnetars.
The mechanics of granitoid systems and maximum entropy production rates.
Hobbs, Bruce E; Ord, Alison
2010-01-13
A model for the formation of granitoid systems is developed involving melt production spatially below a rising isotherm that defines melt initiation. Production of the melt volumes necessary to form granitoid complexes within 10(4)-10(7) years demands control of the isotherm velocity by melt advection. This velocity is one control on the melt flux generated spatially just above the melt isotherm, which is the control valve for the behaviour of the complete granitoid system. Melt transport occurs in conduits initiated as sheets or tubes comprising melt inclusions arising from Gurson-Tvergaard constitutive behaviour. Such conduits appear as leucosomes parallel to lineations and foliations, and ductile and brittle dykes. The melt flux generated at the melt isotherm controls the position of the melt solidus isotherm and hence the physical height of the Transport/Emplacement Zone. A conduit width-selection process, driven by changes in melt viscosity and constitutive behaviour, operates within the Transport Zone to progressively increase the width of apertures upwards. Melt can also be driven horizontally by gradients in topography; these horizontal fluxes can be similar in magnitude to vertical fluxes. Fluxes induced by deformation can compete with both buoyancy and topographic-driven flow over all length scales and results locally in transient 'ponds' of melt. Pluton emplacement is controlled by the transition in constitutive behaviour of the melt/magma from elastic-viscous at high temperatures to elastic-plastic-viscous approaching the melt solidus enabling finite thickness plutons to develop. The system involves coupled feedback processes that grow at the expense of heat supplied to the system and compete with melt advection. The result is that limits are placed on the size and time scale of the system. Optimal characteristics of the system coincide with a state of maximum entropy production rate.
Morrison, Glenn; Shaughnessy, Richard; Shu, Shi
2011-02-01
A Monte Carlo analysis of indoor ozone levels in four cities was applied to provide guidance to regulatory agencies on setting maximum ozone emission rates from consumer appliances. Measured distributions of air exchange rates, ozone decay rates and outdoor ozone levels at monitoring stations were combined with a steady-state indoor air quality model resulting in emission rate distributions (mg h -1) as a function of % of building hours protected from exceeding a target maximum indoor concentration of 20 ppb. Whole-year, summer and winter results for Elizabeth, NJ, Houston, TX, Windsor, ON, and Los Angeles, CA exhibited strong regional differences, primarily due to differences in air exchange rates. Infiltration of ambient ozone at higher average air exchange rates significantly reduces allowable emission rates, even though air exchange also dilutes emissions from appliances. For Houston, TX and Windsor, ON, which have lower average residential air exchange rates, emission rates ranged from -1.1 to 2.3 mg h -1 for scenarios that protect 80% or more of building hours from experiencing ozone concentrations greater than 20 ppb in summer. For Los Angeles, CA and Elizabeth, NJ, with higher air exchange rates, only negative emission rates were allowable to provide the same level of protection. For the 80th percentile residence, we estimate that an 8-h average limit concentration of 20 ppb would be exceeded, even in the absence of an indoor ozone source, 40 or more days per year in any of the cities analyzed. The negative emission rates emerging from the analysis suggest that only a zero-emission rate standard is prudent for Los Angeles, Elizabeth, NJ and other regions with higher summertime air exchange rates. For regions such as Houston with lower summertime air exchange rates, the higher emission rates would likely increase occupant exposure to the undesirable products of ozone reactions, thus reinforcing the need for zero-emission rate standard.
47 CFR 65.700 - Determining the maximum allowable rate of return.
2010-10-01
... CARRIER SERVICES (CONTINUED) INTERSTATE RATE OF RETURN PRESCRIPTION PROCEDURES AND METHODOLOGIES Maximum Allowable Rates of Return § 65.700 Determining the maximum allowable rate of return. (a) The maximum allowable rate of return for any exchange carrier's earnings on any access service category shall...
Kuracina Richard
2015-06-01
Full Text Available The article deals with the measurement of maximum explosion pressure and the maximum rate of exposure pressure rise of wood dust cloud. The measurements were carried out according to STN EN 14034-1+A1:2011 Determination of explosion characteristics of dust clouds. Part 1: Determination of the maximum explosion pressure pmax of dust clouds and the maximum rate of explosion pressure rise according to STN EN 14034-2+A1:2012 Determination of explosion characteristics of dust clouds - Part 2: Determination of the maximum rate of explosion pressure rise (dp/dtmax of dust clouds. The wood dust cloud in the chamber is achieved mechanically. The testing of explosions of wood dust clouds showed that the maximum value of the pressure was reached at the concentrations of 450 g / m3 and its value is 7.95 bar. The fastest increase of pressure was observed at the concentrations of 450 g / m3 and its value was 68 bar / s.
Pan, Sudip; Solà, Miquel; Chattaraj, Pratim K
2013-02-28
Hardness and electrophilicity values for several molecules involved in different chemical reactions are calculated at various levels of theory and by using different basis sets. Effects of these aspects as well as different approximations to the calculation of those values vis-à-vis the validity of the maximum hardness and minimum electrophilicity principles are analyzed in the cases of some representative reactions. Among 101 studied exothermic reactions, 61.4% and 69.3% of the reactions are found to obey the maximum hardness and minimum electrophilicity principles, respectively, when hardness of products and reactants is expressed in terms of their geometric means. However, when we use arithmetic mean, the percentage reduces to some extent. When we express the hardness in terms of scaled hardness, the percentage obeying maximum hardness principle improves. We have observed that maximum hardness principle is more likely to fail in the cases of very hard species like F(-), H(2), CH(4), N(2), and OH appearing in the reactant side and in most cases of the association reactions. Most of the association reactions obey the minimum electrophilicity principle nicely. The best results (69.3%) for the maximum hardness and minimum electrophilicity principles reject the 50% null hypothesis at the 2% level of significance.
The tropical lapse rate steepened during the Last Glacial Maximum
Loomis, S.E.; Russell, J.M.; Verschuren, D.; Morrill, C.; De Cort, G.; Sinninghe Damsté, J.S.; Olago, D.; Eggermont, H.; Street-Perrott, F.A.; Kelly, M.A.
2017-01-01
The gradient of air temperature with elevation (the temperature lapse rate) in the tropics is predicted to become lesssteep during the coming century as surface temperature rises, enhancing the threat of warming in high-mountainenvironments. However, the sensitivity of the lapse rate to climate
The tropical lapse rate steepened during the Last Glacial Maximum
Loomis, Shannon E; Russell, James M; Verschuren, Dirk; Morrill, Carrie; De Cort, Gijs; Sinninghe Damsté, Jaap S|info:eu-repo/dai/nl/07401370X; Olago, Daniel; Eggermont, Hilde; Street-Perrott, F Alayne; Kelly, Meredith A
The gradient of air temperature with elevation (the temperature lapse rate) in the tropics is predicted to become less steep during the coming century as surface temperature rises, enhancing the threat of warming in high-mountain environments. However, the sensitivity of the lapse rate to climate
How is entropy production rate related to chemical reaction rate?
Banerjee, Kinshuk
2013-01-01
The entropy production rate is a key quantity in irreversible thermodynamics. In this work, we concentrate on the realization of entropy production rate in chemical reaction systems in terms of the experimentally measurable reaction rate. Both triangular and linear networks have been studied. They attain either thermodynamic equilibrium or a non-equilibrium steady state, under suitable external constraints. We have shown that the entropy production rate is proportional to the square of the reaction velocity only around equilibrium and not any arbitrary non-equilibrium steady state. This feature can act as a guide in revealing the nature of a steady state, very much like the minimum entropy production principle. A discussion on this point has also been presented.
Reaction rates for mesoscopic reaction-diffusion kinetics.
Hellander, Stefan; Hellander, Andreas; Petzold, Linda
2015-02-01
The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.
Reaction rates for mesoscopic reaction-diffusion kinetics
Hellander, Stefan; Hellander, Andreas; Petzold, Linda
2015-02-01
The mesoscopic reaction-diffusion master equation (RDME) is a popular modeling framework frequently applied to stochastic reaction-diffusion kinetics in systems biology. The RDME is derived from assumptions about the underlying physical properties of the system, and it may produce unphysical results for models where those assumptions fail. In that case, other more comprehensive models are better suited, such as hard-sphere Brownian dynamics (BD). Although the RDME is a model in its own right, and not inferred from any specific microscale model, it proves useful to attempt to approximate a microscale model by a specific choice of mesoscopic reaction rates. In this paper we derive mesoscopic scale-dependent reaction rates by matching certain statistics of the RDME solution to statistics of the solution of a widely used microscopic BD model: the Smoluchowski model with a Robin boundary condition at the reaction radius of two molecules. We also establish fundamental limits on the range of mesh resolutions for which this approach yields accurate results and show both theoretically and in numerical examples that as we approach the lower fundamental limit, the mesoscopic dynamics approach the microscopic dynamics. We show that for mesh sizes below the fundamental lower limit, results are less accurate. Thus, the lower limit determines the mesh size for which we obtain the most accurate results.
Jan Werner; Eva Maria Griebeler
2014-01-01
We tested if growth rates of recent taxa are unequivocally separated between endotherms and ectotherms, and compared these to dinosaurian growth rates. We therefore performed linear regression analyses on the log-transformed maximum growth rate against log-transformed body mass at maximum growth for extant altricial birds, precocial birds, eutherians, marsupials, reptiles, fishes and dinosaurs. Regression models of precocial birds (and fishes) strongly differed from Case's study (1978), which...
A Maximum Information Rate Quaternion Filter for Spacecraft Attitude Estimation
Reijneveld, J.; Maas, A.; Choukroun, D.; Kuiper, J.M.
2011-01-01
Building on previous works, this paper introduces a novel continuous-time stochastic optimal linear quaternion estimator under the assumptions of rate gyro measurements and of vector observations of the attitude. A quaternion observation model, which observation matrix is rank degenerate, is reduced
78 FR 13999 - Maximum Interest Rates on Guaranteed Farm Loans
2013-03-04
... have removed the term. Comment: Don't remove the ``average agricultural loan customer'' definition. The... the following methods: Federal eRulemaking Portal: Go to http://www.regulations.gov . Follow the.... Comment: FSA should let the market dictate what interest rate lenders charge guaranteed borrowers, rather...
Reaction rates for a generalized reaction-diffusion master equation.
Hellander, Stefan; Petzold, Linda
2016-01-01
It has been established that there is an inherent limit to the accuracy of the reaction-diffusion master equation. Specifically, there exists a fundamental lower bound on the mesh size, below which the accuracy deteriorates as the mesh is refined further. In this paper we extend the standard reaction-diffusion master equation to allow molecules occupying neighboring voxels to react, in contrast to the traditional approach, in which molecules react only when occupying the same voxel. We derive reaction rates, in two dimensions as well as three dimensions, to obtain an optimal match to the more fine-grained Smoluchowski model and show in two numerical examples that the extended algorithm is accurate for a wide range of mesh sizes, allowing us to simulate systems that are intractable with the standard reaction-diffusion master equation. In addition, we show that for mesh sizes above the fundamental lower limit of the standard algorithm, the generalized algorithm reduces to the standard algorithm. We derive a lower limit for the generalized algorithm which, in both two dimensions and three dimensions, is of the order of the reaction radius of a reacting pair of molecules.
Reaction rates for a generalized reaction-diffusion master equation
Hellander, Stefan; Petzold, Linda
2016-01-01
It has been established that there is an inherent limit to the accuracy of the reaction-diffusion master equation. Specifically, there exists a fundamental lower bound on the mesh size, below which the accuracy deteriorates as the mesh is refined further. In this paper we extend the standard reaction-diffusion master equation to allow molecules occupying neighboring voxels to react, in contrast to the traditional approach, in which molecules react only when occupying the same voxel. We derive reaction rates, in two dimensions as well as three dimensions, to obtain an optimal match to the more fine-grained Smoluchowski model and show in two numerical examples that the extended algorithm is accurate for a wide range of mesh sizes, allowing us to simulate systems that are intractable with the standard reaction-diffusion master equation. In addition, we show that for mesh sizes above the fundamental lower limit of the standard algorithm, the generalized algorithm reduces to the standard algorithm. We derive a lower limit for the generalized algorithm which, in both two dimensions and three dimensions, is of the order of the reaction radius of a reacting pair of molecules.
Thermonuclear Reaction Rate Parameterization for Nuclear Astrophysics
Sharp, Jacob; Kozub, Raymond L.; Smith, Michael S.; Scott, Jason; Lingerfelt, Eric
2004-10-01
The knowledge of thermonuclear reaction rates is vital to simulate novae, supernovae, X-ray bursts, and other astrophysical events. To facilitate dissemination of this knowledge, a set of tools has been created for managing reaction rates, located at www.nucastrodata.org. One tool is a rate parameterizer, which provides a parameterization for nuclear reaction rate vs. temperature values in the most widely used functional form. Currently, the parameterizer uses the Levenberg-Marquardt method (LMM), which requires an initial estimate of the best-fit parameters. The initial estimate is currently provided randomly from a preselected pool. To improve the quality of fits, a new, active method of selecting parameters has been developed. The parameters of each set in the pool are altered for a few iterations to replicate the input data as closely as possible. Then, the set which most nearly matches the input data (based on chi squared) is used in the LMM as the initial estimate for the final fitting procedure. A description of the new, active algorithm and its performance will be presented. Supported by the U. S. Department of Energy.
Two-temperature reaction and relaxation rates
Kolesnichenko, E.; Gorbachev, Yu.
2016-09-01
Within the method of solving the kinetic equations for gas mixtures with internal degrees of freedom developed by the authors and based on the approximate summational invariants (ASI) concept, gas-dynamic equations for a multi-temperature model for the spatially inhomogeneous case are derived. For the two-temperature case, the expressions for the non-equilibrium reaction and relaxation rates are obtained. Special attention is drawn to corresponding thermodynamic equations. Different possibilities of introducing the gas-dynamic variables related to the internal degrees of freedom are considered. One is based on the choice of quantum numbers as the ASI, while the other is based on the choice of internal (vibrational) energy as the ASI. Limits to a one-temperature situation are considered in all the cases. For the cutoff harmonic oscillator model, explicit expressions for the reaction and relaxation rates are derived.
Quantum theory of chemical reaction rates
Miller, W.H. [Univ. of California, Berkeley, CA (United States). Dept. of Chemistry]|[Lawrence Berkeley Lab., CA (United States). Chemical Sciences Div.
1994-10-01
If one wishes to describe a chemical reaction at the most detailed level possible, i.e., its state-to-state differential scattering cross section, then it is necessary to solve the Schroedinger equation to obtain the S-matrix as a function of total energy E and total angular momentum J, in terms of which the cross sections can be calculated as given by equation (1) in the paper. All other physically observable attributes of the reaction can be derived from the cross sections. Often, in fact, one is primarily interested in the least detailed quantity which characterizes the reaction, namely its thermal rate constant, which is obtained by integrating Eq. (1) over all scattering angles, summing over all product quantum states, and Boltzmann-averaging over all initial quantum states of reactants. With the proper weighting factors, all of these averages are conveniently contained in the cumulative reaction probability (CRP), which is defined by equation (2) and in terms of which the thermal rate constant is given by equation (3). Thus, having carried out a full state-to-state scattering calculation to obtain the S-matrix, one can obtain the CRP from Eq. (2), and then rate constant from Eq. (3), but this seems like ``overkill``; i.e., if one only wants the rate constant, it would clearly be desirable to have a theory that allows one to calculate it, or the CRP, more directly than via Eq. (2), yet also correctly, i.e., without inherent approximations. Such a theory is the subject of this paper.
Reaction Rate Parameterization for Nuclear Astrophysics Research
Scott, J. P.; Lingerfelt, E. J.; Smith, M. S.; Hix, W. R.; Bardayan, D. W.; Sharp, J. E.; Kozub, R. L.; Meyer, R. A.
2004-11-01
Libraries of thermonuclear reaction rates are used in element synthesis models of a wide variety of astrophysical phenomena, such as exploding stars and the inner workings of our sun. These computationally demanding models are more efficient when libraries, which may contain over 60000 rates and vary by 20 orders of magnitude, have a uniform parameterization for all rates. We have developed an on-line tool, hosted at www.nucastrodata.org, to obtain REACLIB parameters (F.-K. Thielemann et al., Adv. Nucl. Astrophysics 525, 1 (1987)) that represent reaction rates as a function of temperature. This helps to rapidly incorporate the latest nuclear physics results in astrophysics models. The tool uses numerous techniques and algorithms in a modular fashion to improve the quality of the fits to the rates. Features, modules, and additional applications of this tool will be discussed. * Managed by UT-Battelle, LLC, for the U.S. D.O.E. under contract DE-AC05-00OR22725 + Supported by U.S. D.O.E. under Grant No. DE-FG02-96ER40955
9 CFR 381.68 - Maximum inspection rates-New turkey inspection system.
2010-01-01
... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Maximum inspection rates-New turkey inspection system. 381.68 Section 381.68 Animals and Animal Products FOOD SAFETY AND INSPECTION SERVICE... Procedures § 381.68 Maximum inspection rates—New turkey inspection system. (a) The maximum inspection...
Jan Werner
Full Text Available We tested if growth rates of recent taxa are unequivocally separated between endotherms and ectotherms, and compared these to dinosaurian growth rates. We therefore performed linear regression analyses on the log-transformed maximum growth rate against log-transformed body mass at maximum growth for extant altricial birds, precocial birds, eutherians, marsupials, reptiles, fishes and dinosaurs. Regression models of precocial birds (and fishes strongly differed from Case's study (1978, which is often used to compare dinosaurian growth rates to those of extant vertebrates. For all taxonomic groups, the slope of 0.75 expected from the Metabolic Theory of Ecology was statistically supported. To compare growth rates between taxonomic groups we therefore used regressions with this fixed slope and group-specific intercepts. On average, maximum growth rates of ectotherms were about 10 (reptiles to 20 (fishes times (in comparison to mammals or even 45 (reptiles to 100 (fishes times (in comparison to birds lower than in endotherms. While on average all taxa were clearly separated from each other, individual growth rates overlapped between several taxa and even between endotherms and ectotherms. Dinosaurs had growth rates intermediate between similar sized/scaled-up reptiles and mammals, but a much lower rate than scaled-up birds. All dinosaurian growth rates were within the range of extant reptiles and mammals, and were lower than those of birds. Under the assumption that growth rate and metabolic rate are indeed linked, our results suggest two alternative interpretations. Compared to other sauropsids, the growth rates of studied dinosaurs clearly indicate that they had an ectothermic rather than an endothermic metabolic rate. Compared to other vertebrate growth rates, the overall high variability in growth rates of extant groups and the high overlap between individual growth rates of endothermic and ectothermic extant species make it impossible to rule
Werner, Jan; Griebeler, Eva Maria
2014-01-01
We tested if growth rates of recent taxa are unequivocally separated between endotherms and ectotherms, and compared these to dinosaurian growth rates. We therefore performed linear regression analyses on the log-transformed maximum growth rate against log-transformed body mass at maximum growth for extant altricial birds, precocial birds, eutherians, marsupials, reptiles, fishes and dinosaurs. Regression models of precocial birds (and fishes) strongly differed from Case's study (1978), which is often used to compare dinosaurian growth rates to those of extant vertebrates. For all taxonomic groups, the slope of 0.75 expected from the Metabolic Theory of Ecology was statistically supported. To compare growth rates between taxonomic groups we therefore used regressions with this fixed slope and group-specific intercepts. On average, maximum growth rates of ectotherms were about 10 (reptiles) to 20 (fishes) times (in comparison to mammals) or even 45 (reptiles) to 100 (fishes) times (in comparison to birds) lower than in endotherms. While on average all taxa were clearly separated from each other, individual growth rates overlapped between several taxa and even between endotherms and ectotherms. Dinosaurs had growth rates intermediate between similar sized/scaled-up reptiles and mammals, but a much lower rate than scaled-up birds. All dinosaurian growth rates were within the range of extant reptiles and mammals, and were lower than those of birds. Under the assumption that growth rate and metabolic rate are indeed linked, our results suggest two alternative interpretations. Compared to other sauropsids, the growth rates of studied dinosaurs clearly indicate that they had an ectothermic rather than an endothermic metabolic rate. Compared to other vertebrate growth rates, the overall high variability in growth rates of extant groups and the high overlap between individual growth rates of endothermic and ectothermic extant species make it impossible to rule out either of
Bayesian Estimation of Thermonuclear Reaction Rates
Iliadis, Christian; Coc, Alain; Timmes, Frank; Starrfield, Sumner
2016-01-01
The problem of estimating non-resonant astrophysical S-factors and thermonuclear reaction rates, based on measured nuclear cross sections, is of major interest for nuclear energy generation, neutrino physics, and element synthesis. Many different methods have been applied in the past to this problem, all of them based on traditional statistics. Bayesian methods, on the other hand, are now in widespread use in the physical sciences. In astronomy, for example, Bayesian statistics is applied to the observation of extra-solar planets, gravitational waves, and type Ia supernovae. However, nuclear physics, in particular, has been slow to adopt Bayesian methods. We present the first astrophysical S-factors and reaction rates based on Bayesian statistics. We develop a framework that incorporates robust parameter estimation, systematic effects, and non-Gaussian uncertainties in a consistent manner. The method is applied to the d(p,$\\gamma$)$^3$He, $^3$He($^3$He,2p)$^4$He, and $^3$He($\\alpha$,$\\gamma$)$^7$Be reactions,...
Bayesian Estimation of Thermonuclear Reaction Rates
Iliadis, C.; Anderson, K. S.; Coc, A.; Timmes, F. X.; Starrfield, S.
2016-11-01
The problem of estimating non-resonant astrophysical S-factors and thermonuclear reaction rates, based on measured nuclear cross sections, is of major interest for nuclear energy generation, neutrino physics, and element synthesis. Many different methods have been applied to this problem in the past, almost all of them based on traditional statistics. Bayesian methods, on the other hand, are now in widespread use in the physical sciences. In astronomy, for example, Bayesian statistics is applied to the observation of extrasolar planets, gravitational waves, and Type Ia supernovae. However, nuclear physics, in particular, has been slow to adopt Bayesian methods. We present astrophysical S-factors and reaction rates based on Bayesian statistics. We develop a framework that incorporates robust parameter estimation, systematic effects, and non-Gaussian uncertainties in a consistent manner. The method is applied to the reactions d(p,γ)3He, 3He(3He,2p)4He, and 3He(α,γ)7Be, important for deuterium burning, solar neutrinos, and Big Bang nucleosynthesis.
CHLORINATION OF AMINO ACIDS: REACTION PATHWAYS AND REACTION RATES.
How, Zuo Tong; Linge, Kathryn; Busetti, Francesco; Joll, Cynthia A
2017-03-15
Chlorination of amino acids can result in the formation of organic monochloramines or organic dichloramines, depending on the chlorine to amino acid ratio (Cl:AA). After formation, organic chloramines degrade into aldehydes, nitriles and N-chloraldimines. In this paper, the formation of organic chloramines from chlorination of lysine, tyrosine and valine were investigated. Chlorination of tyrosine and lysine demonstrated that the presence of a reactive secondary group can increase the Cl:AA ratio required for the formation of N,N-dichloramines, and potentially alter the reaction pathways between chlorine and amino acids, resulting in the formation of unexpected by-products. In a detailed investigation, we report rate constants for all reactions in the chlorination of valine, for the first time, using experimental results and modelling. At Cl:AA = 2.8, the chlorine was found to first react quickly with valine (5.4x104 M-1 s-1) to form N-monochlorovaline, with a slower subsequent reaction with N-monochlorovaline to form N,N-dichlorovaline (4.9x102 M-1 s-1), although some N-monochlorovaline degraded into isobutyraldehyde (1.0x10-4 s-1). The N,N-dichlorovaline then competitively degraded into isobutyronitrile (1.3x10-4 s-1) and N-chloroisobutyraldimine (1.2x10-4 s-1). In conventional drinking water disinfection, N-chloroisobutyraldimine can potentially be formed in concentrations higher than its odour threshold concentration, resulting in aesthetic challenges and an unknown health risk.
Control of serpentinisation rate by reaction-induced cracking
Malvoisin, Benjamin; Brantut, Nicolas; Kaczmarek, Mary-Alix
2017-10-01
Serpentinisation of mantle rocks requires the generation and maintenance of transport pathways for water. The solid volume increase during serpentinisation can lead to stress build-up and trigger cracking, which ease fluid penetration into the rock. The quantitative effect of this reaction-induced cracking mechanism on reactive surface generation is poorly constrained, thus hampering our ability to predict serpentinisation rate in geological environments. Here we use a combined approach with numerical modelling and observations in natural samples to provide estimates of serpentinisation rate at mid-ocean ridges. We develop a micromechanical model to quantify the propagation of serpentinisation-induced cracks in olivine. The maximum crystallisation pressure deduced from thermodynamic calculations reaches several hundreds of megapascals but does not necessary lead to crack propagation if the olivine grain is subjected to high compressive stresses. The micromechanical model is then coupled to a simple geometrical model to predict reactive surface area formation during grain splitting, and thus bulk reaction rate. Our model reproduces quantitatively experimental kinetic data and the typical mesh texture formed during serpentinisation. We also compare the model results with olivine grain size distribution data obtained on natural serpentinised peridotites from the Marum ophiolite and the Papuan ultramafic belt (Papua New Guinea). The natural serpentinised peridotites show an increase of the number of olivine grains for a decrease of the mean grain size by one order of magnitude as reaction progresses from 5 to 40%. These results are in agreement with our model predictions, suggesting that reaction-induced cracking controls the serpentinisation rate. We use our model to estimate that, at mid-ocean ridges, serpentinisation occurs up to 12 km depth and reaction-induced cracking reduces the characteristic time of serpentinisation by one order of magnitude, down to values
O'Hara, Kieran
2007-08-01
In the southern Appalachians, the Blue Ridge-Piedmont crystalline thrust sheet was emplaced onto low-grade Late Precambrian and Paleozoic sedimentary rocks in the footwall along a basal detachment consisting of phyllosilicate-rich mylonites (phyllonites). The phyllonites developed first by mechanical breakdown of feldspar followed by chemical breakdown to white mica in the presence of a pore fluid. Diffusion of solute in the pore fluid is the rate limiting step in controlling reaction rate and also the strain rate. Assuming solute diffusion follows the Stokes-Einstein equation, the shear strain rate is given by ⅆγ/ⅆt=2ωkT/5ηrx for shear stress ≥20 MPa, where n is a constant, ω is a geometric factor, k is Boltzmann's constant, T is absolute temperature, η is water viscosity, r is the atomic radius of the diffusing species, and x is the diffusion distance. A bulk diffusion coefficient in the range of ˜10 -10 to 10 -12 m 2/s over distances of 10-100 m results in strain rates of 10 -14 to 10 -13 s -1 in the temperature range 200-400 °C. It is concluded that greenschist grade crystalline thrust sheets develop on pre-existing basement faults that become weak during reaction softening and localize into high strain phyllonite zones in which pore fluid diffusion controls reaction rate and strain rate.
Saha, Ranajit; Pan, Sudip; Chattaraj, Pratim K
2016-11-05
The validity of the maximum hardness principle (MHP) is tested in the cases of 50 chemical reactions, most of which are organic in nature and exhibit anomeric effect. To explore the effect of the level of theory on the validity of MHP in an exothermic reaction, B3LYP/6-311++G(2df,3pd) and LC-BLYP/6-311++G(2df,3pd) (def2-QZVP for iodine and mercury) levels are employed. Different approximations like the geometric mean of hardness and combined hardness are considered in case there are multiple reactants and/or products. It is observed that, based on the geometric mean of hardness, while 82% of the studied reactions obey the MHP at the B3LYP level, 84% of the reactions follow this rule at the LC-BLYP level. Most of the reactions possess the hardest species on the product side. A 50% null hypothesis is rejected at a 1% level of significance.
Ranajit Saha
2016-11-01
Full Text Available The validity of the maximum hardness principle (MHP is tested in the cases of 50 chemical reactions, most of which are organic in nature and exhibit anomeric effect. To explore the effect of the level of theory on the validity of MHP in an exothermic reaction, B3LYP/6-311++G(2df,3pd and LC-BLYP/6-311++G(2df,3pd (def2-QZVP for iodine and mercury levels are employed. Different approximations like the geometric mean of hardness and combined hardness are considered in case there are multiple reactants and/or products. It is observed that, based on the geometric mean of hardness, while 82% of the studied reactions obey the MHP at the B3LYP level, 84% of the reactions follow this rule at the LC-BLYP level. Most of the reactions possess the hardest species on the product side. A 50% null hypothesis is rejected at a 1% level of significance.
Daniel L. Rabosky
2006-01-01
Full Text Available Rates of species origination and extinction can vary over time during evolutionary radiations, and it is possible to reconstruct the history of diversification using molecular phylogenies of extant taxa only. Maximum likelihood methods provide a useful framework for inferring temporal variation in diversification rates. LASER is a package for the R programming environment that implements maximum likelihood methods based on the birth-death process to test whether diversification rates have changed over time. LASER contrasts the likelihood of phylogenetic data under models where diversification rates have changed over time to alternative models where rates have remained constant over time. Major strengths of the package include the ability to detect temporal increases in diversification rates and the inference of diversification parameters under multiple rate-variable models of diversification. The program and associated documentation are freely available from the R package archive at http://cran.r-project.org.
13 CFR 107.845 - Maximum rate of amortization on Loans and Debt Securities.
2010-01-01
... 13 Business Credit and Assistance 1 2010-01-01 2010-01-01 false Maximum rate of amortization on... ADMINISTRATION SMALL BUSINESS INVESTMENT COMPANIES Financing of Small Businesses by Licensees Structuring... rate of amortization on Loans and Debt Securities. The principal of any Loan (or the loan portion...
The Scaling of Maximum and Basal Metabolic Rates of Mammals and Birds
Barbosa, L A; Silva, J K L; Barbosa, Lauro A.; Garcia, Guilherme J. M.; Silva, Jafferson K. L. da
2004-01-01
Allometric scaling is one of the most pervasive laws in biology. Its origin, however, is still a matter of dispute. Recent studies have established that maximum metabolic rate scales with an exponent larger than that found for basal metabolism. This unpredicted result sets a challenge that can decide which of the concurrent hypotheses is the correct theory. Here we show that both scaling laws can be deduced from a single network model. Besides the 3/4-law for basal metabolism, the model predicts that maximum metabolic rate scales as $M^{6/7}$, maximum heart rate as $M^{-1/7}$, and muscular capillary density as $M^{-1/7}$, in agreement with data.
17 CFR 148.7 - Rulemaking on maximum rates for attorney fees.
2010-04-01
... 17 Commodity and Securities Exchanges 1 2010-04-01 2010-04-01 false Rulemaking on maximum rates for attorney fees. 148.7 Section 148.7 Commodity and Securities Exchanges COMMODITY FUTURES TRADING... increase in the cost of living or by special circumstances (such as limited availability of...
The 220-age equation does not predict maximum heart rate in children and adolescents
Verschuren, Olaf; Maltais, Desiree B.; Takken, Tim
Our primary purpose was to provide maximum heart rate (HR(max)) values for ambulatory children with cerebral palsy (CP). The secondary purpose was to determine the effects of age, sex, ambulatory ability, height, and weight on HR(max). In 362 ambulatory children and adolescents with CP (213 males
The 220-age equation does not predict maximum heart rate in children and adolescents
Verschuren, Olaf; Maltais, Desiree B.; Takken, Tim
2011-01-01
Our primary purpose was to provide maximum heart rate (HR(max)) values for ambulatory children with cerebral palsy (CP). The secondary purpose was to determine the effects of age, sex, ambulatory ability, height, and weight on HR(max). In 362 ambulatory children and adolescents with CP (213 males an
Statistical Methods for Thermonuclear Reaction Rates and Nucleosynthesis Simulations
Iliadis, Christian; Coc, Alain; Timmes, F X; Champagne, Art E
2014-01-01
Rigorous statistical methods for estimating thermonuclear reaction rates and nucleosynthesis are becoming increasingly established in nuclear astrophysics. The main challenge being faced is that experimental reaction rates are highly complex quantities derived from a multitude of different measured nuclear parameters (e.g., astrophysical S-factors, resonance energies and strengths, particle and gamma-ray partial widths). We discuss the application of the Monte Carlo method to two distinct, but related, questions. First, given a set of measured nuclear parameters, how can one best estimate the resulting thermonuclear reaction rates and associated uncertainties? Second, given a set of appropriate reaction rates, how can one best estimate the abundances from nucleosynthesis (i.e., reaction network) calculations? The techniques described here provide probability density functions that can be used to derive statistically meaningful reaction rates and final abundances for any desired coverage probability. Examples ...
Maximum initial growth-rate of strong-shock-driven Richtmyer-Meshkov instability
Dell, Z. R.; Pandian, A.; Bhowmick, A. K.; Swisher, N. C.; Stanic, M.; Stellingwerf, R. F.; Abarzhi, S. I.
2017-09-01
We focus on the classical problem of the dependence on the initial conditions of the initial growth-rate of strong shock driven Richtmyer-Meshkov instability (RMI) by developing a novel empirical model and by employing rigorous theories and Smoothed Particle Hydrodynamics simulations to describe the simulation data with statistical confidence in a broad parameter regime. For the given values of the shock strength, fluid density ratio, and wavelength of the initial perturbation of the fluid interface, we find the maximum value of the RMI initial growth-rate, the corresponding amplitude scale of the initial perturbation, and the maximum fraction of interfacial energy. This amplitude scale is independent of the shock strength and density ratio and is characteristic quantity of RMI dynamics. We discover the exponential decay of the ratio of the initial and linear growth-rates of RMI with the initial perturbation amplitude that excellently agrees with available data.
Enzymatic spectrophotometric reaction rate determination of aspartame
Trifković Kata T.
2015-01-01
Full Text Available Aspartame is an artificial sweetener of low caloric value (approximately 200 times sweeter than sucrose. Aspartame is currently permitted for use in food and beverage production in more than 90 countries. The application of aspartame in food products requires development of rapid, inexpensive and accurate method for its determination. The new assay for determination of aspartame was based on set of reactions that are catalyzed by three different enzymes: α-chymotrypsin, alcohol oxidase and horseradish peroxidase. Optimization of the proposed method was carried out for: (i α-chymotrypsin activity; (ii time allowed for α-chymotrypsin action, (iii temperature. Evaluation of the developed method was done by determining aspartame content in “diet” drinks, as well as in artificial sweetener pills. [Projekat Ministarstva nauke Republike Srbije, br. III46010
Iliadis, Christian; Champagne, Art; Coc, Alain; Fitzgerald, Ryan
2010-01-01
Numerical values of charged-particle thermonuclear reaction rates for nuclei in the A=14 to 40 region are tabulated. The results are obtained using a method, based on Monte Carlo techniques, that has been described in the preceding paper of this series (Paper I). We present a low rate, median rate and high rate which correspond to the 0.16, 0.50 and 0.84 quantiles, respectively, of the cumulative reaction rate distribution. The meaning of these quantities is in general different from the commonly reported, but statistically meaningless expressions, "lower limit", "nominal value" and "upper limit" of the total reaction rate. In addition, we approximate the Monte Carlo probability density function of the total reaction rate by a lognormal distribution and tabulate the lognormal parameters {\\mu} and {\\sigma} at each temperature. We also provide a quantitative measure (Anderson-Darling test statistic) for the reliability of the lognormal approximation. The user can implement the approximate lognormal reaction rat...
Effects of electric field on the maximum electro-spinning rate of silk fibroin solutions.
Park, Bo Kyung; Um, In Chul
2017-02-01
Owing to the excellent cyto-compatibility of silk fibroin (SF) and the simple fabrication of nano-fibrous webs, electro-spun SF webs have attracted much research attention in numerous biomedical fields. Because the production rate of electro-spun webs is strongly dependent on the electro-spinning rate used, the electro-spinning rate becomes more important. In the present study, to improve the electro-spinning rate of SF solutions, various electric fields were applied during electro-spinning of SF, and its effects on the maximum electro-spinning rate of SF solution as well as diameters and molecular conformations of the electro-spun SF fibers were examined. As the electric field was increased, the maximum electro-spinning rate of the SF solution also increased. The maximum electro-spinning rate of a 13% SF solution could be increased 12×by increasing the electric field from 0.5kV/cm (0.25mL/h) to 2.5kV/cm (3.0mL/h). The dependence of the fiber diameter on the present electric field was not significant when using less-concentrated SF solutions (7-9% SF). On the other hand, at higher SF concentrations the electric field had a greater effect on the resulting fiber diameter. The electric field had a minimal effect of the molecular conformation and crystallinity index of the electro-spun SF webs. Copyright © 2016 Elsevier B.V. All rights reserved.
Lin, Haifeng; Bai, Di; Gao, Demin; Liu, Yunfei
2016-07-30
In Rechargeable Wireless Sensor Networks (R-WSNs), in order to achieve the maximum data collection rate it is critical that sensors operate in very low duty cycles because of the sporadic availability of energy. A sensor has to stay in a dormant state in most of the time in order to recharge the battery and use the energy prudently. In addition, a sensor cannot always conserve energy if a network is able to harvest excessive energy from the environment due to its limited storage capacity. Therefore, energy exploitation and energy saving have to be traded off depending on distinct application scenarios. Since higher data collection rate or maximum data collection rate is the ultimate objective for sensor deployment, surplus energy of a node can be utilized for strengthening packet delivery efficiency and improving the data generating rate in R-WSNs. In this work, we propose an algorithm based on data aggregation to compute an upper data generation rate by maximizing it as an optimization problem for a network, which is formulated as a linear programming problem. Subsequently, a dual problem by introducing Lagrange multipliers is constructed, and subgradient algorithms are used to solve it in a distributed manner. At the same time, a topology controlling scheme is adopted for improving the network's performance. Through extensive simulation and experiments, we demonstrate that our algorithm is efficient at maximizing the data collection rate in rechargeable wireless sensor networks.
On the rate of convergence of the maximum likelihood estimator of a k-monotone density
WELLNER; Jon; A
2009-01-01
Bounds for the bracketing entropy of the classes of bounded k-monotone functions on [0,A] are obtained under both the Hellinger distance and the Lp(Q) distance,where 1 p < ∞ and Q is a probability measure on [0,A].The result is then applied to obtain the rate of convergence of the maximum likelihood estimator of a k-monotone density.
On the rate of convergence of the maximum likelihood estimator of a K-monotone density
GAO FuChang; WELLNER Jon A
2009-01-01
Bounds for the bracketing entropy of the classes of bounded K-monotone functions on [0, A] are obtained under both the Hellinger distance and the LP(Q) distance, where 1 ≤ p < ∞ and Q is a probability measure on [0, A]. The result is then applied to obtain the rate of convergence of the maximum likelihood estimator of a K-monotone density.
A real-time maximum-likelihood heart-rate estimator for wearable textile sensors.
Cheng, Mu-Huo; Chen, Li-Chung; Hung, Ying-Che; Yang, Chang Ming
2008-01-01
This paper presents a real-time maximum-likelihood heart-rate estimator for ECG data measured via wearable textile sensors. The ECG signals measured from wearable dry electrodes are notorious for its susceptibility to interference from the respiration or the motion of wearing person such that the signal quality may degrade dramatically. To overcome these obstacles, in the proposed heart-rate estimator we first employ the subspace approach to remove the wandering baseline, then use a simple nonlinear absolute operation to reduce the high-frequency noise contamination, and finally apply the maximum likelihood estimation technique for estimating the interval of R-R peaks. A parameter derived from the byproduct of maximum likelihood estimation is also proposed as an indicator for signal quality. To achieve the goal of real-time, we develop a simple adaptive algorithm from the numerical power method to realize the subspace filter and apply the fast-Fourier transform (FFT) technique for realization of the correlation technique such that the whole estimator can be implemented in an FPGA system. Experiments are performed to demonstrate the viability of the proposed system.
Seymour, Roger S
2010-09-01
Effect of size of inflorescences, flowers and cones on maximum rate of heat production is analysed allometrically in 23 species of thermogenic plants having diverse structures and ranging between 1.8 and 600 g. Total respiration rate (, micromol s(-1)) varies with spadix mass (M, g) according to in 15 species of Araceae. Thermal conductance (C, mW degrees C(-1)) for spadices scales according to C = 18.5M(0.73). Mass does not significantly affect the difference between floral and air temperature. Aroids with exposed appendices with high surface area have high thermal conductance, consistent with the need to vaporize attractive scents. True flowers have significantly lower heat production and thermal conductance, because closed petals retain heat that benefits resident insects. The florets on aroid spadices, either within a floral chamber or spathe, have intermediate thermal conductance, consistent with mixed roles. Mass-specific rates of respiration are variable between species, but reach 900 nmol s(-1) g(-1) in aroid male florets, exceeding rates of all other plants and even most animals. Maximum mass-specific respiration appears to be limited by oxygen delivery through individual cells. Reducing mass-specific respiration may be one selective influence on the evolution of large size of thermogenic flowers.
Jayasinghe, P A; Hettiaratchi, J P A; Mehrotra, A K; Kumar, S
2014-06-01
Augmenting leachate before recirculation with peroxidase enzymes is a novel method to increase the available carbon, and therefore the food supply to microorganisms at the declining phase of the anaerobic landfill bioreactor operation. In order to optimize the enzyme-catalyzed leachate recirculation process, it is necessary to identify the reaction mechanisms and determine rate constants. This paper presents a kinetic model developed to ascertain the reaction mechanisms and determine the rate constants for enzyme catalyzed anaerobic waste degradation. The maximum rate of reaction (Vmax) for MnP enzyme-catalyzed reactors was 0.076 g(TOC)/g(DS).day. The catalytic turnover number (k(cat)) of the MnP enzyme-catalyzed was 506.7 per day while the rate constant (k) of the un-catalyzed reaction was 0.012 per day.
Energy diffusion controlled reaction rate in dissipative Hamiltonian systems
Deng Mao-Lin; Zhu Wei-Qiu
2007-01-01
In this paper the energy diffusion controlled reaction rate in dissipative Hamiltonian systems is investigated by using the stochastic averaging method for quasi Hamiltonian systems. The boundary value problem of mean first-passage time (MFPT) of averaged system is formulated and the energy diffusion controlled reaction rate is obtained as the inverse of MFPT. The energy diffusion controlled reaction rate in the classical Kramers bistable potential and in a two-dimensional bistable potential with a heat bath are obtained by using the proposed approach respectively. The obtained results are then compared with those from Monte Carlo simulation of original systems and from the classical Kramers theory. It is shown that the reaction rate obtained by using the proposed approach agrees well with that from Monte Carlo simulation and is more accurate than the classical Kramers rate.
Philipsen, Kirsten Riber; Christiansen, Lasse Engbo; Mandsberg, Lotte Frigaard
2008-01-01
that best describes data is a model taking into account the full covariance structure. An inference study is made in order to determine whether the growth rate of the five bacteria strains is the same. After applying a likelihood-ratio test to models with a full covariance structure, it is concluded...... that the specific growth rate is the same for all bacteria strains. This study highlights the importance of carrying out an explorative examination of residuals in order to make a correct parametrization of a model including the covariance structure. The ML method is shown to be a strong tool as it enables......The specific growth rate for P. aeruginosa and four mutator strains mutT, mutY, mutM and mutY–mutM is estimated by a suggested Maximum Likelihood, ML, method which takes the autocorrelation of the observation into account. For each bacteria strain, six wells of optical density, OD, measurements...
Quantum Mechanics Rate Constant for the N+ND Reaction
Ai-jie Zhang; Guo-zhong He
2011-01-01
We present nonadiabatic quantum dynamical calculations on the two coupled potential energy surfaces (12A' and 22A') [J.Theor.Comput.Chem.8,849 (2009)] for the reaction.Initial state-resolved reaction probabilities and cross sections for the N+ND→N2+D reaction and N'+ND→N+N'D reaction for collision energies of 5 meV to 1.0 eV are determined,respectively.It is found that the N+ND→N2+D reaction is dominated in the N+ND reaction.In addition,we obtained the rate constants for the N+ND→N2+D reaction which demand further experimental investigations.
Determination of zero-coupon and spot rates from treasury data by maximum entropy methods
Gzyl, Henryk; Mayoral, Silvia
2016-08-01
An interesting and important inverse problem in finance consists of the determination of spot rates or prices of the zero coupon bonds, when the only information available consists of the prices of a few coupon bonds. A variety of methods have been proposed to deal with this problem. Here we present variants of a non-parametric method to treat with such problems, which neither imposes an analytic form on the rates or bond prices, nor imposes a model for the (random) evolution of the yields. The procedure consists of transforming the problem of the determination of the prices of the zero coupon bonds into a linear inverse problem with convex constraints, and then applying the method of maximum entropy in the mean. This method is flexible enough to provide a possible solution to a mispricing problem.
Non-resonant triple alpha reaction rate at low temperature
Itoh, T.; Tamii, A.; Aoi, N.; Fujita, H.; Hashimoto, T.; Miki, K.; Ogata, K. [Research Center for Nuclear Physics, Osaka University, Ibaraki, Osaka 567-0047 (Japan); Carter, J.; Donaldson, L.; Sideras-Haddad, E. [Schools of Physics, University of Witwatersrand, Johannesburg 2050 (South Africa); Furuno, T.; Kawabata, T. [Departments of Physics, Kyoto University, Sakyo, Kyoto, 606-8502 (Japan); Kamimura, M. [RIKEN Nishina Center, Wako, Saitama, 351-0198 (Japan); Nemulodi, F.; Neveling, R.; Smit, F. D.; Swarts, C. [iThemba Laboratory for Accelerator Based Sciences Somerset, West, 7129 (South Africa)
2014-05-02
Our experimental goal is to study the non-resonant triple alpha reaction rate at low temperture (T < 10{sup 8} K). The {sup 13}C(p,d) reaction at 66 MeV has been used to probe the alpha-unbound continuum state in {sup 12}C just below the 2{sup nd} 0{sup +} state at 7.65 MeV. The transition strength to the continuum state is predicted to be sensitive to the non-resonant triple alpha reaction rate. The experiment has been performed at iThemba LABS. We report the present status of the experiment.
Perkell, J S; Hillman, R E; Holmberg, E B
1994-08-01
In previous reports, aerodynamic and acoustic measures of voice production were presented for groups of normal male and female speakers [Holmberg et al., J. Acoust. Soc. Am. 84, 511-529 (1988); J. Voice 3, 294-305 (1989)] that were used as norms in studies of voice disorders [Hillman et al., J. Speech Hear. Res. 32, 373-392 (1989); J. Voice 4, 52-63 (1990)]. Several of the measures were extracted from glottal airflow waveforms that were derived by inverse filtering a high-time-resolution oral airflow signal. Recently, the methods have been updated and a new study of additional subjects has been conducted. This report presents previous (1988) and current (1993) group mean values of sound pressure level, fundamental frequency, maximum airflow declination rate, ac flow, peak flow, minimum flow, ac-dc ratio, inferred subglottal air pressure, average flow, and glottal resistance. Statistical tests indicate overall group differences and differences for values of several individual parameters between the 1988 and 1993 studies. Some inter-study differences in parameter values may be due to sampling effects and minor methodological differences; however, a comparative test of 1988 and 1993 inverse filtering algorithms shows that some lower 1988 values of maximum flow declination rate were due at least in part to excessive low-pass filtering in the 1988 algorithm. The observed differences should have had a negligible influence on the conclusions of our studies of voice disorders.
On the 14C(alpha,gamma) reaction rate
Johnson, E D; Mitchell, J; Miller, L; Kemper, K W
2009-01-01
The 14C(alpha,gamma) reaction rate at temperatures below 0.3 GK depends on the properties of two near threshold resonances in 18O, the 1- at 6.198 MeV and the 3- at 6.404 MeV. The alpha+14C Asymptotic Normalization Coefficients (ANCs) for these resonances were determined using the alpha-transfer reactions 14C(7Li,t) and 14C(6Li,d) at sub-Coulomb energies. The 14C(alpha,gamma) reaction rate at low temperatures has been evaluated. Implications of the new reaction rate on the evolution of accreting helium white dwarfs and on the nucleosynthesis of low mass stars during the asymptotic giant branch (AGB) phase are discussed.
Michael D. Hare
2014-09-01
Full Text Available A field trial in northeast Thailand during 2011–2013 compared the establishment and growth of 2 Panicum maximum cultivars, Mombasa and Tanzania, sown at seeding rates of 2, 4, 6, 8, 10 and 12 kg/ha. In the first 3 months of establishment, higher sowing rates produced significantly more DM than sowing at 2 kg/ha, but thereafter there were no significant differences in total DM production between sowing rates of 2–12 kg/ha. Lower sowing rates produced fewer tillers/m2 than higher sowing rates but these fewer tillers were significantly heavier than the more numerous smaller tillers produced by higher sowing rates. Mombasa produced 23% more DM than Tanzania in successive wet seasons (7,060 vs. 5,712 kg DM/ha from 16 June to 1 November 2011; and 16,433 vs. 13,350 kg DM/ha from 25 April to 24 October 2012. Both cultivars produced similar DM yields in the dry seasons (November–April, averaging 2,000 kg DM/ha in the first dry season and 1,750 kg DM/ha in the second dry season. Mombasa produced taller tillers (104 vs. 82 cm, longer leaves (60 vs. 47 cm, wider leaves (2 vs. 1.8 cm and heavier tillers (1 vs. 0.7 g than Tanzania but fewer tillers/m2 (260 vs. 304. If farmers improve soil preparation and place more emphasis on sowing techniques, there is potential to dramatically reduce seed costs.Keywords: Guinea grass, tillering, forage production, seeding rates, Thailand.DOI: 10.17138/TGFT(2246-253
Evangelia Karagianni
2016-04-01
Full Text Available By utilizing meteorological data such as relative humidity, temperature, pressure, rain rate and precipitation duration at eight (8 stations in Aegean Archipelagos from six recent years (2007 – 2012, the effect of the weather on Electromagnetic wave propagation is studied. The EM wave propagation characteristics depend on atmospheric refractivity and consequently on Rain-Rate which vary in time and space randomly. Therefore the statistics of radio refractivity, Rain-Rate and related propagation effects are of main interest. This work investigates the maximum value of rain rate in monthly rainfall records, for a 5 min interval comparing it with different values of integration time as well as different percentages of time. The main goal is to determine the attenuation level for microwave links based on local rainfall data for various sites in Greece (L-zone, namely Aegean Archipelagos, with a view on improved accuracy as compared with more generic zone data available. A measurement of rain attenuation for a link in the S-band has been carried out and the data compared with prediction based on the standard ITU-R method.
Dependence of Reaction Rate Constants on Density in Supercritical Fluids
WANGTao; SHENZhongyao
2002-01-01
A new method,which correlates rate constants of chemical reactions and density or pressure in supercritical fluids,was developed.Based on the transition state theory and thermodynamic principles, the rate constant can be reasonably correlated with the density of the supercritical fluid,and a correlation equation was obtained. Coupled with the equation of state (EOS) of a supercritical solvent,the effect of pressure on reaction rate constant could be represented.Two typical systems were used to test this method.The result indicates that this method is suitable for dilute supercritical fluid solutions.
Liechty, Derek S.; Lewis, Mark J.
2010-01-01
Recently introduced molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction rate information) are extended to include reactions involving charged particles and electronic energy levels. The proposed extensions include ionization reactions, exothermic associative ionization reactions, endothermic and exothermic charge exchange reactions, and other exchange reactions involving ionized species. The extensions are shown to agree favorably with the measured Arrhenius rates for near-equilibrium conditions.
State Space Path Integrals for Electronically Nonadiabatic Reaction Rates
Duke, Jessica Ryan
2016-01-01
We present a state-space-based path integral method to calculate the rate of electron transfer (ET) in multi-state, multi-electron condensed-phase processes. We employ an exact path integral in discrete electronic states and continuous Cartesian nuclear variables to obtain a transition state theory (TST) estimate to the rate. A dynamic recrossing correction to the TST rate is then obtained from real-time dynamics simulations using mean field ring polymer molecular dynamics. We employ two different reaction coordinates in our simulations and show that, despite the use of mean field dynamics, the use of an accurate dividing surface to compute TST rates allows us to achieve remarkable agreement with Fermi's golden rule rates for nonadiabatic ET in the normal regime of Marcus theory. Further, we show that using a reaction coordinate based on electronic state populations allows us to capture the turnover in rates for ET in the Marcus inverted regime.
Kalafut, Bennett; Visscher, Koen
2008-10-01
Optical tweezers experiments allow us to probe the role of force and mechanical work in a variety of biochemical processes. However, observable states do not usually correspond in a one-to-one fashion with the internal state of an enzyme or enzyme-substrate complex. Different kinetic pathways yield different distributions for the dwells in the observable states. Furthermore, the dwell-time distribution will be dependent upon force, and upon where in the biochemical pathway force acts. I will present a maximum-likelihood method for identifying rate constants and the locations of force-dependent transitions in transcription initiation by T7 RNA Polymerase. This method is generalizable to systems with more complicated kinetic pathways in which there are two observable states (e.g. bound and unbound) and an irreversible final transition.
Asymptotic correctability of Bell-diagonal quantum states and maximum tolerable bit error rates
Ranade, K S; Ranade, Kedar S.; Alber, Gernot
2005-01-01
The general conditions are discussed which quantum state purification protocols have to fulfill in order to be capable of purifying Bell-diagonal qubit-pair states, provided they consist of steps that map Bell-diagonal states to Bell-diagonal states and they finally apply a suitably chosen Calderbank-Shor-Steane code to the outcome of such steps. As a main result a necessary and a sufficient condition on asymptotic correctability are presented, which relate this problem to the magnitude of a characteristic exponent governing the relation between bit and phase errors under the purification steps. These conditions allow a straightforward determination of maximum tolerable bit error rates of quantum key distribution protocols whose security analysis can be reduced to the purification of Bell-diagonal states.
Phylogenetic prediction of the maximum per capita rate of population growth.
Fagan, William F; Pearson, Yanthe E; Larsen, Elise A; Lynch, Heather J; Turner, Jessica B; Staver, Hilary; Noble, Andrew E; Bewick, Sharon; Goldberg, Emma E
2013-07-22
The maximum per capita rate of population growth, r, is a central measure of population biology. However, researchers can only directly calculate r when adequate time series, life tables and similar datasets are available. We instead view r as an evolvable, synthetic life-history trait and use comparative phylogenetic approaches to predict r for poorly known species. Combining molecular phylogenies, life-history trait data and stochastic macroevolutionary models, we predicted r for mammals of the Caniformia and Cervidae. Cross-validation analyses demonstrated that, even with sparse life-history data, comparative methods estimated r well and outperformed models based on body mass. Values of r predicted via comparative methods were in strong rank agreement with observed values and reduced mean prediction errors by approximately 68 per cent compared with two null models. We demonstrate the utility of our method by estimating r for 102 extant species in these mammal groups with unknown life-history traits.
Statistical properties of the maximum Lyapunov exponent calculated via the divergence rate method.
Franchi, Matteo; Ricci, Leonardo
2014-12-01
The embedding of a time series provides a basic tool to analyze dynamical properties of the underlying chaotic system. To this purpose, the choice of the embedding dimension and lag is crucial. Although several methods have been devised to tackle the issue of the optimal setting of these parameters, a conclusive criterion to make the most appropriate choice is still lacking. An accepted procedure to rank different embedding methods relies on the evaluation of the maximum Lyapunov exponent (MLE) out of embedded time series that are generated by chaotic systems with explicit analytic representation. The MLE is evaluated as the local divergence rate of nearby trajectories. Given a system, embedding methods are ranked according to how close such MLE values are to the true MLE. This is provided by the so-called standard method in a way that exploits the mathematical description of the system and does not require embedding. In this paper we study the dependence of the finite-time MLE evaluated via the divergence rate method on the embedding dimension and lag in the case of time series generated by four systems that are widely used as references in the scientific literature. We develop a completely automatic algorithm that provides the divergence rate and its statistical uncertainty. We show that the uncertainty can provide useful information about the optimal choice of the embedding parameters. In addition, our approach allows us to find which systems provide suitable benchmarks for the comparison and ranking of different embedding methods.
Reaction rate in an evanescent random walkers system
Ré, Miguel A
2015-01-01
Diffusion mediated reaction models are particularly ubiquitous in the description of physical, chemical or biological processes. The random walk schema is a useful tool for formulating these models. Recently, evanescent random walk models have received attention in order to include finite lifetime processes. For instance, activated chemical reactions, such as laser photolysis, exhibit a different asymptotic limit when compared with immortal walker models. A diffusion limited reaction model based on a one dimensional continuous time random walk on a lattice with evanescent walkers is presented here. The absorption probability density and the reaction rate are analytically calculated in the Laplace domain. A finite absorption rate is considered, a model usually referred to as imperfect trapping. Short and long time behaviors are analyzed.
Effects of Surfactants on the Rate of Chemical Reactions
B. Samiey
2014-01-01
Full Text Available Surfactants are self-assembled compounds that depend on their structure and electric charge can interact as monomer or micelle with other compounds (substrates. These interactions which may catalyze or inhibit the reaction rates are studied with pseudophase, cooperativity, and stoichiometric (classical models. In this review, we discuss applying these models to study surfactant-substrate interactions and their effects on Diels-Alder, redox, photochemical, decomposition, enzymatic, isomerization, ligand exchange, radical, and nucleophilic reactions.
Reaction rates between water and the Karl Fischer reagent.
Cedergren, A
1974-04-01
Reaction rates between water and the Karl Fischer reagent have been determined by potentiometric measurement for various compositions of the Karl Fischer reagent. The study has been made with an iodine complex concentration of 0.3-1.2 mM and sulphur dioxide complex at 0.01-0.5M. The concentration of excess of pyridine had no measurable effect on the rate of the main reaction. The reaction was found to be first-order with respect to iodine complex, to sulphur dioxide complex, and to water. The rate constant was (1.2+/-0.2) x 10(3) 1(2). mole(-2). sec(-1). In an ordinary titration it is therefore essential to keep the sulphur dioxide concentration high for the reaction to go to completion within a reasonable time. The extent of side-reactions was found to be independent of the iodine concentration at low concentrations. The side-reactions increased somewhat with increasing sulphur dioxide pyridine concentrations and decreased to about 60% when the temperature was lowered from 24 degrees to 7 degrees.
RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics
Suleimanov, Yu.V.
2013-03-01
We present RPMDrate, a computer program for the calculation of gas phase bimolecular reaction rate coefficients using the ring polymer molecular dynamics (RPMD) method. The RPMD rate coefficient is calculated using the Bennett-Chandler method as a product of a static (centroid density quantum transition state theory (QTST) rate) and a dynamic (ring polymer transmission coefficient) factor. The computational procedure is general and can be used to treat bimolecular polyatomic reactions of any complexity in their full dimensionality. The program has been tested for the H+H2, H+CH 4, OH+CH4 and H+C2H6 reactions. © 2012 Elsevier B.V. All rights reserved.
Liquid Film Diffusion on Reaction Rate in Submerged Biofilters
Christiansen, Pia; Hollesen, Line; Harremoës, Poul
1995-01-01
Experiments were carried out in order to investigate the influence of liquid film diffusion on reaction rate in a submerged biofilter with denitrification and in order to compare with a theoretical study of the mass transfer coefficient. The experiments were carried out with varied flow, identified...... by the empty bed velocity of inflow and recirculation, respectively 1.3, 2.8, 5.6 and 10.9 m/h. The filter material consisted of 3 mm biostyren spheres. The results indicate that the influence of liquid film diffusion on reaction rate can be ignored....
Alvah C. Stahlnecker IV
2008-12-01
Full Text Available A percentage of either measured or predicted maximum heart rate is commonly used to prescribe and measure exercise intensity. However, maximum heart rate in athletes may be greater during competition or training than during laboratory exercise testing. Thus, the aim of the present investigation was to determine if endurance-trained runners train and compete at or above laboratory measures of 'maximum' heart rate. Maximum heart rates were measured utilising a treadmill graded exercise test (GXT in a laboratory setting using 10 female and 10 male National Collegiate Athletic Association (NCAA division 2 cross-country and distance event track athletes. Maximum training and competition heart rates were measured during a high-intensity interval training day (TR HR and during competition (COMP HR at an NCAA meet. TR HR (207 ± 5.0 b·min-1; means ± SEM and COMP HR (206 ± 4 b·min-1 were significantly (p < 0.05 higher than maximum heart rates obtained during the GXT (194 ± 2 b·min-1. The heart rate at the ventilatory threshold measured in the laboratory occurred at 83.3 ± 2.5% of the heart rate at VO2 max with no differences between the men and women. However, the heart rate at the ventilatory threshold measured in the laboratory was only 77% of the maximal COMP HR or TR HR. In order to optimize training-induced adaptation, training intensity for NCAA division 2 distance event runners should not be based on laboratory assessment of maximum heart rate, but instead on maximum heart rate obtained either during training or during competition
Massive Star Evolution Nucleosynthesis and Nuclear Reaction Rate Uncertainties
Heger, A; Rauscher, T; Hoffman, R D; Boyes, M M
2002-01-01
We present a nucleosynthesis calculation of a 25 solar mass star of solar composition that includes all relevant isotopes up to polonium. In particular, all stable isotopes and necessary nuclear reaction rates are covered. We follow the stellar evolution from hydrogen burning till iron core collapse and simulate the explosion using a ``piston'' approach. We discuss the influence of two key nuclear reaction rates, C12(a,g) and Ne22(a,n), on stellar evolution and nucleosynthesis. The former significantly influences the resulting core sizes (iron, silicon, oxygen) and the overall presupernova structure of the star. It thus has significant consequences for the supernova explosion itself and the compact remnant formed. The later rate considerably affects the s-process in massive stars and we demonstrate the changes that different currently suggested values for this rate cause.
A compilation of charged-particle induced thermonuclear reaction rates
Angulo, C; Rayet, M; Descouvemont, P; Baye, D; Leclercq-Willain, C; Coc, A; Barhoumi, S; Aguer, P; Rolfs, C; Kunz, R; Hammer, J W; Mayer, A; Paradelis, T; Kossionides, S; Chronidou, C; Spyrou, K; Degl'Innocenti, S; Fiorentini, G; Ricci, B; Zavatarelli, S; Providência, C; Wolters, H; Soares, J; Grama, C; Rahighi, J; Shotter, A; Rachti, M L
1999-01-01
Low-energy cross section data for 86 charged-particle induced reactions involving light (1 <= Z <= 14), mostly stable, nuclei are compiled. The corresponding Maxwellian-averaged thermonuclear reaction rates of relevance in astrophysical plasmas at temperatures in the range from 10 sup 6 K to 10 sup 1 sup 0 K are calculated. These evaluations assume either that the target nuclei are in their ground state, or that the target states are thermally populated following a Maxwell-Boltzmann distribution, except in some cases involving isomeric states. Adopted values complemented with lower and upper limits of the rates are presented in tabular form. Analytical approximations to the adopted rates, as well as to the inverse/direct rate ratios, are provided.
A compilation of charged-particle induced thermonuclear reaction rates
Angulo, C.; Arnould, M.; Rayet, M.; Descouvemont, P.; Baye, D.; Leclercq-Willain, C.; Coc, A.; Barhoumi, S.; Aguer, P.; Rolfs, C.; Kunz, R.; Hammer, J.W.; Mayer, A.; Paradellis, T.; Kossionides, S.; Chronidou, C.; Spyrou, K.; Degl' Innocenti, S.; Fiorentini, G.; Ricci, B.; Zavatarelli, S.; Providencia, C.; Wolters, H.; Soares, J.; Grama, C.; Rahighi, J.; Shotter, A.; Rachti, M. Lamehi
1999-08-23
Low-energy cross section data for 86 charged-particle induced reactions involving light (1 {<=} Z {<=} 14), mostly stable, nuclei are compiled. The corresponding Maxwellian-averaged thermonuclear reaction rates of relevance in astrophysical plasmas at temperatures in the range from 10{sup 6} K to 10{sup 10} K are calculated. These evaluations assume either that the target nuclei are in their ground state, or that the target states are thermally populated following a Maxwell-Boltzmann distribution, except in some cases involving isomeric states. Adopted values complemented with lower and upper limits of the rates are presented in tabular form. Analytical approximations to the adopted rates, as well as to the inverse/direct rate ratios, are provided.
Nuclear reaction rates and opacity in massive star evolution calculations
Bahena, D [Astronomical Institute of the Academy of Sciences, BocnI II 1401, 14131 Praha 4 (Czech Republic); Klapp, J [Instituto Nacional de Investigaciones Nucleares, Km. 36.5 Carr. Mexico-Toluca, 52750 Edo. de Mexico (Mexico); Dehnen, H, E-mail: jaime.klapp@inin.gob.m [Universitaet Konstanz, Fachbereich Physik, Fach M568, D-78457 Konstanz (Germany)
2010-07-01
Nuclear reaction rates and opacity are important parameters in stellar evolution. The input physics in a stellar evolution code determines the main theoretical characteristics of the stellar structure, evolution and nucleosynthesis of a star. For different input physics, in this work we calculate stellar evolution models of very massive first stars during the hydrogen and helium burning phases. We have considered 100 and 200M{sub s}un galactic and pregalactic stars with metallicity Z = 10{sup -6} and 10{sup 9}, respectively. The results show important differences from old to new formulations for the opacity and nuclear reaction rates, in particular the evolutionary tracks are significantly affected, that indicates the importance of using up to date and reliable input physics. The triple alpha reaction activates sooner for pregalactic than for galactic stars.
Prediction of Rate Constants for Catalytic Reactions with Chemical Accuracy.
Catlow, C Richard A
2016-08-01
Ex machina: A computational method for predicting rate constants for reactions within microporous zeolite catalysts with chemical accuracy has recently been reported. A key feature of this method is a stepwise QM/MM approach that allows accuracy to be achieved while using realistic models with accessible computer resources.
Helium Burning Reaction Rate Uncertainties and Consequences for Supernovae
Tur, C.; Heger, A.; Austin, S. M.
2007-10-01
The triple alpha and ^12C(,)^16O reaction rates determine the carbon to oxygen ratio at the completion of core helium burning in stars, which, in turn, influences the later stellar burning stages. We explored the dependence of massive star evolution and nucleosynthesis yields on the experimental uncertainties in the triple alpha rate (10 to 12%) and the ^12C(,)^16O rate (25 to 35%) using full stellar models followed to core collapse and including supernova explosion. The production factors of medium-weight elements obtained by using the Lodders (2003) solar abundances for the initial star composition, rather than the abundances of Anders & Grevesse (1989), provide a less stringent constraint on the ^12C(,)^16O rate. Variations within the current uncertainties in both reaction rates, however, induce significant changes in the central carbon abundance at core carbon ignition and in the mass of the supernova remnant. An experiment is being carried out by an NSCL/WMU collaboration to improve the accuracy of the triple alpha reaction rate.
Noise slows the rate of Michaelis-Menten reactions.
Van Dyken, J David
2017-10-07
Microscopic randomness and the small volumes of living cells combine to generate random fluctuations in molecule concentrations called "noise". Here I investigate the effect of noise on biochemical reactions obeying Michaelis-Menten kinetics, concluding that substrate noise causes these reactions to slow. I derive a general expression for the time evolution of the joint probability density of chemical species in arbitrarily connected networks of non-linear chemical reactions in small volumes. This equation is a generalization of the chemical master equation (CME), a common tool for investigating stochastic chemical kinetics, extended to reaction networks occurring in small volumes, such as living cells. I apply this equation to a generalized Michaelis-Menten reaction in an open system, deriving the following general result: 〈p〉≤p¯ and 〈s〉≥s¯, where s¯ and p¯ denote the deterministic steady-state concentration of reactant and product species, respectively, and 〈s〉 and 〈p〉 denote the steady-state ensemble average over independent realizations of a stochastic reaction. Under biologically realistic conditions, namely when substrate is degraded or diluted by cell division, 〈p〉≤p¯. Consequently, noise slows the rate of in vivo Michaelis-Menten reactions. These predictions are validated by extensive stochastic simulations using Gillespie's exact stochastic simulation algorithm. I specify the conditions under which these effects occur and when they vanish, therefore reconciling discrepancies among previous theoretical investigations of stochastic biochemical reactions. Stochastic slowdown of reaction flux caused by molecular noise in living cells may have functional consequences, which the present theory may be used to quantify. Copyright © 2017 Elsevier Ltd. All rights reserved.
Amason, Charlee; Dreyfuss, Alison; Launey, Kristina; Draayer, Jerry
2017-01-01
We use the ab initio (first-principle) symmetry-adapted no-core shell model (SA-NCSM) to calculate reaction rates of significance to type I X-ray burst nucleosynthesis. We consider the 18O(p,γ)19F reaction, which may influence the production of fluorine, as well as the 16O(α,γ)20Ne reaction, which is key to understanding the production of heavier elements in the universe. Results are compared to those obtained in the no-core sympletic shell model (NCSpM) with a schematic interaction. We discuss how these reaction rates affect the relevant elemental abundances. We thank the NSF for supporting this work through the REU Site in Physics & Astronomy (NSF grant #1560212) at Louisiana State University. This work was also supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248).
Astrophysical reaction rate for $\\alpha(\\alpha n,\\gamma)$
Sumiyoshi, K; Goko, S; Kajino, T
2002-01-01
We study the astrophysical reaction rate for the formation of $^{9}$Be through the three body reaction $\\alpha(\\alpha n,\\gamma)$. This reaction is one of the key reactions which could bridge the mass gap at A = 8 nuclear systems to produce intermediate-to-heavy mass elements in alpha- and neutron-rich environments such as r-process nucleosynthesis in supernova explosions, s-process nucleosynthesis in asymptotic giant branch (AGB) stars, and primordial nucleosynthesis in baryon inhomogeneous cosmological models. To calculate the thermonuclear reaction rate in a wide range of temperatures, we numerically integrate the thermal average of cross sections assuming a two-steps formation through a metastable $^{8}$Be. Off-resonant and on-resonant contributions from the ground state in $^{8}$Be are taken into account. As input cross section, we adopt the latest experimental data by photodisintegration of $^{9}$Be with laser-electron photon beams, which covers all relevant resonances in $^{9}$Be. We provide the reactio...
The temperature-dependence of elementary reaction rates: beyond Arrhenius.
Smith, Ian W M
2008-04-01
The rates of chemical reactions and the dependence of their rate constants on temperature are of central importance in chemistry. Advances in the temperature-range and accuracy of kinetic measurements, principally inspired by the need to provide data for models of combustion, atmospheric, and astrophysical chemistry, show up the inadequacy of the venerable Arrhenius equation--at least, over wide ranges of temperature. This critical review will address the question of how to reach an understanding of the factors that control the rates of 'non-Arrhenius' reactions. It makes use of a number of recent kinetic measurements and shows how developments in advanced forms of transition state theory provide satisfactory explanations of complex kinetic behaviour (72 references).
Why does steady-state magnetic reconnection have a maximum local rate of order 0.1?
Liu, Yi-Hsin; Guo, F; Daughton, W; Li, H; Cassak, P A; Shay, M A
2016-01-01
Simulations suggest collisionless steady-state magnetic reconnection of Harris-type current sheets proceeds with a rate of order 0.1, independent of dissipation mechanism. We argue this long-standing puzzle is a result of constraints at the magnetohydrodynamic (MHD) scale. We perform a scaling analysis of the reconnection rate as a function of the opening angle made by the upstream magnetic fields, finding a maximum reconnection rate close to 0.2. The predictions compare favorably to particle-in-cell simulations of relativistic electron-positron and non-relativistic electron-proton reconnection. The fact that simulated reconnection rates are close to the predicted maximum suggests reconnection proceeds near the most efficient state allowed at the MHD-scale. The rate near the maximum is relatively insensitive to the opening angle, potentially explaining why reconnection has a similar fast rate in differing models.
Rate Constant Calculation for Thermal Reactions Methods and Applications
DaCosta, Herbert
2011-01-01
Providing an overview of the latest computational approaches to estimate rate constants for thermal reactions, this book addresses the theories behind various first-principle and approximation methods that have emerged in the last twenty years with validation examples. It presents in-depth applications of those theories to a wide range of basic and applied research areas. When doing modeling and simulation of chemical reactions (as in many other cases), one often has to compromise between higher-accuracy/higher-precision approaches (which are usually time-consuming) and approximate/lower-preci
Benício, Kadja; Dias, Fernando A. L.; Gualdi, Lucien P.; Aliverti, Andrea; Resqueti, Vanessa R.; Fregonezi, Guilherme A. F.
2015-01-01
OBJECTIVE: To assess the influence of diaphragmatic activation control (diaphC) on Sniff Nasal-Inspiratory Pressure (SNIP) and Maximum Relaxation Rate of inspiratory muscles (MRR) in healthy subjects. METHOD: Twenty subjects (9 male; age: 23 (SD=2.9) years; BMI: 23.8 (SD=3) kg/m2; FEV1/FVC: 0.9 (SD=0.1)] performed 5 sniff maneuvers in two different moments: with or without instruction on diaphC. Before the first maneuver, a brief explanation was given to the subjects on how to perform the sniff test. For sniff test with diaphC, subjects were instructed to perform intense diaphragm activation. The best SNIP and MRR values were used for analysis. MRR was calculated as the ratio of first derivative of pressure over time (dP/dtmax) and were normalized by dividing it by peak pressure (SNIP) from the same maneuver. RESULTS: SNIP values were significantly different in maneuvers with and without diaphC [without diaphC: -100 (SD=27.1) cmH2O/ with diaphC: -72.8 (SD=22.3) cmH2O; p<0.0001], normalized MRR values were not statistically different [without diaphC: -9.7 (SD=2.6); with diaphC: -8.9 (SD=1.5); p=0.19]. Without diaphC, 40% of the sample did not reach the appropriate sniff criteria found in the literature. CONCLUSION: Diaphragmatic control performed during SNIP test influences obtained inspiratory pressure, being lower when diaphC is performed. However, there was no influence on normalized MRR. PMID:26578254
Application of semiclassical methods to reaction rate theory
Hernandez, R.
1993-11-01
This work is concerned with the development of approximate methods to describe relatively large chemical systems. This effort has been divided into two primary directions: First, we have extended and applied a semiclassical transition state theory (SCTST) originally proposed by Miller to obtain microcanonical and canonical (thermal) rates for chemical reactions described by a nonseparable Hamiltonian, i.e. most reactions. Second, we have developed a method to describe the fluctuations of decay rates of individual energy states from the average RRKM rate in systems where the direct calculation of individual rates would be impossible. Combined with the semiclassical theory this latter effort has provided a direct comparison to the experimental results of Moore and coworkers. In SCTST, the Hamiltonian is expanded about the barrier and the ``good`` action-angle variables are obtained perturbatively; a WKB analysis of the effectively one-dimensional reactive direction then provides the transmission probabilities. The advantages of this local approximate treatment are that it includes tunneling effects and anharmonicity, and it systematically provides a multi-dimensional dividing surface in phase space. The SCTST thermal rate expression has been reformulated providing increased numerical efficiency (as compared to a naive Boltzmann average), an appealing link to conventional transition state theory (involving a ``prereactive`` partition function depending on the action of the reactive mode), and the ability to go beyond the perturbative approximation.
Al-haj Ali, Mohammad; Betlem, Ben; Roffel, Brian; Weickert, Günter
2007-01-01
The use of pressure-drop and constant-pressure dilatometry for obtaining rate data for liquid propylene polymerization in filled batch reactors was examined. The first method uses reaction temperature and pressure as well as the compressibility of the reactor contents to calculate the polymerization
1984-04-04
The objetive of this work is to determine the changes in the particle structure of coal as it undergoes the carbon/carbon dioxide reaction (C + CO/sub 2/ ..-->.. 2CO). Char was produced by heating the coal at a rate of 25/sup 0/C/min to the reaction temperatures of 800/sup 0/C, 900/sup 0/C, 1000/sup 0/C and 1100/sup 0/C. The changes in surface area and effective diffusivity as a result of devolitization were determined. Changes in effective diffusivity and surface area as a function of conversion have been measured for reactions conducted at 800, 900, 1000 and 1100/sup 0/C for Wyodak coal char. The surface areas exhibit a maximum as a function of conversion in all cases. For the reaction at 1000/sup 0/C the maximum in surface area is greater than the maxima determined at all other reaction temperatures. Thermogravimetric rate data were obtained for five coal chars; Wyodak, Wilcox, Cimmeron, Illinois number 6 and Pittsburgh number 6 over the temperature range 800-1100/sup 0/C. All coal chars exhibit a maximum in reaction rate. Five different models for gas-solid reactions were evaluated. The Bhatia/Perlmutter model seems to best represent the data. 129 references, 67 figures, 37 tables.
Optimum poultry litter rates for maximum profit vs. yield in cotton production
Cotton lint yield responds well to increasing rates of poultry litter fertilization, but little is known of how optimum rates for yield compare with optimum rates for profit. The objectives of this study were to analyze cotton lint yield response to poultry litter application rates, determine and co...
Optimized reaction mechanism rate rules for ignition of normal alkanes
Cai, Liming
2016-08-11
The increasing demand for cleaner combustion and reduced greenhouse gas emissions motivates research on the combustion of hydrocarbon fuels and their surrogates. Accurate detailed chemical kinetic models are an important prerequisite for high fidelity reacting flow simulations capable of improving combustor design and operation. The development of such models for many new fuel components and/or surrogate molecules is greatly facilitated by the application of reaction classes and rate rules. Accurate and versatile rate rules are desirable to improve the predictive accuracy of kinetic models. A major contribution in the literature is the recent work by Bugler et al. (2015), which has significantly improved rate rules and thermochemical parameters used in kinetic modeling of alkanes. In the present study, it is demonstrated that rate rules can be used and consistently optimized for a set of normal alkanes including n-heptane, n-octane, n-nonane, n-decane, and n-undecane, thereby improving the predictive accuracy for all the considered fuels. A Bayesian framework is applied in the calibration of the rate rules. The optimized rate rules are subsequently applied to generate a mechanism for n-dodecane, which was not part of the training set for the optimized rate rules. The developed mechanism shows accurate predictions compared with published well-validated mechanisms for a wide range of conditions.
无
2008-01-01
Quasi-likelihood nonlinear models (QLNM) include generalized linear models as a special case.Under some regularity conditions,the rate of the strong consistency of the maximum quasi-likelihood estimation (MQLE) is obtained in QLNM.In an important case,this rate is O(n-1/2(loglogn)1/2),which is just the rate of LIL of partial sums for I.I.d variables,and thus cannot be improved anymore.
On the maximum rate of change in sunspot number growth and the size of the sunspot cycle
Wilson, Robert M.
1990-01-01
Statistically significant correlations exist between the size (maximum amplitude) of the sunspot cycle and, especially, the maximum value of the rate of rise during the ascending portion of the sunspot cycle, where the rate of rise is computed either as the difference in the month-to-month smoothed sunspot number values or as the 'average rate of growth' in smoothed sunspot number from sunspot minimum. Based on the observed values of these quantities (equal to 10.6 and 4.63, respectively) as of early 1989, it is inferred that cycle 22's maximum amplitude will be about 175 + or - 30 or 185 + or - 10, respectively, where the error bars represent approximately twice the average error found during cycles 10-21 from the two fits.
Toward understanding the rates of reactions at mineral surfaces
Casey, W.H. [Univ. of California Davis, CA (United States). Dept. of Land, Air and Water Resources and Dept. of Geology; Ludwig, C. [EAWAG, Swiss Federal Institute for Environmental Science and Technolgy, Dubendorf (Switzerland). Dept. of Resources and Waste management; Holmen, B. [Univ. of California Davis, CA (United States). Dept. of Land, Air and Water Resources
1998-12-31
Environmental geo chemists are commonly called upon to make predictions over long scales of time and distance. In many cases, these predictions involve disequilibrium reactions, such as the decomposition of ozone-depleting gases or the migration rates of groundwater contaminants. These groundwater contaminants interact with mineral surfaces in a complicated fashion that is not understood quantitatively. However, in a real sense, mineral dissolution studies are to the aqueous geo chemists what Escherichia coli are to microbiologists: an inexpensive model system to map out important kinetic relations that can then be extended qualitatively to other settings. This chapter explains that is enormously useful to draw analogies between reactions at mineral surfaces and at dissolved metal-ligand complexes. In this approach, the reactivities of bond between a metal and a water molecule or ligand in the inner-coordination-sphere of the dissolved complex are proxies for bonds between a metal and oxygen at the mineral surface, which cannot be studied directly.
Reaction rate constant for radiative association of CF{sup +}
Öström, Jonatan, E-mail: jonatan.ostrom@gmail.com; Gustafsson, Magnus, E-mail: magnus.gustafsson@ltu.se [Applied Physics, Division of Materials Science, Department of Engineering Science and Mathematics, Luleå University of Technology, 97187 Luleå (Sweden); Bezrukov, Dmitry S. [Department of Chemistry, M. V. Lomonosov Moscow State University, Moscow, 119991 (Russian Federation); Nyman, Gunnar [Department of Chemistry and Molecular Biology, University of Gothenburg, 41296 Gothenburg (Sweden)
2016-01-28
Reaction rate constants and cross sections are computed for the radiative association of carbon cations (C{sup +}) and fluorine atoms (F) in their ground states. We consider reactions through the electronic transition 1{sup 1}Π → X{sup 1}Σ{sup +} and rovibrational transitions on the X{sup 1}Σ{sup +} and a{sup 3}Π potentials. Semiclassical and classical methods are used for the direct contribution and Breit–Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius–Kooij formula in five temperature intervals with a relative difference of <3%. The fit parameters will be added to the online database KIDA. For a temperature of 10–250 K, the rate constant is about 10{sup −21} cm{sup 3} s{sup −1}, rising toward 10{sup −16} cm{sup 3} s{sup −1} for a temperature of 30 000 K.
Reaction Rate Constant for Radiative Association of CF$^+$
Öström, Jonatan; Nyman, Gunnar; Gustafsson, Magnus
2015-01-01
Reaction rate constants and cross sections are computed for the radiative association of carbon cations ($\\text{C}^+$) and fluorine atoms ($\\text{F}$) in their ground states. We consider reactions through the electronic transition $1^1\\Pi \\rightarrow X^1\\Sigma^+$ and rovibrational transitions on the $X^1\\Sigma^+$ and $a^3\\Pi$ potentials. Semiclassical and classical methods are used for the direct contribution and Breit--Wigner theory for the resonance contribution. Quantum mechanical perturbation theory is used for comparison. A modified formulation of the classical method applicable to permanent dipoles of unequally charged reactants is implemented. The total rate constant is fitted to the Arrhenius--Kooij formula in five temperature intervals with a relative difference of $<3\\:\\%$. The fit parameters will be added to the online database KIDA. For a temperature of $10$ to $250\\:\\text{K}$, the rate constant is about $10^{-21}\\:\\text{cm}^3\\text{s}^{-1}$, rising toward $10^{-16}\\:\\text{cm}^3\\text{s}^{-1}$ fo...
Jensen, Randall L; Ebben, William P
2007-08-01
Because the intensity of plyometric exercises usually is based simply upon anecdotal recommendations rather than empirical evidence, this study sought to quantify a variety of these exercises based on forces placed upon the knee. Six National Collegiate Athletic Association Division I athletes who routinely trained with plyometric exercises performed depth jumps from 46 and 61 cm, a pike jump, tuck jump, single-leg jump, countermovement jump, squat jump, and a squat jump holding dumbbells equal to 30% of 1 repetition maximum (RM). Ground reaction forces obtained via an AMTI force plate and video analysis of markers placed on the left hip, knee, lateral malleolus, and fifth metatarsal were used to estimate rate of eccentric force development (E-RFD), peak ground reaction forces (GRF), ground reaction forces relative to body weight (GRF/BW), knee joint reaction forces (K-JRF), and knee joint reaction forces relative to body weight (K-JRF/BW) for each plyometric exercise. One-way repeated measures analysis of variance indicated that E-RFD, K-JRF, and K-JRF/BW were different across the conditions (p 0.05). Results indicate that there are quantitative differences between plyometric exercises in the rate of force development during landing and the forces placed on the knee, though peak GRF forces associated with landing may not differ.
Evaluation of antioxidants using oxidation reaction rate constants
SHI Yan; ZHAN Xiancheng; MA Lie; LI Linli; LI Chengrong
2007-01-01
An evaluation method for the capacity of antioxidants to protect drugs against oxidation is presented.As a new viewpoint,to determine the priority of the competitive oxidations between the antioxidant and the protected drug,and to compare the drug-protection capacity of antioxidants,it is important to determine their oxidation rate constants using chemical kinetics instead of standard oxidation (or reduction) potentials.Sodium sulfite,sodium bisulfite and sodium pyrosulfite were used as models for the determination of oxidation reaction rate constants in aqueous solutions.In the experiments,sufficient air was continually infused into the solution to keep the concentration of dissolved oxygen constant.The residual concentrations of the antioxidants were determined by iodimetry,and the concentration of dissolved oxygen by oxygen electrode.The data were fitted by linear regressions to obtain the reaction rate constants.It was found that the degradation of sodium sulfite,sodium bisulfite or sodium pyrosulfite obeyed pseudo zero-order kinetics in the buffer solutions.Because of the ionization equilibrium,these three antioxidants have the same ion form in solutions at a definite pH value and therefore their apparent rate constants were essentially the same.The average apparent rate constants of the three antioxidants at 25~C are (1.34±0.03)×10-3 at pH 6.8,(1.20±0.02) x 10-3 at pH 4.0 and (6.58±0.02)×10-3 mol.L-1.h-1 at pH 9.2,respectively.
Helium Ignition on Accreting Neutron Stars with a New Triple-α Reaction Rate
Peng, Fang; Ott, Christian D.
2010-12-01
We investigate the effect of a new triple-α reaction rate from Ogata et al. on helium ignition conditions on accreting neutron stars and on the properties of the subsequent type I X-ray burst. We find that the new rate leads to significantly lower ignition column density for accreting neutron stars at low accretion rates. We compare the results of our ignition models for a pure helium accretor to observations of bursts in ultracompact X-ray binaries (UCXBs), which are believed to have nearly pure helium donors. For \\dot{m}> 0.001 \\dot{m}_{{Edd}}, the new triple-α reaction rate from Ogata et al. predicts a maximum helium ignition column of ~3 × 109 g cm-2, corresponding to a burst energy of ~4 × 1040 erg. For \\dot{m}˜ 0.01 \\dot{m}_{{Edd}} at which intermediate long bursts occur, the predicted burst energies are at least a factor of 10 too low to explain the observed energies of such bursts in UCXBs. This finding adds to the doubts cast on the triple-α reaction rate of Ogata et al. by the low-mass stellar evolution results of Dotter & Paxton.
Helium Ignition on Accreting Neutron Stars with a New Triple-alpha Reaction Rate
Peng, Fang
2010-01-01
We investigate the effect of a new triple-alpha reaction rate from Ogata et al. (2009) on helium ignition conditions on accreting neutron stars and on the properties of the subsequent type I X-ray burst. We find that the new rate leads to significantly lower ignition column density for accreting neutron stars at low accretion rates. We compare the results of our ignition models for a pure helium accretor to observations of bursts in ultra-compact X-ray binary (UCXBs), which are believed to have nearly pure helium donors. For mdot > 0.001 mdot_Edd, the new triple-alpha reaction rate from Ogata et al. (2009) predicts a maximum helium ignition column of ~ 3 x 10^9 g cm^{-2}, corresponding to a burst energy of ~ 4 x 10^{40} ergs. For mdot ~ 0.01 mdot_Edd at which intermediate long bursts occur, the predicted burst energies are at least a factor of 10 too low to explain the observed energies of such bursts in UCXBs. This finding adds to the doubts cast on the triple-alpha reaction rate of Ogata et al. (2009) by th...
Ambarita, Himsar; Kishinami, Koki; Daimaruya, Mashashi; Tokura, Ikuo; Kawai, Hideki; Suzuki, Jun; Kobiyama, Mashayosi; Ginting, Armansyah
The present paper is a study on the optimum plate to plate spacing for maximum heat transfer rate from a flat plate type heat exchanger. The heat exchanger consists of a number of parallel flat plates. The working fluids are flowed at the same operational conditions, either fixed pressure head or fixed fan power input. Parallel and counter flow directions of the working fluids were considered. While the volume of the heat exchanger is kept constant, plate number was varied. Hence, the spacing between plates as well as heat transfer rate will vary and there exists a maximum heat transfer rate. The objective of this paper is to seek the optimum plate to plate spacing for maximum heat transfer rate. In order to solve the problem, analytical and numerical solutions have been carried out. In the analytical solution, the correlations of the optimum plate to plate spacing as a function of the non-dimensional parameters were developed. Furthermore, the numerical simulation is carried out to evaluate the correlations. The results show that the optimum plate to plate spacing for a counter flow heat exchanger is smaller than parallel flow ones. On the other hand, the maximum heat transfer rate for a counter flow heat exchanger is bigger than parallel flow ones.
Hora, Heinrich; Miley, George
2007-03-01
One of the most convincing facts about LENR due to deuterons (ds) or protons of very high concentration in host metals of palladium is the measurement of the large scale minimum in the reaction probability with product elements centered around the nucleon number A = 153. The local maximum was measured in this region is similar to fission of uranium at A = 119 where the local maximum follows the Maruhn-Greiner mechanism^1. We suggest this phenomenon can be explained by the strong screening of the Maxwellian ds on the degenerate rigid electron background within the swimming electrons at the metal surface or thin filem interfaces. The deuterons behave like neutrals at distances of above 2 picometers (pm) and form clusters due to soft attraction in the range of thermal energy; 10 pm diameter clusters can react over long time scales (10^6 s) with Pd leading to double magic number compound nuclei 306x126 decaying via fission to an A=153 element distribution. J. Maruhn et al, Phys. Rev. Letters 32, 548 (1974) H. Hora, G.H. Miley, CzechJ. Phys. 48, 1111 (1998)
李志宏; 郭冰; 李云居; 苏俊; 李二涛; 白希祥; 王友宝; 曾晟; 王宝祥; 颜胜权; 李志常; 刘建成; 连钢; 金孙均; 刘鑫; 柳卫平
2012-01-01
The radiative capture reaction plays an important role in nuclear astrophysics. We have indirectly measured the astrophysical S(E) factors for some proton capture reactions and reaction rates for several neutron capture reactions with one nucleon transfer reactions at HI-13 tandem accelerator in recent years. Some of them are compiled into IAEA EXFOR database and JINA REACLIB project, and used in the network calculations of Big Bang nucleosynthesis and type-I X-ray bursts.
THE ASYMPTOTIC LIMIT FOR A COMBUSTION MODEL IN REGARD TO INFINITE REACTION RATE
Ying Longan
2008-01-01
The Zeldovich-von Neumann-Doring model and the Chapman-Jouguet model for a simplified combustion model-Majda's model is studied. The author proves a uniform maximum norm estimate, then proves that as the rate of chemical reaction tends to infinity the solutions to the Zeldovich-von Neumann-Doring model tend to that of the Chapman-Jouguet model. The type of combustion waves is studied. This result is compared with the result of the projection and finite difference method for the same model.
Maximum Acceptable Vibrato Excursion as a Function of Vibrato Rate in Musicians and Non-musicians
Vatti, Marianna; Santurette, Sébastien; Pontoppidan, Niels H.
and, in most listeners, exhibited a peak at medium vibrato rates (5–7 Hz). Large across-subject variability was observed, and no significant effect of musical experience was found. Overall, most listeners were not solely sensitive to the vibrato excursion and there was a listener-dependent rate...
Maximum Acceptable Vibrato Excursion as a Function of Vibrato Rate in Musicians and Non-musicians
Vatti, Marianna; Santurette, Sébastien; Pontoppidan, Niels H.
2014-01-01
and, in most listeners, exhibited a peak at medium vibrato rates (5–7 Hz). Large across-subject variability was observed, and no significant effect of musical experience was found. Overall, most listeners were not solely sensitive to the vibrato excursion and there was a listener-dependent rate...
7 CFR 1.187 - Rulemaking on maximum rates for attorney fees.
2010-01-01
... the types of proceedings in which the rate should be used. It also should explain fully the reasons... certain types of proceedings), the Department may adopt regulations providing that attorney fees may be awarded at a rate higher than $125 per hour in some or all of the types of proceedings covered by...
Maximum likelihood methods for investigating reporting rates of rings on hunter-shot birds
Conroy, M.J.; Morgan, B.J.T.; North, P.M.
1985-01-01
It is well known that hunters do not report 100% of the rings that they find on shot birds. Reward studies can be used to estimate what this reporting rate is, by comparison of recoveries of rings offering a monetary reward, to ordinary rings. A reward study of American Black Ducks (Anas rubripes) is used to illustrate the design, and to motivate the development of statistical models for estimation and for testing hypotheses of temporal and geographic variation in reporting rates. The method involves indexing the data (recoveries) and parameters (reporting, harvest, and solicitation rates) by geographic and temporal strata. Estimates are obtained under unconstrained (e.g., allowing temporal variability in reporting rates) and constrained (e.g., constant reporting rates) models, and hypotheses are tested by likelihood ratio. A FORTRAN program, available from the author, is used to perform the computations.
Rate of strong consistency of quasi maximum likelihood estimate in generalized linear models
无
2004-01-01
［1］McCullagh, P., Nelder, J. A., Generalized Linear Models, New York: Chapman and Hall, 1989.［2］Wedderbum, R. W. M., Quasi-likelihood functions, generalized linear models and Gauss-Newton method,Biometrika, 1974, 61:439-447.［3］Fahrmeir, L., Maximum likelihood estimation in misspecified generalized linear models, Statistics, 1990, 21:487-502.［4］Fahrmeir, L., Kaufmann, H., Consistency and asymptotic normality of the maximum likelihood estimator in generalized linear models, Ann. Statist., 1985, 13: 342-368.［5］Melder, J. A., Pregibon, D., An extended quasi-likelihood function, Biometrika, 1987, 74: 221-232.［6］Bennet, G., Probability inequalities for the sum of independent random variables, JASA, 1962, 57: 33-45.［7］Stout, W. F., Almost Sure Convergence, New York:Academic Press, 1974.［8］Petrov, V, V., Sums of Independent Random Variables, Berlin, New York: Springer-Verlag, 1975.
Reaction rate theory of radiation exposure: Effects of the dose rate on mutation frequencies
Manabe, Yuichiro; Nakamura, Issei
2014-01-01
We develop a kinetic reaction model for the cells having the irradiated DNA molecules due to the ionizing radiation exposure. Our theory simultaneously accounts for the time-dependent reactions of the DNA damage, the DNA mutation, the DNA repair, and the proliferation and apoptosis of cells in a tissue with a minimal set of model parameters. In contrast to the existing theories for the radiation exposition, we do not assume the relationships between the total dose and the induced mutation frequency. We show good agreement between theory and experiment. Importantly, our result shows a new perspective that the key ingredient in the study of the irradiated cells is the rate constants depending on the dose rate. Moreover, we discuss the universal scaling function for mutation frequencies due to the irradiation at low dose rates.
McCarthy, C M; Taylor, M A; Dennis, M W
1987-01-01
Mycobacterium avium is a human pathogen which may cause either chronic or disseminated disease and the organism exhibits a slow rate of growth. This study provides information on the growth rate of the organism in chronically infected mice and its maximal growth rate in vitro. M. avium was grown in continuous culture, limited for nitrogen with 0.5 mM ammonium chloride and dilution rates that ranged from 0.054 to 0.153 h-1. The steady-state concentration of ammonia nitrogen and M. avium cells for each dilution rate were determined. The bacterial saturation constant for growth-limiting ammonia was 0.29 mM (4 micrograms nitrogen/ml) and, from this, the maximal growth rate for M. avium was estimated to be 0.206 h-1 or a doubling time of 3.4 h. BALB/c mice were infected intravenously with 3 x 10(6) colony-forming units and a chronic infection resulted, typical of virulent M. avium strains. During a period of 3 months, the number of mycobacteria remained constant in the lungs, but increased 30-fold and 8,900-fold, respectively, in the spleen and mesenteric lymph nodes. The latter increase appeared to be due to proliferation in situ. The generation time of M. avium in the mesenteric lymph nodes was estimated to be 7 days.
Quinn, T Alexander; Kohl, Peter
2016-12-01
Mechanical stimulation (MS) represents a readily available, non-invasive means of pacing the asystolic or bradycardic heart in patients, but benefits of MS at higher heart rates are unclear. Our aim was to assess the maximum rate and sustainability of excitation by MS vs. electrical stimulation (ES) in the isolated heart under normal physiological conditions. Trains of local MS or ES at rates exceeding intrinsic sinus rhythm (overdrive pacing; lowest pacing rates 2.5±0.5 Hz) were applied to the same mid-left ventricular free-wall site on the epicardium of Langendorff-perfused rabbit hearts. Stimulation rates were progressively increased, with a recovery period of normal sinus rhythm between each stimulation period. Trains of MS caused repeated focal ventricular excitation from the site of stimulation. The maximum rate at which MS achieved 1:1 capture was lower than during ES (4.2±0.2 vs. 5.9±0.2 Hz, respectively). At all overdrive pacing rates for which repetitive MS was possible, 1:1 capture was reversibly lost after a finite number of cycles, even though same-site capture by ES remained possible. The number of MS cycles until loss of capture decreased with rising stimulation rate. If interspersed with ES, the number of MS to failure of capture was lower than for MS only. In this study, we demonstrate that the maximum pacing rate at which MS can be sustained is lower than that for same-site ES in isolated heart, and that, in contrast to ES, the sustainability of successful 1:1 capture by MS is limited. The mechanism(s) of differences in MS vs. ES pacing ability, potentially important for emergency heart rhythm management, are currently unknown, thus warranting further investigation. © The Author 2016. Published by Oxford University Press on behalf of the European Society of Cardiology.
Maximum Rate of Growth of Enstrophy in Solutions of the Fractional Burgers Equation
Yun, Dongfang
2016-01-01
This investigation is a part of a research program aiming to characterize the extreme behavior possible in hydrodynamic models by probing the sharpness of estimates on the growth of certain fundamental quantities. We consider here the rate of growth of the classical and fractional enstrophy in the fractional Burgers equation in the subcritical, critical and supercritical regime. First, we obtain estimates on these rates of growth and then show that these estimates are sharp up to numerical prefactors. In particular, we conclude that the power-law dependence of the enstrophy rate of growth on the fractional dissipation exponent has the same global form in the subcritical, critical and parts of the supercritical regime. This is done by numerically solving suitably defined constrained maximization problems and then demonstrating that for different values of the fractional dissipation exponent the obtained maximizers saturate the upper bounds in the estimates as the enstrophy increases. In addition, nontrivial be...
Modeling microbial reaction rates in a submarine hydrothermal vent chimney wall
LaRowe, Douglas E.; Dale, Andrew W.; Aguilera, David R.; L'Heureux, Ivan; Amend, Jan P.; Regnier, Pierre
2014-01-01
The fluids emanating from active submarine hydrothermal vent chimneys provide a window into subseafloor processes and, through mixing with seawater, are responsible for steep thermal and compositional gradients that provide the energetic basis for diverse biological communities. Although several models have been developed to better understand the dynamic interplay of seawater, hydrothermal fluid, minerals and microorganisms inside chimney walls, none provide a fully integrated approach to quantifying the biogeochemistry of these hydrothermal systems. In an effort to remedy this, a fully coupled biogeochemical reaction-transport model of a hydrothermal vent chimney has been developed that explicitly quantifies the rates of microbial catalysis while taking into account geochemical processes such as fluid flow, solute transport and oxidation-reduction reactions associated with fluid mixing as a function of temperature. The metabolisms included in the reaction network are methanogenesis, aerobic oxidation of hydrogen, sulfide and methane and sulfate reduction by hydrogen and methane. Model results indicate that microbial catalysis is generally fastest in the hottest habitable portion of the vent chimney (77-102 °C), and methane and sulfide oxidation peak near the seawater-side of the chimney. The fastest metabolisms are aerobic oxidation of H2 and sulfide and reduction of sulfate by H2 with maximum rates of 140, 900 and 800 pmol cm-3 d-1, respectively. The maximum rate of hydrogenotrophic methanogenesis is just under 0.03 pmol cm-3 d-1, the slowest of the metabolisms considered. Due to thermodynamic inhibition, there is no anaerobic oxidation of methane by sulfate (AOM). These simulations are consistent with vent chimney metabolic activity inferred from phylogenetic data reported in the literature. The model developed here provides a quantitative approach to describing the rates of biogeochemical transformations in hydrothermal systems and can be used to constrain the
Rate of strong consistency of quasi maximum likelihood estimate in generalized linear models
YUE Li; CHEN Xiru
2004-01-01
Under the assumption that in the generalized linear model (GLM) the expectation of the response variable has a correct specification and some other smooth conditions,it is shown that with probability one the quasi-likelihood equation for the GLM has a solution when the sample size n is sufficiently large. The rate of this solution tending to the true value is determined. In an important special case, this rate is the same as specified in the LIL for iid partial sums and thus cannot be improved anymore.
Riisgård, Hans Ulrik; Larsen, Poul Scheel; Pleissner, Daniel
2014-01-01
rate (F, l h-1), W (g), and L (mm) as described by the equations: FW = aWb and FL = cLd, respectively. This is done by using available and new experimental laboratory data on M. edulis obtained by members of the same research team using different methods and controlled diets of cultivated algal cells...
Improved resonance reaction rate calculation for lattice physics subsystem
Finch, D.R.
1974-02-08
The resonance capture calculations of the HAMMER System and HAMBUR System are derived from a consistent statement of the integral slowing down equation and definitions of the resonance integral. The assumptions made in these treatments are explicitly stated, and and an attempt is made to estimate the possible error in the resonance integral arising from these assumptions. This analysis is made to pin-point those parts of the calculation that can be improved and updated. Based on the analysis of existing calculations a method of calculation is derived which avoids most of the problems encountered in HAMMER and HAMBUR. The chief improvements that result are as follows: Careful attention is paid to calculation of the resonance flux as most errors in existing calculations result from consistently overpredicting fluxes in all regions of a lattice cell. The calculation can be modified to produce as crude or detailed a resonance calculation, at the expense of computer time, as required by the user. Resonances that overlap group boundaries contribute the correct contribution to each group's reaction rates. Overlap between resonances of different isotopes is correctly accounted for. Up-to-date resonance formalisms are used including the Adler-Adler multi-level formulations. Provision is made to easily add new formalisms when required. Streaming effects from neutron leaking into a cell may optionally be included in the calculation of resonance reaction rates. A complete description of the physics contained in this new computational module is provided along with additional information on the numerical techniques employed in the module.
Analysis of reaction rates of single molecules on metal surfaces
Ueba, H.
2017-10-01
The experimental results of the action spectra i.e., reaction rate R(V) as a function of a bias voltage V are analyzed for rotation of a single CCH (D) molecule on a Cu (100) surface [5] and hopping of a single H(D)2O molecule on Pd(111) surface [6]. In the former system it is identified that rotation occurs if enough energy stored in the C-H (D) in-plane bending (IPB) mode excited by tunneling electron is transferred to the C-H (D) out of plane bending (OPB) mode (reaction coordinate mode) via the anharmonic mode coupling in a single electron process. The calculated R(V) shows an excellent agreement with the experimental results except at the low bias voltages below V ≃ 60 mV where no experimental data is available for the nonlinear current I dependence of R(I). A reproduction of the experimental R(V) at the higher voltage region allows us to determine the vibrational density of states of the C-H IPB mode and its coupling rate to the C-H (D) OPB mode as well as the inelastic tunneling current to excite IPB mode. A change of a conductance upon excitation of the C-H IPB mode enables us to evaluate the electron-vibration coupling strength inducing the rotation motion of CCH molecule. In the latter system investigated at a high temperature of about 40 K, the constant R(V) due to thermal hopping followed by the rapid increase is satisfactory explained by anharmonic inter-mode coupling between the scissor mode excited by tunneling electrons and the frustrated translation mode for H(D)2O molecule on Pd(111).
Maximum organic loading rate for the single-stage wet anaerobic digestion of food waste.
Nagao, Norio; Tajima, Nobuyuki; Kawai, Minako; Niwa, Chiaki; Kurosawa, Norio; Matsuyama, Tatsushi; Yusoff, Fatimah Md; Toda, Tatsuki
2012-08-01
Anaerobic digestion of food waste was conducted at high OLR from 3.7 to 12.9 kg-VS m(-3) day(-1) for 225 days. Periods without organic loading were arranged between the each loading period. Stable operation at an OLR of 9.2 kg-VS (15.0 kg-COD) m(-3) day(-1) was achieved with a high VS reduction (91.8%) and high methane yield (455 mL g-VS-1). The cell density increased in the periods without organic loading, and reached to 10.9×10(10) cells mL(-1) on day 187, which was around 15 times higher than that of the seed sludge. There was a significant correlation between OLR and saturated TSS in the sludge (y=17.3e(0.1679×), r(2)=0.996, P<0.05). A theoretical maximum OLR of 10.5 kg-VS (17.0 kg-COD) m(-3) day(-1) was obtained for mesophilic single-stage wet anaerobic digestion that is able to maintain a stable operation with high methane yield and VS reduction.
Manual Choice Reaction Times in the Rate-Domain
Chris eHarris
2014-06-01
Full Text Available Over the last 150 years, human manual reaction times (RTs have been recorded countless times. Yet, our understanding of them remains remarkably poor. RTs are highly variable with positively skewed frequency distributions, often modelled as an inverse Gaussian distribution reflecting a stochastic rise to threshold (diffusion process. However, latency distribution of saccades are very close to the reciprocal Normal, suggesting that ‘rate’ (reciprocal RT may be the more fundamental variable. We explored whether this phenomenon extends to choice manual RTs. We recorded two-alternative choice RTs from 24 subjects, each with 4 blocks of 200 trials with two task difficulties (easy vs. difficult discrimination and two instruction sets (urgent vs. accurate. We found that rate distributions were, indeed, very close to Normal, shifting to lower rates with increasing difficulty and accuracy, and for some blocks subjects they appeared to become left-truncated, but still close to Normal. Using autoregressive techniques, we found temporal sequential dependencies for lags of at least 3. We identified a transient and steady-state component in each block. Because rates were Normal, we were able to estimate autoregressive weights using the Box-Jenkins technique, and convert to a moving average model using z-transforms to show explicit dependence on stimulus input. We also found a spatial sequential dependence for the previous 3 lags depending on whether the laterality of previous trials was repeated or alternated. This was partially dissociated from temporal dependency as it only occurred in the easy tasks. We conclude that 2-alternative choice manual RT distributions are close to reciprocal Normal and not the inverse Gaussian. This is not consistent with stochastic rise to threshold models, and we propose a simple optimality model in which reward is maximized to yield to an optimal rate, and hence an optimal time to respond. We discuss how it might be
Validity of heart rate based nomogram fors estimation of maximum oxygen uptake in Indian population.
Kumar, S Krishna; Khare, P; Jaryal, A K; Talwar, A
2012-01-01
Maximal oxygen uptake (VO2max) during a graded maximal exercise test is the objective method to assess cardiorespiratory fitness. Maximal oxygen uptake testing is limited to only a few laboratories as it requires trained personnel and strenuous effort by the subject. At the population level, submaximal tests have been developed to derive VO2max indirectly based on heart rate based nomograms or it can be calculated using anthropometric measures. These heart rate based predicted standards have been developed for western population and are used routinely to predict VO2max in Indian population. In the present study VO2max was directly measured by maximal exercise test using a bicycle ergometer and was compared with VO2max derived by recovery heart rate in Queen's College step test (QCST) (PVO2max I) and with VO2max derived from Wasserman equation based on anthropometric parameters and age (PVO2max II) in a well defined age group of healthy male adults from New Delhi. The values of directly measured VO2max showed no significant correlation either with the estimated VO2max with QCST or with VO2max predicted by Wasserman equation. Bland and Altman method of approach for limit of agreement between VO2max and PVO2max I or PVO2max II revealed that the limits of agreement between directly measured VO2max and PVO2max I or PVO2max II was large indicating inapplicability of prediction equations of western population in the population under study. Thus it is evident that there is an urgent need to develop nomogram for Indian population, may be even for different ethnic sub-population in the country.
Longitudinal Examination of Age-Predicted Symptom-Limited Exercise Maximum Heart Rate
Zhu, Na; Suarez, Jose; Sidney, Steve; Sternfeld, Barbara; Schreiner, Pamela J.; Carnethon, Mercedes R.; Lewis, Cora E.; Crow, Richard S.; Bouchard, Claude; Haskell, William; Jacobs, David R.
2010-01-01
Purpose To estimate the association of age with maximal heart rate (MHR). Methods Data were obtained in the Coronary Artery Risk Development in Young Adults (CARDIA) study. Participants were black and white men and women aged 18-30 in 1985-86 (year 0). A symptom-limited maximal graded exercise test was completed at years 0, 7, and 20 by 4969, 2583, and 2870 participants, respectively. After exclusion 9622 eligible tests remained. Results In all 9622 tests, estimated MHR (eMHR, beats/minute) had a quadratic relation to age in the age range 18 to 50 years, eMHR=179+0.29*age-0.011*age2. The age-MHR association was approximately linear in the restricted age ranges of consecutive tests. In 2215 people who completed both year 0 and 7 tests (age range 18 to 37), eMHR=189–0.35*age; and in 1574 people who completed both year 7 and 20 tests (age range 25 to 50), eMHR=199–0.63*age. In the lowest baseline BMI quartile, the rate of decline was 0.20 beats/minute/year between years 0-7 and 0.51 beats/minute/year between years 7-20; while in the highest baseline BMI quartile there was a linear rate of decline of approximately 0.7 beats/minute/year over the full age of 18 to 50 years. Conclusion Clinicians making exercise prescriptions should be aware that the loss of symptom-limited MHR is much slower at young adulthood and more pronounced in later adulthood. In particular, MHR loss is very slow in those with lowest BMI below age 40. PMID:20639723
Philipsen, Kirsten Riber; Christiansen, Lasse Engbo; Mandsberg, Lotte Frigaard
2008-01-01
with an exponentially decaying function of the time between observations is suggested. A model with a full covariance structure containing OD-dependent variance and an autocorrelation structure is compared to a model with variance only and with no variance or correlation implemented. It is shown that the model...... are used for parameter estimation. The data is log-transformed such that a linear model can be applied. The transformation changes the variance structure, and hence an OD-dependent variance is implemented in the model. The autocorrelation in the data is demonstrated, and a correlation model...... that best describes data is a model taking into account the full covariance structure. An inference study is made in order to determine whether the growth rate of the five bacteria strains is the same. After applying a likelihood-ratio test to models with a full covariance structure, it is concluded...
Noise-induced convergence of the low flow rate chaos in the Belousov-Zhabotinsky reaction
Yoshimoto, Minoru; Nakaiwa, Masaru; Akiya, Takaji; Ohmori, Takao; Yamaguchi, Tomohiko
The effect of noise on the low flow-rate chaos in the Belousov-Zhabotinsky (BZ) reaction was studied. The chaos was simulated using the three-variable model of Györgyi and Field. Gaussian white noise was imposed on the flow-rate of the reactant solutions fed into CSTR to simulate the so-called type P noise. The range of average noise amplitudes was chosen between 0.01% and 1% related to the inverse residence time. The calculated time series were analyzed on the basis of their Fourier spectra, maximum Lyapunov exponent, Kolmogorov entropies, return maps and invariant density. We found that the noise induces partial order of the period-3-like oscillations in the low flowrate chaos.
Żebrowska, Magdalena; Posch, Martin; Magirr, Dominic
2016-05-30
Consider a parallel group trial for the comparison of an experimental treatment to a control, where the second-stage sample size may depend on the blinded primary endpoint data as well as on additional blinded data from a secondary endpoint. For the setting of normally distributed endpoints, we demonstrate that this may lead to an inflation of the type I error rate if the null hypothesis holds for the primary but not the secondary endpoint. We derive upper bounds for the inflation of the type I error rate, both for trials that employ random allocation and for those that use block randomization. We illustrate the worst-case sample size reassessment rule in a case study. For both randomization strategies, the maximum type I error rate increases with the effect size in the secondary endpoint and the correlation between endpoints. The maximum inflation increases with smaller block sizes if information on the block size is used in the reassessment rule. Based on our findings, we do not question the well-established use of blinded sample size reassessment methods with nuisance parameter estimates computed from the blinded interim data of the primary endpoint. However, we demonstrate that the type I error rate control of these methods relies on the application of specific, binding, pre-planned and fully algorithmic sample size reassessment rules and does not extend to general or unplanned sample size adjustments based on blinded data. © 2015 The Authors. Statistics in Medicine Published by John Wiley & Sons Ltd.
Snelling, Edward P; Seymour, Roger S; Matthews, Philip G D; Runciman, Sue; White, Craig R
2011-10-01
The hemimetabolous migratory locust Locusta migratoria progresses through five instars to the adult, increasing in size from 0.02 to 0.95 g, a 45-fold change. Hopping locomotion occurs at all life stages and is supported by aerobic metabolism and provision of oxygen through the tracheal system. This allometric study investigates the effect of body mass (Mb) on oxygen consumption rate (MO2, μmol h(-1)) to establish resting metabolic rate (MRO2), maximum metabolic rate during hopping (MMO2) and maximum metabolic rate of the hopping muscles (MMO2,hop) in first instar, third instar, fifth instar and adult locusts. Oxygen consumption rates increased throughout development according to the allometric equations MRO2=30.1Mb(0.83±0.02), MMO2=155Mb(1.01±0.02), MMO2,hop=120Mb(1.07±0.02) and, if adults are excluded, MMO2,juv=136Mb(0.97±0.02) and MMO2,juv,hop=103Mb(1.02±0.02). Increasing body mass by 20-45% with attached weights did not increase mass-specific MMO2 significantly at any life stage, although mean mass-specific hopping MO2 was slightly higher (ca. 8%) when juvenile data were pooled. The allometric exponents for all measures of metabolic rate are much greater than 0.75, and therefore do not support West, Brown and Enquist’s optimised fractal network model, which predicts that metabolism scales with a 3⁄4-power exponent owing to limitations in the rate at which resources can be transported within the body.
魏彤彤; 蒋慧灵
2012-01-01
In order to design the relief system size of di-tert-butyl peroxide（DTBP） storage tanks,the runaway re-action of DTBP was simulated by accelerating rate calorimeter（ARC）.The results indicated that under adiabatic conditions the initial exothermic temperature was 102.6 ℃,the maximum self-heating rate was 3.095×107 ℃·min-1,the maximum self-heating temperature was 375.9 ℃,and the pressure produced by unit mass was 4.512 MPa·g-1.Judged by ARC test,the emergency relief system for DTBP was a hybrid system.Based on Design Institute for Emergency Relief System（DIERS） method,the releasing mass flow rate W was determined by Leung methods,and the mass velocity G was calculated by two modified Omega methods.The two relief sizes calculated by monograph Omega method and arithmetic Omega method are close,with only 0.63% relative error.The monograph Omega method is more convenient to apply.
Vorotilin, V. P.
2017-01-01
A generalization of the theory of chemical transformation processes under turbulent mixing of reactants and arbitrary values of the rate of molecular reactions is presented that was previously developed for the variant of an instantaneous reaction [13]. The use of the features of instantaneous reactions when considering the general case, namely, the introduction of the concept of effective reaction for the reactant volumes and writing a closing conservation equation for these volumes, became possible due to the partition of the whole amount of reactants into "active" and "passive" classes; the reactants of the first class are not mixed and react by the mechanism of instantaneous reactions, while the reactants of the second class approach each other only through molecular diffusion, and therefore their contribution to the reaction process can be neglected. The physical mechanism of reaction for the limit regime of an ideal mixing reactor (IMR) is revealed and described. Although formally the reaction rate in this regime depends on the concentration of passive fractions of the reactants, according to the theory presented, the true (hidden) mechanism of the reaction is associated only with the reaction of the active fractions of the reactants with vanishingly small concentration in the volume of the reactor. It is shown that the rate constant of fast chemical reactions can be evaluated when the mixing intensity of reactants is much less than that needed to reach the mixing conditions in an IMR.
Schröder, Henning; Sawall, Mathias; Kubis, Christoph; Selent, Detlef; Hess, Dieter; Franke, Robert; Börner, Armin; Neymeyr, Klaus
2016-07-13
If for a chemical reaction with a known reaction mechanism the concentration profiles are accessible only for certain species, e.g. only for the main product, then often the reaction rate constants cannot uniquely be determined from the concentration data. This is a well-known fact which includes the so-called slow-fast ambiguity. This work combines the question of unique or non-unique reaction rate constants with factor analytic methods of chemometrics. The idea is to reduce the rotational ambiguity of pure component factorizations by considering only those concentration factors which are possible solutions of the kinetic equations for a properly adapted set of reaction rate constants. The resulting set of reaction rate constants corresponds to those solutions of the rate equations which appear as feasible factors in a pure component factorization. The new analysis of the ambiguity of reaction rate constants extends recent research activities on the Area of Feasible Solutions (AFS). The consistency with a given chemical reaction scheme is shown to be a valuable tool in order to reduce the AFS. The new methods are applied to model and experimental data.
Molecule-based approach for computing chemical-reaction rates in upper atmosphere hypersonic flows.
Gallis, Michail A.; Bond, Ryan Bomar; Torczynski, John Robert
2009-08-01
This report summarizes the work completed during FY2009 for the LDRD project 09-1332 'Molecule-Based Approach for Computing Chemical-Reaction Rates in Upper-Atmosphere Hypersonic Flows'. The goal of this project was to apply a recently proposed approach for the Direct Simulation Monte Carlo (DSMC) method to calculate chemical-reaction rates for high-temperature atmospheric species. The new DSMC model reproduces measured equilibrium reaction rates without using any macroscopic reaction-rate information. Since it uses only molecular properties, the new model is inherently able to predict reaction rates for arbitrary nonequilibrium conditions. DSMC non-equilibrium reaction rates are compared to Park's phenomenological non-equilibrium reaction-rate model, the predominant model for hypersonic-flow-field calculations. For near-equilibrium conditions, Park's model is in good agreement with the DSMC-calculated reaction rates. For far-from-equilibrium conditions, corresponding to a typical shock layer, the difference between the two models can exceed 10 orders of magnitude. The DSMC predictions are also found to be in very good agreement with measured and calculated non-equilibrium reaction rates. Extensions of the model to reactions typically found in combustion flows and ionizing reactions are also found to be in very good agreement with available measurements, offering strong evidence that this is a viable and reliable technique to predict chemical reaction rates.
Dang, Cuong Cao; Lefort, Vincent; Le, Vinh Sy; Le, Quang Si; Gascuel, Olivier
2011-10-01
Amino acid replacement rate matrices are an essential basis of protein studies (e.g. in phylogenetics and alignment). A number of general purpose matrices have been proposed (e.g. JTT, WAG, LG) since the seminal work of Margaret Dayhoff and co-workers. However, it has been shown that matrices specific to certain protein groups (e.g. mitochondrial) or life domains (e.g. viruses) differ significantly from general average matrices, and thus perform better when applied to the data to which they are dedicated. This Web server implements the maximum-likelihood estimation procedure that was used to estimate LG, and provides a number of tools and facilities. Users upload a set of multiple protein alignments from their domain of interest and receive the resulting matrix by email, along with statistics and comparisons with other matrices. A non-parametric bootstrap is performed optionally to assess the variability of replacement rate estimates. Maximum-likelihood trees, inferred using the estimated rate matrix, are also computed optionally for each input alignment. Finely tuned procedures and up-to-date ML software (PhyML 3.0, XRATE) are combined to perform all these heavy calculations on our clusters. http://www.atgc-montpellier.fr/ReplacementMatrix/ olivier.gascuel@lirmm.fr Supplementary data are available at http://www.atgc-montpellier.fr/ReplacementMatrix/
Quantifying metabolic rates in submarine hydrothermal vent chimneys: A reaction transport model
LaRowe, D.; Dale, A.; Aguilera, D.; Amend, J. P.; Regnier, P.
2012-12-01
The fluids emanating from active submarine hydrothermal vent chimneys provide a window into subseafloor processes and, through mixing with seawater, are responsible for steep thermal and compositional gradients that provide the energetic basis for diverse biological communities. Although several models have been developed to better understand the dynamic interplay of seawater, hydrothermal fluid, minerals and microorganisms inside chimney walls, none provide a fully integrated approach to quantifying the biogeochemistry of these hydrothermal systems. In an effort to remedy this, a fully coupled biogeochemical reaction transport model of a hydrothermal vent chimney has been developed that explicitly quantifies the rate of microbial catalysis while taking into account geochemical processes such as fluid flow, solute transport and oxidation-reduction reactions associated with fluid mixing as a function of temperature. Methanogenesis, hydrogen oxidation by oxygen and sulfate, sulfide oxidation by oxygen and methane oxidation by oxygen and sulfate are the metabolisms included in the reaction network. Model results indicate that microbial catalysis is fastest in the hottest habitable portion of the vent chimney except for methane oxidation by oxygen, which peaks near the seawater-side of the chimney at 20 nmol /cm^3 yr. The dominant metabolisms in the chimney are hydrogen oxidation by sulfate and oxygen and sulfide oxidation at peak rates 3200 , 300 and 900 nmol /cm^3 yr, respectively. The maximum rate of hydrogenotrophic methanogensis is just under 0.07 nmol /cm^3 yr, the slowest of the metabolisms considered. Due to thermodynamic inhibition, there is no anaerobic oxidation of methane by sulfate (AOM). The model developed here provides a quantitative approach to understanding the rates of biogeochemical transformations in hydrothermal systems and can be used to better understand the role of microbial activity in the deep subsurface.
Kruse, Marcelo Lapa; Kruse, José Cláudio Lupi; Leiria, Tiago Luiz Luz; Pires, Leonardo Martins; Gensas, Caroline Saltz; Gomes, Daniel Garcia; Boris, Douglas; Mantovani, Augusto; Lima, Gustavo Glotz de
2014-12-01
Occurrences of asymptomatic atrial fibrillation (AF) are common. It is important to identify AF because it increases morbidity and mortality. 24-hour Holter has been used to detect paroxysmal AF (PAF). The objective of this study was to investigate the relationship between occurrence of PAF in 24-hour Holter and the symptoms of the population studied. Cross-sectional study conducted at a cardiology hospital. 11,321 consecutive 24-hour Holter tests performed at a referral service were analyzed. Patients with pacemakers or with AF throughout the recording were excluded. There were 75 tests (0.67%) with PAF. The mean age was 67 ± 13 years and 45% were female. The heart rate (HR) over the 24 hours was a minimum of 45 ± 8 bpm, mean of 74 ± 17 bpm and maximum of 151 ± 32 bpm. Among the tests showing PAF, only 26% had symptoms. The only factor tested that showed a correlation with symptomatic AF was maximum HR (165 ± 34 versus 147 ± 30 bpm) (P = 0.03). Use of beta blockers had a protective effect against occurrence of PAF symptoms (odds ratio: 0.24, P = 0.031). PAF is a rare event in 24-hour Holter. The maximum HR during the 24 hours was the only factor correlated with symptomatic AF, and use of beta blockers had a protective effect against AF symptom occurrence.
New Astrophysical Reaction Rate for the $^{12}\\textrm{C}(\\alpha,\\gamma)^{16}\\textrm{O}$ Reaction
An, Z D; Fan, G T; Li, Y J; Chen, Z P; Sun, Y Y
2016-01-01
A new astrophysical reaction rate for $^{12}$C($\\alpha,\\gamma$)$^{16}$O has been evaluated on the basis of a global R-matrix fitting to the available experimental data. The reaction rates of $^{12}$C($\\alpha,\\gamma$)$^{16}$O for stellar temperatures between 0.04 $\\leq$ $T_9$ $\\leq$ 10 are provided in a tabular form and by an analytical fitting expression. At $T_9$ = 0.2, the reaction rate is (7.83 $\\pm$ 0.35)$\\times10^{15}$ $\\rm{cm^3 mol^{-1} s^{-1}}$, where stellar helium burning occurs.
Refit to numerically problematic UMIST reaction rate coefficients
Röllig, M
2011-01-01
Aims. Chemical databases such as the UMIST Database for Astrochemistry (UDFA) are indispensable in the numerical modeling of astrochemical networks. Several of the listed reactions in the UDFA have properties that are problematic in numerical computations: Some are parametrized in a way that leads to extremely divergent behavior for low kinetic temperatures. Other reactions possess multiple entries that are each valid in a different temperature regime, but have no smooth transition when switching from one to another. Numerically, this introduces many difficulties.We present corrected parametrizations for these sets of reactions in the UDFA06 database. Methods. From the tabulated parametrization in UDFA, we created artificial data points and used a Levenberg-Marquardt algorithm to find a set of improved fit parameters without divergent behavior for low temperatures. For reactions with multiple entries in the database that each possess a different temperature regime, we present one joint parametrization that is...
Karia Ritesh M
2012-04-01
Full Text Available Objective: Objectives of this study is to study effect of smoking on Peak Expiratory Flow Rate and Maximum Voluntary Ventilation in apparently healthy tobacco smokers and non-smokers and to compare the result of both the studies to assess the effects of smoking Method: The present study was carried out by computerized software of Pulmonary Function Test named ‘Spiro Excel’ on 50 non-smokers and 50 smokers. Smokers are divided in three gropus. Full series of test take 4 to 5 minutes. Tests were compared in the both smokers and non-smokers group by the ‘unpaired t test’. Statistical significance was indicated by ‘p’ value < 0.05. Results: From the result it is found that actual value of Peak Expiratory Flow Rate and Maximum Voluntary Ventilation are significantly lower in all smokers group than non-smokers. The difference of actual mean value is increases as the degree of smoking increases. [National J of Med Res 2012; 2(2.000: 191-193
Siegler, Jason C; Marshall, Paul W M; Raftry, Sean; Brooks, Cristy; Dowswell, Ben; Romero, Rick; Green, Simon
2013-12-01
The purpose of this investigation was to assess the influence of sodium bicarbonate supplementation on maximal force production, rate of force development (RFD), and muscle recruitment during repeated bouts of high-intensity cycling. Ten male and female (n = 10) subjects completed two fixed-cadence, high-intensity cycling trials. Each trial consisted of a series of 30-s efforts at 120% peak power output (maximum graded test) that were interspersed with 30-s recovery periods until task failure. Prior to each trial, subjects consumed 0.3 g/kg sodium bicarbonate (ALK) or placebo (PLA). Maximal voluntary contractions were performed immediately after each 30-s effort. Maximal force (F max) was calculated as the greatest force recorded over a 25-ms period throughout the entire contraction duration while maximal RFD (RFD max) was calculated as the greatest 10-ms average slope throughout that same contraction. F max declined similarly in both the ALK and PLA conditions, with baseline values (ALK: 1,226 ± 393 N; PLA: 1,222 ± 369 N) declining nearly 295 ± 54 N [95% confidence interval (CI) = 84-508 N; P force vs. maximum rate of force development during a whole body fatiguing task.
Pop-It Beads to Introduce Catalysis of Reaction Rate and Substrate Depletion Effects
Gehret, Austin U.
2017-01-01
A kinesthetic classroom activity was designed to help students understand enzyme activity and catalysis of reaction rate. Students served the role of enzymes by manipulating Pop-It Beads as the catalytic event. This activity illuminates the relationship between reaction rate and reaction progress by allowing students to experience first-hand the…
Apparent Rate Constant for Diffusion-Controlled Three molecular (catalytic) reaction
Burlatsky, S. F.; Moreau, M
1996-01-01
We present simple explicit estimates for the apparent reaction rate constant for three molecular reactions, which are important in catalysis. For small concentrations and $d> 1$, the apparent reaction rate constant depends only on the diffusion coefficients and sizes of the particles. For small concentrations and $d\\le 1$, it is also time -- dependent. For large concentrations, it gains the dependence on concentrations.
Larson, Eric D.; St. Clair, Joshua R.; Sumner, Whitney A.; Bannister, Roger A.; Proenza, Cathy
2013-01-01
An inexorable decline in maximum heart rate (mHR) progressively limits human aerobic capacity with advancing age. This decrease in mHR results from an age-dependent reduction in “intrinsic heart rate” (iHR), which is measured during autonomic blockade. The reduced iHR indicates, by definition, that pacemaker function of the sinoatrial node is compromised during aging. However, little is known about the properties of pacemaker myocytes in the aged sinoatrial node. Here, we show that depressed excitability of individual sinoatrial node myocytes (SAMs) contributes to reductions in heart rate with advancing age. We found that age-dependent declines in mHR and iHR in ECG recordings from mice were paralleled by declines in spontaneous action potential (AP) firing rates (FRs) in patch-clamp recordings from acutely isolated SAMs. The slower FR of aged SAMs resulted from changes in the AP waveform that were limited to hyperpolarization of the maximum diastolic potential and slowing of the early part of the diastolic depolarization. These AP waveform changes were associated with cellular hypertrophy, reduced current densities for L- and T-type Ca2+ currents and the “funny current” (If), and a hyperpolarizing shift in the voltage dependence of If. The age-dependent reduction in sinoatrial node function was not associated with changes in β-adrenergic responsiveness, which was preserved during aging for heart rate, SAM FR, L- and T-type Ca2+ currents, and If. Our results indicate that depressed excitability of individual SAMs due to altered ion channel activity contributes to the decline in mHR, and thus aerobic capacity, during normal aging. PMID:24128759
Reaction rate oscillations during catalytic CO oxidation: A brief overview
Tsotsis, T. T.; Sane, R. C.
1987-04-01
It is not the intent here to present a comprehensive review of the dynamic behavior of the catalytic oxidation of CO. This reaction is one of the most widely studied in the field of catalysis. A review paper by Engel and Ertl has examined the basic kinetic and mechanistic aspects, and a comprehensive paper by Razon and Schmitz was recently devoted to its dynamic behavior. Those interested in further study of the subject should consult these reviews and a number of general review papers on catalytic reaction dynamics. The goal is to present a brief overview of certain interesting aspects of the dynamic behavior of this reaction and to discuss a few questions and issues, which are still the subject of study and debate.
"Depletion": A Game with Natural Rules for Teaching Reaction Rate Theory.
Olbris, Donald J.; Herzfeld, Judith
2002-01-01
Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Presents the game with a set of follow-up questions suitable for either a quiz or discussion. Also describes student reaction to the game. (MM)
Loyka, Sergey; Gagnon, Francois
2009-01-01
Motivated by a recent surge of interest in convex optimization techniques, convexity/concavity properties of error rates of the maximum likelihood detector operating in the AWGN channel are studied and extended to frequency-flat slow-fading channels. Generic conditions are identified under which the symbol error rate (SER) is convex/concave for arbitrary multi-dimensional constellations. In particular, the SER is convex in SNR for any one- and two-dimensional constellation, and also in higher dimensions at high SNR. Pairwise error probability and bit error rate are shown to be convex at high SNR, for arbitrary constellations and bit mapping. Universal bounds for the SER 1st and 2nd derivatives are obtained, which hold for arbitrary constellations and are tight for some of them. Applications of the results are discussed, which include optimum power allocation in spatial multiplexing systems, optimum power/time sharing to decrease or increase (jamming problem) error rate, an implication for fading channels ("fa...
Quick and Easy Rate Equations for Multistep Reactions
Savage, Phillip E.
2008-01-01
Students rarely see closed-form analytical rate equations derived from underlying chemical mechanisms that contain more than a few steps unless restrictive simplifying assumptions (e.g., existence of a rate-determining step) are made. Yet, work published decades ago allows closed-form analytical rate equations to be written quickly and easily for…
Alexander, A. J.; Aoiz, F. J.; Bañares, L.; Brouard, M.; Herrero, V. J.; Simons, J. P.
1997-10-01
Reaction probabilitiers total reaction cross sections as a function of collision energy, and rate constants have been calculated using the quasi-classical trajectory (QCT) method for the O( 1D) + H 2 reaction on several ab initio potential energy surfaces (PES), including the recent one by Ho, Hollebeck, Rabitz, Harding and Schatz. Detailed QCT results on the Schinke and Lester PES are compared with recent time-dependent wavepacket calculations on the same PES, showing good agreement. The QCT thermal rate constants calculated on the PES of Ho et al. are in better accord with the experimental determinations than those calculated on the Schinke-Lester PES.
Rezaeian Mahdi
2015-01-01
Full Text Available Containment of a transport cask during both normal and accident conditions is important to the health and safety of the public and of the operators. Based on IAEA regulations, releasable activity and maximum permissible volumetric leakage rate within the cask containing fuel samples of Tehran Research Reactor enclosed in an irradiated capsule are calculated. The contributions to the total activity from the four sources of gas, volatile, fines, and corrosion products are treated separately. These calculations are necessary to identify an appropriate leak test that must be performed on the cask and the results can be utilized as the source term for dose evaluation in the safety assessment of the cask.
Kobayashi, Daisuke; Honma, Chiemi; Matsumoto, Hideyuki; Takahashi, Tomoki; Kuroda, Chiaki; Otake, Katsuto; Shono, Atsushi
2014-07-01
Ultrasound has been used as an advanced oxidation method for wastewater treatment. Sonochemical degradation of organic compounds in aqueous solution occurs by pyrolysis and/or reaction with hydroxyl radicals. Moreover, kinetics of sonochemical degradation has been proposed. However, the effect of ultrasonic frequency on degradation rate has not been investigated. In our previous study, a simple model for estimating the apparent degradation rate of methylene blue was proposed. In this study, sonochemical degradation of methylene blue was performed at various frequencies. Apparent degradation rate constant was evaluated assuming that sonochemical degradation of methylene blue was a first-order reaction. Specifically, we focused on effects of ultrasonic frequency and power on rate constant, and the applicability of our proposed model was demonstrated. Using this approach, maximum sonochemical degradation rate was observed at 490 kHz, which agrees with a previous investigation into the effect of frequency on the sonochemical efficiency value evaluated by KI oxidation dosimetry. Degradation rate increased with ultrasonic power at every frequency. It was also observed that threshold power must be reached for the degradation reaction to progress. The initial methylene blue concentration and the apparent degradation rate constant have a relation of an inverse proportion. Our proposed model for estimating the apparent degradation rate constant using ultrasonic power and sonochemical efficiency value can apply to this study which extended the frequency and initial concentration range.
Isacco, L; Thivel, D; Duclos, M; Aucouturier, J; Boisseau, N
2014-06-01
Fat mass localization affects lipid metabolism differently at rest and during exercise in overweight and normal-weight subjects. The aim of this study was to investigate the impact of a low vs high ratio of abdominal to lower-body fat mass (index of adipose tissue distribution) on the exercise intensity (Lipox(max)) that elicits the maximum lipid oxidation rate in normal-weight women. Twenty-one normal-weight women (22.0 ± 0.6 years, 22.3 ± 0.1 kg.m(-2)) were separated into two groups of either a low or high abdominal to lower-body fat mass ratio [L-A/LB (n = 11) or H-A/LB (n = 10), respectively]. Lipox(max) and maximum lipid oxidation rate (MLOR) were determined during a submaximum incremental exercise test. Abdominal and lower-body fat mass were determined from DXA scans. The two groups did not differ in aerobic fitness, total fat mass, or total and localized fat-free mass. Lipox(max) and MLOR were significantly lower in H-A/LB vs L-A/LB women (43 ± 3% VO(2max) vs 54 ± 4% VO(2max), and 4.8 ± 0.6 mg min(-1)kg FFM(-1)vs 8.4 ± 0.9 mg min(-1)kg FFM(-1), respectively; P normal-weight women, a predominantly abdominal fat mass distribution compared with a predominantly peripheral fat mass distribution is associated with a lower capacity to maximize lipid oxidation during exercise, as evidenced by their lower Lipox(max) and MLOR. Copyright © 2014 Elsevier Masson SAS. All rights reserved.
Rate constants of reactions of {kappa}-carrageenan with hydrated electron and hydroxyl radical
Abad, L.V. [Nuclear Professional School, School of Engineering Laboratory, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Philippine Nuclear Research Institute, Commonwealth Avenue, Diliman, Quezon City (Philippines)], E-mail: lvabad@pnri.dost.gov.ph; Saiki, S.; Kudo, H.; Muroya, Y.; Katsumura, Y. [Nuclear Professional School, School of Engineering Laboratory, University of Tokyo, 2-22 Shirakata-Shirane, Tokai, Naka, Ibaraki 319-1188 (Japan); Rosa, A.M. de la [Philippine Nuclear Research Institute, Commonwealth Avenue, Diliman, Quezon City (Philippines)
2007-12-15
The rate constants for the reactions of {kappa}-carrageenan with hydrated electron and hydroxyl radical was investigated by pulse radiolysis and laser photolysis. The kinetics of the reaction of hydrated electron indicates no seeming reaction with {kappa}-carrageenan. On the other hand, hydroxyl radical reacts very rapidly with {kappa}-carrageenan at a rate constant of approximately 1.2 x 10{sup 9} M{sup -1} s{sup -1}. This rate constant varies with pH.
for the inference of Furan combustion reaction rate
Long, Quan
2016-01-06
We carry out the design of experiments for the identification of the reaction parameters in Furan combustion. The lacks of information on the true value of the control parameters, specifically, the initial temperature and the initial TBHP concentration, are considered in the design procedure by errors-invariables models. We use two types of observables. The first is a scaler observable, i.e., half decay time of the [TBHP]. The second is the time history of the concentration.
Collective plasma corrections to thermonuclear reactions rates in dense plasmas
Tsytovich, V.N. [General Physics Institute, Moscow (Russian Federation)
2002-01-01
General kinetic equations for nuclear reaction in dense plasmas are obtained. They take into account the first order collective plasma effects. Together with previously known corrections proportional to Z{sub i}Z{sub j}, the product of the charges Z{sub i} and Z{sub j} of two interacting nuclei, it is shown that there exist corrections proportional to the squares Z{sub i}{sup 2} and Z{sub j}{sup 2} of the charges. It is shown that the Salpeter's [1] correction due to the plasma screening of the interaction potential is at least r/d smaller (r is the nuclei size and d is Debye screening length) than previously thought and is zero in the approximation when the terms of the order r/d are neglected. But the correlation effects in the first approximation in the parameter 1/N{sub d} (where N{sub d} is the number of particle in the Debye sphere) give corrections which often coincide with the first order Salpeter's corrections (found by expansion in another small parameter, the ratio of thermal energy to Gamov's energy). The correlation corrections are {proportional_to} Z{sub i}Z{sub j}, have a different physical meaning than the corrections [1], can have a different sign and are present for reactions where the Salpeter's corrections are zero. Previously in astrophysical applications it was widely used the interpolation formulas between weak and strong Salpeter's screening corrections. Since the correlation correction take place the previously known Salpeter's corrections and the strong correlation corrections is difficult to describe analytically, the interpolation formulas between the weak and strong correlations cannot be yet found. A new type of corrections are found here which are proportional to the square of the charges. They are due to collective change in electrostatic self-energy of the plasma system during the nuclear reactions. The latter corrections are found by taking into account the changes of plasma particle fluctuations by
Zheng, Jingjing; Truhlar, Donald G
2012-01-01
Complex molecules often have many structures (conformations) of the reactants and the transition states, and these structures may be connected by coupled-mode torsions and pseudorotations; some but not all structures may have hydrogen bonds in the transition state or reagents. A quantitative theory of the reaction rates of complex molecules must take account of these structures, their coupled-mode nature, their qualitatively different character, and the possibility of merging reaction paths at high temperature. We have recently developed a coupled-mode theory called multi-structural variational transition state theory (MS-VTST) and an extension, called multi-path variational transition state theory (MP-VTST), that includes a treatment of the differences in the multi-dimensional tunneling paths and their contributions to the reaction rate. The MP-VTST method was presented for unimolecular reactions in the original paper and has now been extended to bimolecular reactions. The MS-VTST and MP-VTST formulations of variational transition state theory include multi-faceted configuration-space dividing surfaces to define the variational transition state. They occupy an intermediate position between single-conformation variational transition state theory (VTST), which has been used successfully for small molecules, and ensemble-averaged variational transition state theory (EA-VTST), which has been used successfully for enzyme kinetics. The theories are illustrated and compared here by application to three thermal rate constants for reactions of ethanol with hydroxyl radical--reactions with 4, 6, and 14 saddle points.
Jorge Cuadrado Reyes
2011-05-01
Full Text Available Abstract This research developed a logarithms for calculating the maximum heart rate (max. HR for players in team sports in game situations. The sample was made of thirteen players (aged 24 ± 3 to a Division Two Handball team. HR was initially measured by Course Navette test. Later, twenty one training sessions were conducted in which HR and Rate of Perceived Exertion (RPE, were continuously monitored, in each task. A lineal regression analysis was done to help find a max. HR prediction equation from the max. HR of the three highest intensity sessions. Results from this equation correlate significantly with data obtained in the Course Navette test and with those obtained by other indirect methods. The conclusion of this research is that this equation provides a very useful and easy way to measure the max. HR in real game situations, avoiding non-specific analytical tests and, therefore laboratory testing.. Key words: workout control, functional evaluation, prediction equation.
Murata, T; Sato, T; Nakamura, S X
2016-01-01
The maximum entropy method is examined as a new tool for solving the ill-posed inversion problem involved in the Lorentz integral transformation (LIT) method. As an example, we apply the method to the spin-dipole strength function of 4He. We show that the method can be successfully used for inversion of LIT, provided the LIT function is available with a sufficient accuracy.
Interlaboratory reaction rate program. 12th progress report, November 1976-October 1979
Lippincott, E.P.; McElroy, W.N.; Preston, C.C. (comps.)
1980-09-01
The Interlaboratory Reaction Rate UILRR) program is establishing the capability to accurately measure neutron-induced reactions and reaction rates for reactor fuels and materials development programs. The goal for the principal fission reactions, /sup 235/U, /sup 238/U and /sup 239/Pu, is an accuracy to within +- 5% at the 95% confidence level. Accurate measurement of other fission and nonfission reactions is also required, but to a lesser accuracy, between +- 5% and 10% at the 95% confidence level. A secondary program objective is improvement in knowledge of the nuclear parameters involved in the standarization of fuels and materials dosimetry measurements of neutron flux, spectra, fluence and burnup.
Evolutionary implications of the new triple-alpha nuclear reaction rate for low mass stars
Dotter, Aaron
2009-01-01
Context: Ogata et al. (2009; hereafter OKK) presented a theoretical determination of the triple-alpha nuclear reaction rate. Their rate differs from the NACRE rate by many orders of magnitude at temperatures relevant for low mass stars. Aims: We explore the evolutionary implications of adopting the OKK triple-alpha reaction rate in low mass stars and compare the results with those obtained using the NACRE rate. Methods: The triple-alpha reaction rates are compared by following the evolution of stellar models at 1 and 1.5 Msol with Z=0.0002 and Z=0.02. Results: Results show that the OKK rate has severe consequences for the late stages of stellar evolution in low mass stars. Most notable is the shortening--or disappearance--of the red giant phase. Conclusions: The OKK triple-alpha reaction rate is incompatible with observations of extended red giant branches and He burning stars in old stellar systems.
Katsuma, M
2015-01-01
The radiative capture cross sections of $^{12}$C($\\alpha$,$\\gamma$)$^{16}$O and derived reaction rates are calculated from the direct capture potential model. The resulting $S$-factor at low energies is found to be dominated by $E$2 transition to the $^{16}$O ground state. The $E$1 and $E$2 $S$-factors at $E_{c.m.}=0.3$ MeV are $S_{E1}\\approx3$ keV~b and $S_{E2}=150^{+41}_{-17}$ keV~b, respectively. The sum of the cascade transition through the excited state of $^{16}$O is $S_{\\rm casc}= 18\\pm4.5$ keV~b. The derived reaction rates at low temperatures seem to be concordant with those from the previous evaluation. For astrophysical applications, our reaction rates below $T_9=3$ are provided in an analytic expression.
Saito, Fumito; Noda, Hidetoshi; Bode, Jeffrey W
2015-04-17
Chemoselective ligation reactions have contributed immensely to the development of organic synthesis and chemical biology. However, the ligation of stoichiometric amounts of large molecules for applications such as protein-protein conjugates is still challenging. Conjugation reactions need to be fast enough to proceed under dilute conditions and chemoselective in the presence of unprotected functional groups; the starting materials and products must be stable under the reaction conditions. To compare known ligation reactions for their suitability under these conditions, we determined the second-order rate constants of ligation reactions using peptide substrates with unprotected functional groups. The reaction conditions, the chemoselectivity of the reactions, and the stability of the starting materials and products were carefully evaluated. In some cases, the stability could be improved by modifying the substrate structure. These data obtained under the ligation conditions provide a useful guide to choose an appropriate ligation reaction for synthesis of large molecules by covalent ligation reactions of unprotected substrates in water.
Reaction rates between water and some modified rapidly-reacting Karl Fischer reagents.
Cedergren, A
1978-04-01
Rate constants were determined for the reaction between water and various modified Karl Fischer reagents containing formamide, dimethylformamide or N-methylformamide. It was shown that the reaction rate can be increased by a factor of 100 by using a reagent containing 40% v/v formamide in pyridine compared to that obtained by use of the conventional methanolic reagent.
Rate of reaction of dimethylmercury with oxygen atoms in the gas phase
Egsgaard, Helge
1986-01-01
The rate constant for the reaction of atomic oxygen (O(3P)) with dimethylmercury has been measured at room temperature at a pressure of about 1 Torr using a fast flow system with electron paramagnetic resonance and mass spectrometric detection. Some reaction products were identified. The rate...
Chattaraj, Pratim K; Ayers, Paul W; Melin, Junia
2007-08-07
Ayers, Parr, and Pearson recently showed that insight into the hard/soft acid/base (HSAB) principle could be obtained by analyzing the energy of reactions in hard/soft exchange reactions, i.e., reactions in which a soft acid replaces a hard acid or a soft base replaces a hard base [J. Chem. Phys., 2006, 124, 194107]. We show, in accord with the maximum hardness principle, that the hardness increases for favorable hard/soft exchange reactions and decreases when the HSAB principle indicates that hard/soft exchange reactions are unfavorable. This extends the previous work of the authors, which treated only the "double hard/soft exchange" reaction [P. K. Chattaraj and P. W. Ayers, J. Chem. Phys., 2005, 123, 086101]. We also discuss two different approaches to computing the hardness of molecules from the hardness of the composing fragments, and explain how the results differ. In the present context, it seems that the arithmetic mean of fragment softnesses is the preferable definition.
Peira, Nathalie; Fredrikson, Mats; Pourtois, Gilles
2014-03-01
When regulating negative emotional reactions, one goal is to reduce physiological reactions. However, not all regulation strategies succeed in doing that. We tested whether heart rate biofeedback helped participants reduce physiological reactions in response to negative and neutral pictures. When viewing neutral pictures, participants could regulate their heart rate whether the heart rate feedback was real or not. In contrast, when viewing negative pictures, participants could regulate heart rate only when feedback was real. Ratings of task success paralleled heart rate. Participants' general level of anxiety, emotion awareness, or cognitive emotion regulation strategies did not influence the results. Our findings show that accurate online heart rate biofeedback provides an efficient way to down-regulate autonomic physiological reactions when encountering negative stimuli.
Aikawa, M; Goriely, S; Jorissen, A; Takahashi, K
2005-01-01
Nuclear reaction rates are quantities of fundamental importance in astrophysics. Substantial efforts have been devoted in the last decades to measure or calculate them. The present paper presents for the first time a detailed description of the Brussels nuclear reaction rate library BRUSLIB and of the nuclear network generator NETGEN so as to make these nuclear data packages easily accessible to astrophysicists for a large variety of applications. BRUSLIB is made of two parts. The first one contains the 1999 NACRE compilation based on experimental data for 86 reactions with (mainly) stable targets up to Si. The second part of BRUSLIB concerns nuclear reaction rate predictions calculated within a statistical Hauser-Feshbach approximation, which limits the reliability of the rates to reactions producing compound nuclei with a high enough level density. These calculations make use of global and coherent microscopic nuclear models for the quantities entering the rate calculations. The use of such models is utterl...
2010-07-01
... PREPARING TOMORROW'S TEACHERS TO USE TECHNOLOGY § 614.6 What is the maximum indirect cost rate for all... requirements; or (3) Charged by the grantee to another Federal award. (Authority: 20 U.S.C. 6832)...
Trapp, Oliver; Bremer, Sabrina; Weber, Sven K
2009-11-01
An extension of the unified equation of chromatography to directly access reaction rate constants k(1) of first-order reaction in on-column chromatography is presented. This extended equation reflects different response factors in the detection of the reaction educt and product which arise from structural changes by elimination or addition, e.g., under pseudo-first-order reaction conditions. The reaction rate constants k(1) and Gibbs activation energies DeltaG(double dagger) of first-order reactions taking place in a chromatographic system can be directly calculated from the chromatographic parameters, i.e., retention times of the educt E and product P (t(R)(A) and t(R)(B)), peak widths at half height (w(A) and w(B)), the relative plateau height (h(p)) of the conversion profile, and the individual response factors f(A) and f(B). The evaluation of on-column reaction gas chromatographic experiments is exemplified by the evaluation of elution profiles obtained by ring-closing metathesis reaction of N,N-diallytrifluoroacetamide in presence of Grubbs second-generation catalyst, dissolved in polydimethylsiloxane (GE SE 30).
Simulation of biochemical reactions with time-dependent rates by the rejection-based algorithm
Thanh, Vo Hong, E-mail: vo@cosbi.eu [The Microsoft Research - University of Trento Centre for Computational and Systems Biology, Piazza Manifattura 1, Rovereto 38068 (Italy); Priami, Corrado, E-mail: priami@cosbi.eu [The Microsoft Research - University of Trento Centre for Computational and Systems Biology, Piazza Manifattura 1, Rovereto 38068 (Italy); Department of Mathematics, University of Trento, Trento (Italy)
2015-08-07
We address the problem of simulating biochemical reaction networks with time-dependent rates and propose a new algorithm based on our rejection-based stochastic simulation algorithm (RSSA) [Thanh et al., J. Chem. Phys. 141(13), 134116 (2014)]. The computation for selecting next reaction firings by our time-dependent RSSA (tRSSA) is computationally efficient. Furthermore, the generated trajectory is exact by exploiting the rejection-based mechanism. We benchmark tRSSA on different biological systems with varying forms of reaction rates to demonstrate its applicability and efficiency. We reveal that for nontrivial cases, the selection of reaction firings in existing algorithms introduces approximations because the integration of reaction rates is very computationally demanding and simplifying assumptions are introduced. The selection of the next reaction firing by our approach is easier while preserving the exactness.
Maher, K.; Steefel, C. I.; White, A.F.; Stonestrom, D.A.
2009-02-25
In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka marine terrace chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized (White et al., 2008, GCA) and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisser and [2006] or the aluminum inhibition model proposed by Oelkers et al. [1994], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Observed maximum clay abundances in the argillic horizons occur at the depth and time where the reaction fronts of the primary minerals overlap. The modeling indicates that the argillic horizon at Santa Cruz can be explained almost entirely by weathering of primary minerals and in situ clay precipitation accompanied by undersaturation of kaolinite at the top of the profile. The rate constant for kaolinite precipitation was also determined based on model simulations of mineral abundances and dissolved Al, SiO{sub 2}(aq) and pH in pore waters. Changes in the rate of kaolinite precipitation or the flow rate do not affect the gradient of the primary mineral weathering profiles, but instead control the rate of propagation of the primary mineral weathering fronts and thus total
Cannon, William R.; Baker, Scott E.
2017-10-01
Comprehensive and predictive simulation of coupled reaction networks has long been a goal of biology and other fields. Currently, metabolic network models that utilize enzyme mass action kinetics have predictive power but are limited in scope and application by the fact that the determination of enzyme rate constants is laborious and low throughput. We present a statistical thermodynamic formulation of the law of mass action for coupled reactions at both steady states and non-stationary states. The formulation uses chemical potentials instead of rate constants. When used to model deterministic systems, the method corresponds to a rescaling of the time dependent reactions in such a way that steady states can be reached on the same time scale but with significantly fewer computational steps. The relationships between reaction affinities, free energy changes and generalized detailed balance are central to the discussion. The significance for applications in systems biology are discussed as is the concept and assumption of maximum entropy production rate as a biological principle that links thermodynamics to natural selection.
A simple expression for the apparent reaction rate of large wood char gasification with steam.
Umeki, Kentaro; Roh, Seon-Ah; Min, Tai-Jin; Namioka, Tomoaki; Yoshikawa, Kunio
2010-06-01
A simple expression for the apparent reaction rate of large wood char gasification with steam is proposed. Large char samples were gasified under steam atmosphere using a thermo-balance reactor. The apparent reaction rate was expressed as the product of the intrinsic rate and the effective factor. The effective factor was modified to include the effect of change in char diameter and intrinsic reaction rate during the reaction. Assuming uniform conversion ratio throughout a particle, the simplified reaction scheme was divided into three stages. In the initial stage, the local conversion ratio increases without particle shrinkage. In the middle stage, the particle shrinks following the shrinking core model without change in the local conversion ratio. In the final stage, the local conversion ratio increases without particle shrinkage. The validity of the modified effective value was confirmed by comparison with experimental results.
Rate constants for the reaction of CF3O radicals with hydrocarbons at 298 K
Kelly, C.; Treacy, J.; Sidebottom, H.W.;
1993-01-01
Rate constant ratios of the reactions of CF3O radicals with a number of hydrocarbons have been determined at 298 +/- 2 K and atmospheric pressure using a relative rate method. Using a previously determined value k(CF30 + C2H6) = 1.2 x 10(-12) cm3 molecule-1 s-1 these rate constant ratios provide......-1. The importance of the reactions of CF3O radicals with hydrocarbons under atmospheric conditions is discussed....
VizieR Online Data Catalog: Brussels nuclear reaction rate library (Aikawa+, 2005)
Aikawa, M.; Arnould, M.; Goriely, S.; Jorissen, A.; Takahashi, K.
2005-07-01
The present data is part of the Brussels nuclear reaction rate library (BRUSLIB) for astrophysics applications and concerns nuclear reaction rate predictions calculated within the statistical Hauser-Feshbach approximation and making use of global and coherent microscopic nuclear models for the quantities (nuclear masses, nuclear structure properties, nuclear level densities, gamma-ray strength functions, optical potentials) entering the rate calculations. (4 data files).
Sada, H
1978-10-01
Effects of phentolamine (13.3, 26.5 and 53.0 micron), alprenolol (3.5, 7.0 and 17.5 micron) and prenylamine (2.4, 4.8 and 11.9 micron) on the transmembrane potential were studied in isolated guinea-pig papillary muscles, superfused with Tyrode's solution. 1. Phentolamine, alprenolol and prenylamine reduced the maximum rate of rise of action potential (.Vmax) dose-dependently. Higher concentrations of phentolamine and prenylamine caused a loss of plateau in a majority of the preparations. Resting potential was not altered by any of the drugs. Readmittance of drug-free Tyrode's solution reversed these changes induced by 13.3 micron of phentolamine and all conconcentrations of alprenolol almost completely but those induced by higher concentrations of phentolamine and all concentrations of prenylamine only slightly. 2. .Vmax at steady state was increased with decreasing driving frequencies (0.5 and 0.25 Hz) and was decreased with increasing ones (2--5 Hz) in comparison with that at 1 Hz. Such changes were all exaggerated by the above drugs, particularly by prenylamine. 3. Prenylamine and, to a lesser degree, phentolamine and alprenolol delayed dose-dependently the recovery process of .Vmax in premature responses. 4. .Vmax in the first response after interruption of stimulation recovered toward the predrug value in the presence of the above three drugs. The time constants of recovery process ranged between 10.5 and 15.0s for phentolamine, between 4.5 and 15.5s for alprenolol. The time constant of the main component was estimated to be approximately 2s for the recovery process with prenylamine. 5. On the basis of the model recently proposed by Hondeghem and Katzung (1977), it is suggested that the drug molecules associate with the open sodium channels and dissociated slowly from the closed channels and that the inactivation parameter in the drug-associated channels is shifted in the hyperpolarizing direction.
Mazhar A. Memon
2016-04-01
Full Text Available ABSTRACT Objective: To evaluate correlation between visual prostate score (VPSS and maximum flow rate (Qmax in men with lower urinary tract symptoms. Material and Methods: This is a cross sectional study conducted at a university Hospital. Sixty-seven adult male patients>50 years of age were enrolled in the study after signing an informed consent. Qmax and voided volume recorded at uroflowmetry graph and at the same time VPSS were assessed. The education level was assessed in various defined groups. Pearson correlation coefficient was computed for VPSS and Qmax. Results: Mean age was 66.1±10.1 years (median 68. The mean voided volume on uroflowmetry was 268±160mL (median 208 and the mean Qmax was 9.6±4.96mLs/sec (median 9.0. The mean VPSS score was 11.4±2.72 (11.0. In the univariate linear regression analysis there was strong negative (Pearson's correlation between VPSS and Qmax (r=848, p<0.001. In the multiple linear regression analyses there was a significant correlation between VPSS and Qmax (β-http://www.blogapaixonadosporviagens.com.br/p/caribe.html after adjusting the effect of age, voided volume (V.V and level of education. Multiple linear regression analysis done for independent variables and results showed that there was no significant correlation between the VPSS and independent factors including age (p=0.27, LOE (p=0.941 and V.V (p=0.082. Conclusion: There is a significant negative correlation between VPSS and Qmax. The VPSS can be used in lieu of IPSS score. Men even with limited educational background can complete VPSS without assistance.
Characterization of shock-dependent reaction rates in an aluminum/perfluoropolyether pyrolant
Wilson, Dennis; Granier, John; Johnson, Richard; Littrell, Donald
2017-01-01
Energetic formulations of perfluoropolyether (PFPE) and aluminum are highly non-ideal. They release energy via a fast self-oxidized combustion wave rather than a true self-sustaining detonation. Unlike high explosives, the reactions are shock dependent and can be overdriven to control energy release rate. Reaction rate experiments show that the velocity can vary from 1.25 to 3 km/s. This paper examines the effect of the initial shock conditions upon the reaction rate of the explosive. The following conditions were varied in a series of reaction rate experiments: the high explosive booster mass and geometry; shock attenuation; confinement; and rate stick diameter and length. Several experiments designed to isolate and quantify these dependencies are described and summarized.
Saadah, Nicholas H; van Hout, Fabienne M A; Schipperus, Martin R; le Cessie, Saskia; Middelburg, Rutger A; Wiersum-Osselton, Johanna C; van der Bom, Johanna G
2017-09-01
We estimated rates for common plasma-associated transfusion reactions and compared reported rates for various plasma types. We performed a systematic review and meta-analysis of peer-reviewed articles that reported plasma transfusion reaction rates. Random-effects pooled rates were calculated and compared between plasma types. Meta-regression was used to compare various plasma types with regard to their reported plasma transfusion reaction rates. Forty-eight studies reported transfusion reaction rates for fresh-frozen plasma (FFP; mixed-sex and male-only), amotosalen INTERCEPT FFP, methylene blue-treated FFP, and solvent/detergent-treated pooled plasma. Random-effects pooled average rates for FFP were: allergic reactions, 92/10(5) units transfused (95% confidence interval [CI], 46-184/10(5) units transfused); febrile nonhemolytic transfusion reactions (FNHTRs), 12/10(5) units transfused (95% CI, 7-22/10(5) units transfused); transfusion-associated circulatory overload (TACO), 6/10(5) units transfused (95% CI, 1-30/10(5) units transfused); transfusion-related acute lung injury (TRALI), 1.8/10(5) units transfused (95% CI, 1.2-2.7/10(5) units transfused); and anaphylactic reactions, 0.8/10(5) units transfused (95% CI, 0-45.7/10(5) units transfused). Risk differences between plasma types were not significant for allergic reactions, TACO, or anaphylactic reactions. Methylene blue-treated FFP led to fewer FNHTRs than FFP (risk difference = -15.3 FNHTRs/10(5) units transfused; 95% CI, -24.7 to -7.1 reactions/10(5) units transfused); and male-only FFP led to fewer cases of TRALI than mixed-sex FFP (risk difference = -0.74 TRALI/10(5) units transfused; 95% CI, -2.42 to -0.42 injuries/10(5) units transfused). Meta-regression demonstrates that the rate of FNHTRs is lower for methylene blue-treated compared with FFP, and the rate of TRALI is lower for male-only than for mixed-sex FFP; whereas no significant differences are observed between plasma types for allergic
Astrophysical Reaction Rates of the 8Li(p,γ)9Beg.s. Direct Capture Reaction
Su Jun; WANG You-Bao; LI Zhi-Hong; GUO Bing; LIU Wei-Ping; BAI Xi-Xiang; ZENG Sheng; LIAN Gang; YAN Sheng-Quan; WANG Bao-Xiang
2006-01-01
Based 0n the angular distribution of the 8Li(d,n)9Beg.s. reaction at Ec.m.=8.0 MeV and distorted wave Born approximation analysis,the single particle spectroscopic factor S1,3/2 for the ground state of 9Be=8Li(×)p is derived to be 0.64±0.21.In addition,we deduce the astrophysical S-factors and rates of the 8Li(p,γ)9Beg.s. direct capture reaction at energies of astrophysical interests.
Astrophysical S-Factors and Reaction Rates of Threshold (p, n)-Reactions on 99-102Ru
Skakun, Ye.; Rauscher, T.
2010-08-01
Astrophysical S-factors of (p, n) reactions on 99Ru, 100Ru, 101Ru, and 102Ru were derived from the sum of experimental isomeric and ground states cross sections measured in the incident proton energy range of 5-9 MeV. They were compared with Hauser-Feshbach statistical model predictions of the NON-SMOKER code. Good agreement was found in the majority of cases. Reaction rates were derived up to 8.7 GK stellar temperature by combining experiment and theory.
Combustion of Bimodal Nano/Micro Aluminum Suspension with New Reaction Rate Model
M. Bidabadi
2008-01-01
Full Text Available In this study a mathematical model for combustion of bimodal particle in lean flow was developed. The difference between structure of flame in this work and previous ones was that, in those flame was divided by five zones and reaction rate was considered to be constant in reaction zones and also zero in post flame zone. In reality it was obvious with respect to shape and size of different particles in dust, reaction didn't end suddenly. In the present research the heat loss term, which was assumed to be linearly proportional to temperature difference, was added to the energy conservation equation and reaction rate was considered proportional to available amount of fuel, leading to exponentially decreasing of reaction rate. The flame speed and temperature distribution were obtained by solving the energy equation in each zone and matching the temperature and heat flux at the interfacial boundaries. Calculated values of flame speed were in good agreement with experimental data.
Reaction rate estimation of controlled-release antifouling paint binders: Rosin-based systems
Meseguer Yebra, Diego; Kiil, Søren; Dam-Johansen, Kim
2005-01-01
at product optimisation and innovation (e.g. incorporation of natural active agents). This study seeks to attain scientifically founded knowledge of the reaction mechanisms and the rate of reaction with sea water of a Zn-carboxylate of a synthetic rosin compound. The kinetic expression attained can be used...... have shown that mathematical coating models based on a fundamental knowledge of the underlying mechanisms of A/F paints is a promising tool for accelerated product testing at different operational conditions of a sailing ship or a paint rotor. Such models can also be used for generation of ideas aiming...... rather than pointing at a certain diffusion control in the reaction rate experiments. The reverse reaction is found not to affect the hydrolysis rate within the pores, of antifouling paints significantly. It is concluded, from the reaction mechanism proposed, that the observed partial exchange of Zn2...
2007-11-02
Tucker, manuscript in preparation. “Examination of Nonequilibrium Solvent Effects on an SN2 Reaction in Supercritical Water,” R. Behera, B...DATES COVERED Final: 7/1/99 - 12/31/02 4. TITLE AND SUBTITLE Development of theoretical methods for predicting solvent effects on reactions ...computational methods for predicting how reaction rate constants will vary with thermodynamic condition in supercritical water (SCW). Towards this
The Relation Between Damping and Reaction Rates of Fermions in Hot Gauge Theories
Ayala, A P; Weber, A; Ayala, Alejandro; Olivo, Juan Carlos D'; Weber, Axel
1998-01-01
We examine the relation between the damping rate of a chiral fermion mode propagating in a hot plasma and the rate at which the mode approaches equilibrium. We show that these two quantities, obtained from the imaginary part of the fermion self-energy, are equal provided the reaction rate is defined using the appropriate wave function of the mode in the medium.
Elhkim, Mostafa Ould; Héraud, Fanny; Bemrah, Nawel; Gauchard, Françoise; Lorino, Tristan; Lambré, Claude; Frémy, Jean Marc; Poul, Jean-Michel
2007-04-01
Tartrazine is an artificial azo dye commonly used in human food and pharmaceutical products. Since the last assessment carried out by the JECFA in 1964, many new studies have been conducted, some of which have incriminated tartrazine in food intolerance reactions. The aims of this work are to update the hazard characterization and to revaluate the safety of tartrazine. Our bibliographical review of animal studies confirms the initial hazard assessment conducted by the JECFA, and accordingly the ADI established at 7.5mg/kg bw. From our data, in France, the estimated maximum theoretical intake of tartrazine in children is 37.2% of the ADI at the 97.5th percentile. It may therefore be concluded that from a toxicological point of view, tartrazine does not represent a risk for the consumer. It appears more difficult to show a clear relationship between ingestion of tartrazine and the development of intolerance reactions in patients. These reactions primarily occur in patients who also suffer from recurrent urticaria or asthma. The link between tartrazine consumption and these reactions is often overestimated, and the pathogenic mechanisms remain poorly understood. The prevalence of tartrazine intolerance is estimated to be less than 0.12% in the general population. Generally, the population at risk is aware of the importance of food labelling, with the view of avoiding consumption of tartrazine. However, it has to be mentioned that products such as ice creams, desserts, cakes and fine bakery are often sold loose without any labelling.
The Reaction Mechanism and Rate Constants in the Radiolysis of Fe2+-Cu2+ Solutions
Bjergbakke, Erling; Sehested, Knud; Rasmussen, O. Lang
1976-01-01
Pulse radiolysis and gamma radiolysis have been used to study the reaction mechanism in the radiolysis of aqueous solutions of Fe2+ and Cu2+. A reaction scheme has been developed and confirmed by computation of the corresponding complete set of differential equations. The rate constants for some...
Casal, J; Arias, J M; Gómez-Camacho, J
2016-01-01
A relationship between the Coulomb inclusive break-up probability and the radiative capture reaction rate for weakly-bound three-body systems is established. This direct link provides a robust procedure to estimate the reaction rate for nuclei of astrophysical interest by measuring inclusive break-up processes at different energies and angles. This might be an advantageous alternative to the determination of reaction rates from the measurement of $B(E1)$ distributions through exclusive Coulomb break-up experiments. In addition, it provides a reference to assess the validity of different theoretical approaches that have been used to calculate reaction rates. The procedure is applied to $^{11}$Li ($^{9}$Li+n+n) and $^6$He ($^{4}$He+n+n) three-body systems for which some data exist.
Casal, J.; Rodríguez-Gallardo, M.; Arias, J. M.; Gómez-Camacho, J.
2016-04-01
A relationship between the Coulomb inclusive break-up probability and the radiative capture reaction rate for weakly bound three-body systems is established. This direct link provides a robust procedure to estimate the reaction rate for nuclei of astrophysical interest by measuring inclusive break-up processes at different energies and angles. This might be an advantageous alternative to the determination of reaction rates from the measurement of B (E 1 ) distributions through exclusive Coulomb break-up experiments. In addition, it provides a reference to assess the validity of different theoretical approaches that have been used to calculate reaction rates. The procedure is applied to 11Li (9Li+n +n ) and 6He (4He+n +n ) three-body systems for which some data exist.
Neutron Scattering in Hydrogenous Moderators, Studied by Time Dependent Reaction Rate Method
Larsson, L.G.; Moeller, E.; Purohit, S.N.
1966-03-15
The moderation and absorption of a neutron burst in water, poisoned with the non-1/v absorbers cadmium and gadolinium, has been followed on the time scale by multigroup calculations, using scattering kernels for the proton gas and the Nelkin model. The time dependent reaction rate curves for each absorber display clear differences for the two models, and the separation between the curves does not depend much on the absorber concentration. An experimental method for the measurement of infinite medium reaction rate curves in a limited geometry has been investigated. This method makes the measurement of the time dependent reaction rate generally useful for thermalization studies in a small geometry of a liquid hydrogenous moderator, provided that the experiment is coupled to programs for the calculation of scattering kernels and time dependent neutron spectra. Good agreement has been found between the reaction rate curve, measured with cadmium in water, and a calculated curve, where the Haywood kernel has been used.
Beatty, Garrett F; Fawver, Bradley; Hancock, Gabriella M; Janelle, Christopher M
2014-02-01
We investigated how emotion regulation (ER) strategies influence the execution of a memory guided, ballistic pinch grip. Participants (N=33) employed ER strategies (expressive suppression, emotional expression, and attentional deployment) while viewing emotional stimuli (IAPS images). Upon stimulus offset, participants produced a targeted pinch force aimed at 10% of their maximum voluntary contraction. Performance measures included reaction time (RT), rate of force production, and performance accuracy. As hypothesized, attentional deployment resulted in the slowest RT, largest rate of force production, and poorest performance accuracy. In contrast, expressive suppression reduced the rate of force production and increased performance accuracy relative to emotional expression and attentional deployment. Findings provide evidence that emotion regulation strategies uniquely influence human movement. Future work should further delineate the interacting role that emotion regulation strategies have in modulating both affective experience and motor performance.
Boeltzig, A. [Gran Sasso Science Institute, L' Aquila (Italy); Bruno, C.G.; Davinson, T. [University of Edinburgh, SUPA, School of Physics and Astronomy, Edinburgh (United Kingdom); Cavanna, F.; Ferraro, F. [Dipartimento di Fisica, Universita di Genova (Italy); INFN, Genova (Italy); Cristallo, S. [Osservatorio Astronomico di Collurania, INAF, Teramo (Italy); INFN, Napoli (Italy); Depalo, R. [Dipartimento di Fisica e Astronomia, Universita di Padova, Padova (Italy); INFN, Padova (Italy); DeBoer, R.J.; Wiescher, M. [University of Notre Dame, Institute for Structure and Nuclear Astrophysics, Joint Institute for Nuclear Astrophysics, Notre Dame, Indiana (United States); Di Leva, A.; Imbriani, G. [Dipartimento di Fisica, Universita di Napoli Federico II, Napoli (Italy); INFN, Napoli (Italy); Marigo, P. [Dipartimento di Fisica e Astronomia, Universita di Padova, Padova (Italy); Terrasi, F. [Dipartimento di Matematica e Fisica Seconda Universita di Napoli, Caserta (Italy); INFN, Napoli (Italy)
2016-04-15
The nucleosynthesis of light elements, from helium up to silicon, mainly occurs in Red Giant and Asymptotic Giant Branch stars and Novae. The relative abundances of the synthesized nuclides critically depend on the rates of the nuclear processes involved, often through non-trivial reaction chains, combined with complex mixing mechanisms. In this paper, we summarize the contributions made by LUNA experiments in furthering our understanding of nuclear reaction rates necessary for modeling nucleosynthesis in AGB stars and Novae explosions. (orig.)
The Effect of the Triple-α Reaction Rate on Stellar Evolution at Low-Metallicity
Suda, Takuma; Hirschi, Raphael; Fujimoto, Masayuki Y.
2010-06-01
We investigate the effect of the triple-α reaction rates on the evolution of low-mass stars and massive stars. The former is compared with the observations of metal-poor stars known to date. For the latter, we discuss the impact of recent calculation of triple-α reaction rate by Ogata et al. (2009, PTP, 122, 1055) on the evolution until carbon burning.
Sodium Enrichment in Yellow Supergiants: a Perspective from the Uncertainties of Reaction Rates
无
2008-01-01
Sodium overabundance in yellow supergiants has stumped people for more than 20 years. The purpose of this paper is to explore this problem from the perspective of nuclear physics. We investigate carefully the CNO and NeNa cycles that are responsible for sodium production. We investigate some key reactions in the appropriate network. We show whether and how the sodium output can be affected by the rate uncertainties in these reactions. In this way, we evaluate if a reaction is important enough to deserve a better determination of its rate in terrestrial laboratories.
STARLIB: A Next-Generation Reaction-Rate Library for Nuclear Astrophysics
Sallaska, A L; Champagne, A E; Goriely, S; Starrfield, S; Timmes, F X
2013-01-01
STARLIB is a next-generation, all-purpose nuclear reaction-rate library. For the first time, this library provides the rate probability density at all temperature grid points for convenient implementation in models of stellar phenomena. The recommended rate and its associated uncertainties are also included. Currently, uncertainties are absent from all other rate libraries, and, although estimates have been attempted in previous evaluations and compilations, these are generally not based on rigorous statistical definitions. A common standard for deriving uncertainties is clearly warranted. STARLIB represents a first step in addressing this deficiency by providing a tabular, up-to-date database that supplies not only the rate and its uncertainty but also its distribution. Because a majority of rates are lognormally distributed, this allows the construction of rate probability densities from the columns of STARLIB. This structure is based on a recently suggested Monte Carlo method to calculate reaction rates, w...
New determination of 12C(α,γ)16O reaction rate
Oulebsir, N.
2015-12-01
The reaction 12C(α,γ)16O was investigated through the direct α-transfer reaction (7Li,t) at 28 and 34 MeV incident energies. We determined the reduced α-widths of the sub-threshold 2+ and 1- states of 16O from the DWBA analysis of the transfer reaction 12C(7Li,t)16O performed at two incident energies. The obtained result for the 2+ and 1- sub-threshold resonances as introduced in the R-matrix fitting of radiative capture and elastic-scattering data to determine the E2 and E1 S-factor from 0.01MeV to 4.2MeV in the center-of-mass energy. After determining the astrophysic factor of 12C(α,γ)16O S(E) with Pierre Descouvement code, I determined numerically the new reaction rate of this reaction at a different stellar temperature (0.06 Gk-2 GK). The 12C(α,γ)16O reaction rate at T9 = 0.2 is [7.21-2.25+2.15] × 10-15 cm3 s-1 mol-1. Some comparisons and discussions about our new 12C(α,γ)16O reaction rate are presented. The agreements of the reaction rate below T9 = 2 between our results and with those proposed by NACRE indicate that our results are reliable, and they could be included in the astrophysical reaction rate network.
Stolarski, R. S.; Butler, D. M.; Rundel, R. D.
1977-01-01
A concise stratospheric model was used in a Monte-Carlo analysis of the propagation of reaction rate uncertainties through the calculation of an ozone perturbation due to the addition of chlorine. Two thousand Monte-Carlo cases were run with 55 reaction rates being varied. Excellent convergence was obtained in the output distributions because the model is sensitive to the uncertainties in only about 10 reactions. For a 1 ppby chlorine perturbation added to a 1.5 ppby chlorine background, the resultant 1 sigma uncertainty on the ozone perturbation is a factor of 1.69 on the high side and 1.80 on the low side. The corresponding 2 sigma factors are 2.86 and 3.23. Results are also given for the uncertainties, due to reaction rates, in the ambient concentrations of stratospheric species.
The Effects of Thermonuclear Reaction Rate Variations on Nova Nucleosynthesis A Sensitivity Study
Iliadis, C; José, J; Starrfield, S; Tupper, P; Iliadis, Christian; Champagne, Art; Jose, Jordi; Starrfield, Sumner; Tupper, Paul
2002-01-01
We investigate the effects of thermonuclear reaction rate uncertainties on nova nucleosynthesis. One-zone nucleosynthesis calculations have been performed by adopting temperature-density-time profiles of the hottest hydrogen-burning zone (i.e., the region in which most of the nucleosynthesis takes place). We obtain our profiles from 7 different, recently published, hydrodynamic nova simulations covering peak temperatures in the range from Tpeak=0.145-0.418 GK. For each of these profiles, we individually varied the rates of 175 reactions within their associated errors and analyzed the resulting abundance changes of 142 isotopes in the mass range below A=40. In total, we performed 7350 nuclear reaction network calculations. We use the most recent thermonuclear reaction rate evaluations for the mass ranges A=1-20 and A=20-40. For the theoretical astrophysicist, our results indicate the extent to which nova nucleosynthesis calculations depend on presently uncertain nuclear physics input, while for the experimenta...
Calorimetric determination of rate constants and enthalpy changes for zero-order reactions.
Almeida e Sousa, Luis; Beezer, Anthony E; Hansen, Lee D; Clapham, David; Connor, Joseph A; Gaisford, Simon
2012-06-07
Calorimetry is a general method for determination of the rates of zero-order processes, but analysis of the data for the rate constant and reaction enthalpy is difficult because these occur as a product in the rate equation so evaluation of one requires knowledge of the other. Three methods for evaluation of both parameters, without prior knowledge, are illustrated with examples and compared with literature data. Method 1 requires the reaction to be studied in two buffers with different enthalpies of ionization. Method 2 is based on calculation of reaction enthalpy from group additivity functions. Method 3 applies when reaction progresses to completion. The methods are applied to the enzymatic hydrolysis of urea, the hydrolysis of acetylsalicylic acid, and the photodegradation of nifedipine, respectively.
Aikawa, M.; Arnould, M.; Goriely, S.; Jorissen, A.; Takahashi, K.
2005-10-01
Nuclear reaction rates are quantities of fundamental importance in astrophysics. Substantial efforts have been devoted in the last decades to measuring or calculating them. This paper presents a detailed description of the Brussels nuclear reaction rate library BRUSLIB and of the nuclear network generator NETGEN. BRUSLIB is made of two parts. The first one contains the 1999 NACRE compilation based on experimental data for 86 reactions with (mainly) stable targets up to Si. BRUSLIB provides an electronic link to the published, as well as to a large body of unpublished, NACRE data containing adopted rates, as well as lower and upper limits. The second part of BRUSLIB concerns nuclear reaction rate predictions to complement the experimentally-based rates. An electronic access is provided to tables of rates calculated within a statistical Hauser-Feshbach approximation, which limits the reliability of the rates to reactions producing compound nuclei with a high enough level density. These calculations make use of global and coherent microscopic nuclear models for the quantities entering the rate calculations. The use of such models makes the BRUSLIB rate library unique. A description of the Nuclear Network Generator NETGEN that complements the BRUSLIB package is also presented. NETGEN is a tool to generate nuclear reaction rates for temperature grids specified by the user. The information it provides can be used for a large variety of applications, including Big Bang nucleosynthesis, the energy generation and nucleosynthesis associated with the non-explosive and explosive hydrogen to silicon burning stages, or the synthesis of the heavy nuclides through the s-, α- and r-, rp- or p-processes.
Maher, K.; Steefel, Carl; White, A.F.; Stonestrom, D.A.
2009-01-01
In order to explore the reasons for the apparent discrepancy between laboratory and field weathering rates and to determine the extent to which weathering rates are controlled by the approach to thermodynamic equilibrium, secondary mineral precipitation, and flow rates, a multicomponent reactive transport model (CrunchFlow) was used to interpret soil profile development and mineral precipitation and dissolution rates at the 226 ka Marine Terrace Chronosequence near Santa Cruz, CA. Aqueous compositions, fluid chemistry, transport, and mineral abundances are well characterized [White A. F., Schulz M. S., Vivit D. V., Blum A., Stonestrom D. A. and Anderson S. P. (2008) Chemical weathering of a Marine Terrace Chronosequence, Santa Cruz, California. I: interpreting the long-term controls on chemical weathering based on spatial and temporal element and mineral distributions. Geochim. Cosmochim. Acta 72 (1), 36-68] and were used to constrain the reaction rates for the weathering and precipitating minerals in the reactive transport modeling. When primary mineral weathering rates are calculated with either of two experimentally determined rate constants, the nonlinear, parallel rate law formulation of Hellmann and Tisserand [Hellmann R. and Tisserand D. (2006) Dissolution kinetics as a function of the Gibbs free energy of reaction: An experimental study based on albite feldspar. Geochim. Cosmochim. Acta 70 (2), 364-383] or the aluminum inhibition model proposed by Oelkers et al. [Oelkers E. H., Schott J. and Devidal J. L. (1994) The effect of aluminum, pH, and chemical affinity on the rates of aluminosilicate dissolution reactions. Geochim. Cosmochim. Acta 58 (9), 2011-2024], modeling results are consistent with field-scale observations when independently constrained clay precipitation rates are accounted for. Experimental and field rates, therefore, can be reconciled at the Santa Cruz site. Additionally, observed maximum clay abundances in the argillic horizons occur at
Determination of the enzyme reaction rate in a differential fixed-bed reactor: a case study
Baruque Filho E.A.
2001-01-01
Full Text Available The reaction rate of starch hydrolysis catalyzed by a glucoamylase covalently bound to chitin particles was measured in a Differential Fixed-Bed Reactor (DFBR. Under selected test conditions the initial reaction rate may represent biocatalyst activity. Some aspects which influence measurement of the initial reaction rate of an immobilized enzyme were studied: the amount of desorbed enzyme and its hydrolytic activity, the extent of pore blockage of the biocatalyst caused by substrate solution impurities and the internal and external diffusional mass transfer effects. The results showed that the enzyme glucoamylase was firmly bound to the support, as indicated by the very low amount of desorbed protein found in the recirculating liquid. Although this protein was very active, its contribution to the overall reaction rate was negligible. It was observed that the biocatalyst pores were susceptible to being blocked by the impurities of the starch solution. This latter effect was accumulative, increasing with the number of sequential experiments carried out. When the substrate solution was filtered before use, very reliable determinations of immobilized enzyme reaction rates could be performed in the DFBR. External and internal diffusional resistences usually play a significant role in fixed-bed reactors. However, for the experimental system studied, internal mass transfer effects were not significant, and it was possible to select an operational condition (recirculation flow rate value that minimized the external diffusional limitations.
REACLIB: A Reaction Rate Library for the Era of Collaborative Science
Meisel, Zachary
2008-10-01
Thermonuclear reaction rates and weak decay rates are of great importance to modern nuclear astrophysics. They are critical in the study of many topics such as Big Bang Nucleosynthesis, X-ray bursts, Supernovae, and S-process element formation, among others. The Joint Institute for Nuclear Astrophysics (JINA) has been created to increase connectivity amongst nuclear astrophysicists in our modern age of highly collaborative science. Within JINA there has been an effort to create a frequently updated and readily accessible database of thermonuclear reactions and weak decay rates. This database is the REACLIB library, which can be accessed at the web address: http://www.nscl.msu.edu/˜nero/db/. Here I will discuss the JINA REACLIB Project, including a new procedure to fit reaction rates as a function of temperature that takes full advantage of physicality. With these updated reaction rates, astrophysical modelers will no longer have to worry about the adverse effects of using obsolete reaction rate libraries lacking physical behavior.
Rate constant and reaction coordinate of Trp-cage folding in explicit water
Juraszek, J.; Bolhuis, P.G.
2008-01-01
We report rate constant calculations and a reaction coordinate analysis of the rate-limiting folding and unfolding process of the Trp-cage mini-protein in explicit solvent using transition interface sampling. Previous transition path sampling simulations revealed that in this (un)folding process the
Chemical Reaction Rates from Ring Polymer Molecular Dynamics: Theory and Practical Applications
Suleimanov, Yury V; Guo, Hua
2016-01-01
This Feature Article presents an overview of the current status of Ring Polymer Molecular Dynamics (RPMD) rate theory. We first analyze theory and its connection to quantum transition state theory. We then focus on its practical application to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rates in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rates. We also hope it will motivate further applications of RPMD to various chemical reactions.
Suleimanov, Yury V; Aoiz, F Javier; Guo, Hua
2016-11-03
This Feature Article presents an overview of the current status of ring polymer molecular dynamics (RPMD) rate theory. We first analyze the RPMD approach and its connection to quantum transition-state theory. We then focus on its practical applications to prototypical chemical reactions in the gas phase, which demonstrate how accurate and reliable RPMD is for calculating thermal chemical reaction rate coefficients in multifarious cases. This review serves as an important checkpoint in RPMD rate theory development, which shows that RPMD is shifting from being just one of recent novel ideas to a well-established and validated alternative to conventional techniques for calculating thermal chemical rate coefficients. We also hope it will motivate further applications of RPMD to various chemical reactions.
Shim S.M.
2012-01-01
Full Text Available The performance of the CO2 absorber column using mono-ethanolamine (MEA solution as chemical solvent are predicted by a One-Dimensional (1-D rate based model in the present study. 1-D Mass and heat balance equations of vapor and liquid phase are coupled with interfacial mass transfer model and vapor-liquid equilibrium model. The two-film theory is used to estimate the mass transfer between the vapor and liquid film. Chemical reactions in MEA-CO2-H2O system are considered to predict the equilibrium pressure of CO2 in the MEA solution. The mathematical and reaction kinetics models used in this work are calculated by using in-house code. The numerical results are validated in the comparison of simulation results with experimental and simulation data given in the literature. The performance of CO2 absorber column is evaluated by the 1-D rate based model using various reaction rate coefficients suggested by various researchers. When the rate of liquid to gas mass flow rate is about 8.3, 6.6, 4.5 and 3.1, the error of CO2 loading and the CO2 removal efficiency using the reaction rate coefficients of Aboudheir et al. is within about 4.9 % and 5.2 %, respectively. Therefore, the reaction rate coefficient suggested by Aboudheir et al. among the various reaction rate coefficients used in this study is appropriate to predict the performance of CO2 absorber column using MEA solution. [Acknowledgement. This research was supported by the Basic Science Research Program through the National Research Foundation of Korea (NRF, funded by the Ministry of Education, Science and Technology (2011-0017220].
Dependence of X-Ray Burst Models on Nuclear Reaction Rates
Cyburt, R. H.; Amthor, A. M.; Heger, A.; Johnson, E.; Keek, L.; Meisel, Z.; Schatz, H.; Smith, K.
2016-10-01
X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars, and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p, γ), (α, γ), and (α, p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to match calculations with a state-of-the-art 1D multi-zone model based on the Kepler stellar evolution code. All relevant reaction rates on neutron-deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 changes in reaction rate with the highest impact were then repeated in the 1D multi-zone model. We find a number of uncertain reaction rates that affect predictions of light curves and burst ashes significantly. The results provide insights into the nuclear processes that shape observables from X-ray bursts, and guidance for future nuclear physics work to reduce nuclear uncertainties in X-ray burst models.
Ab Initio Calculation of Rate Constants for Molecule–Surface Reactions with Chemical Accuracy
Piccini, GiovanniMaria; Alessio, Maristella
2016-01-01
Abstract The ab initio prediction of reaction rate constants for systems with hundreds of atoms with an accuracy that is comparable to experiment is a challenge for computational quantum chemistry. We present a divide‐and‐conquer strategy that departs from the potential energy surfaces obtained by standard density functional theory with inclusion of dispersion. The energies of the reactant and transition structures are refined by wavefunction‐type calculations for the reaction site. Thermal effects and entropies are calculated from vibrational partition functions, and the anharmonic frequencies are calculated separately for each vibrational mode. This method is applied to a key reaction of an industrially relevant catalytic process, the methylation of small alkenes over zeolites. The calculated reaction rate constants (free energies), pre‐exponential factors (entropies), and enthalpy barriers show that our computational strategy yields results that agree with experiment within chemical accuracy limits (less than one order of magnitude). PMID:27008460
Kinetics of the benzyl + O(3P) reaction: a quantum chemical/statistical reaction rate theory study.
da Silva, Gabriel; Bozzelli, Joseph W
2012-12-14
The resonance stabilized benzyl radical is an important intermediate in the combustion of aromatic hydrocarbons and in polycyclic aromatic hydrocarbon (PAH) formation in flames. Despite being a free radical, benzyl is relatively stable in thermal, oxidizing environments, and is predominantly removed through bimolecular reactions with open-shell species other than O(2). In this study the reaction of benzyl with ground-state atomic oxygen, O((3)P), is examined using quantum chemistry and statistical reaction rate theory. C(7)H(7)O energy surfaces are generated at the G3SX level, and include several novel pathways. Transition state theory is used to describe elementary reaction kinetics, with canonical variational transition state theory applied for barrierless O atom association with benzyl. Apparent rate constants and branching ratios to different product sets are obtained as a function of temperature and pressure from solving the time-dependent master equation, with RRKM theory for microcanonical k(E). These simulations indicate that the benzyl + O reaction predominantly forms the phenyl radical (C(6)H(5)) plus formaldehyde (HCHO), with lesser quantities of the C(7)H(6)O products benzaldehyde, ortho-quinone methide, and para-quinone methide (+H), along with minor amounts of the formyl radical (HCO) + benzene. Addition of O((3)P) to the methylene site in benzyl produces a highly vibrationally excited C(7)H(7)O* adduct, the benzoxyl radical, which can β-scission to benzaldehyde + H and phenyl + HCHO. In order to account for the experimental observation of benzene as the major reaction product, a roaming radical mechanism is proposed that converts the nascent products phenyl and HCHO to benzene + HCO. Oxygen atom addition at the ortho and para ring sites in benzyl, which has not been previously considered, is shown to lead to the quinone methides + H; these species are less-stable isomers of benzaldehyde that are proposed as important combustion intermediates, but
Depletion: A Game with Natural Rules for Teaching Reaction Rate Theory
Olbris, Donald J.; Herzfeld, Judith
2002-10-01
Depletion is a game that reinforces central concepts of reaction rate theory through simulation. Each player buys chemicals and guides them through a series of reactions, thereby earning money to buy more chemicals. The reactions occur when players roll a high enough value on two dice to overcome an activation barrier. The reactions may be accelerated by buying heat (which allows the player to roll three dice instead of two) or catalysts (which lower the activation barrier). The value of acceleration derives from the increasing price of fresh chemicals as resources are depleted and waste products accumulate. The player who nets the most money wins the game. The details of the game are presented, with a set of follow-up questions suitable for either a quiz or discussion. Student reaction to the game is also described.
34 CFR 694.9 - What is the maximum indirect cost rate for an agency of a State or local government?
2010-07-01
... for an agency of a State or local government? Notwithstanding 34 CFR 75.560-75.562 and 34 CFR 80.22, the maximum indirect cost rate that an agency of a State or local government receiving funds under... a State or local government? 694.9 Section 694.9 Education Regulations of the Offices of...
Minakata, Daisuke; Li, Ke; Westerhoff, Paul; Crittenden, John
2009-08-15
The hydroxyl radical (HO*) is a strong oxidant that reacts with electron-rich sites of organic compounds and initiates complex chain mechanisms. In order to help understand the reaction mechanisms, a rule-based model was previously developed to predict the reaction pathways. For a kinetic model, there is a need to develop a rate constant estimator that predicts the rate constants for a variety of organic compounds. In this study, a group contribution method (GCM) is developed to predict the aqueous phase HO* rate constants for the following reaction mechanisms: (1) H-atom abstraction, (2) HO* addition to alkenes, (3) HO* addition to aromatic compounds, and (4) HO* interaction with sulfur (S)-, nitrogen (N)-, or phosphorus (P)-atom-containing compounds. The GCM hypothesizes that an observed experimental rate constant for a given organic compound is the combined rate of all elementary reactions involving HO*, which can be estimated using the Arrhenius activation energy, E(a), and temperature. Each E(a) for those elementary reactions can be comprised of two parts: (1) a base part that includes a reactive bond in each reaction mechanism and (2) contributions from its neighboring functional groups. The GCM includes 66 group rate constants and 80 group contribution factors, which characterize each HO* reaction mechanism with steric effects of the chemical structure groups and impacts of the neighboring functional groups, respectively. Literature-reported experimental HO* rate constants for 310 and 124 compounds were used for calibration and prediction, respectively. The genetic algorithms were used to determine the group rate constants and group contribution factors. The group contribution factors for H-atom abstraction and HO* addition to the aromatic compounds were found to linearly correlate with the Taft constants, sigma*, and electrophilic substituent parameters, sigma+, respectively. The best calibrations for 83% (257 rate constants) and predictions for 62% (77
Trapp, O
2006-01-01
A unified equation to evaluate elution profiles of reversible as well as irreversible (pseudo-) first-order reactions in dynamic chromatography and on-column reaction chromatography has been derived. Rate constants k1 and k(-1) and Gibbs activation energies are directly obtained from the chromatographic parameters (retention times tR(A) and tR(B) of the interconverting or reacting species A and B, the peak widths at half-height wA and wB, and the relative plateau height h(p)), the initial amounts A0 and B0 of the reacting species, and the equilibrium constant K(A/B). The calculation of rate constants requires only a few iterative steps without the need of performing a computationally extensive simulation of elution profiles. The unified equation was validated by comparison with a data set of 125,000 simulated elution profiles to confirm the quality of this equation by statistical means and to predict the minimal experimental requirements. Surprisingly, the recovery rate from a defined data set is on average 35% higher using the unified equation compared to the evaluation by iterative computer simulation.
Generalization of the Activated Complex Theory of Reaction Rates. I. Quantum Mechanical Treatment
Marcus, R. A.
1964-01-01
In its usual form activated complex theory assumes a quasi-equilibrium between reactants and activated complex, a separable reaction coordinate, a Cartesian reaction coordinate, and an absence of interaction of rotation with internal motion in the complex. In the present paper a rate expression is derived without introducing the Cartesian assumption. The expression bears a formal resemblance to the usual one and reduces to it when the added assumptions of the latter are introduced.
Measurement of reaction rates of interest in stellar structure and evolution
Terrasi, F.; D`Onofrio, A. [Dipt. di Scienze Ambientali, Seconda Univ. di Napoli, Caserta (Italy)]|[INFN, Napoli (Italy); Campajola, L.; Imbriani, G. [INFN, Napoli (Italy)]|[Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); Gialanella, L. [INFN, Napoli (Italy)]|[Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy)]|[Inst. fuer Experimentalphysik III, Ruhr-Univ. Bochum, Bochum (Germany); Greife, U.; Rolfs, C.; Strieder, F.; Trautvetter, H.P. [Inst. fuer Experimentalphysik III, Ruhr-Univ. Bochum, Bochum (Germany); Roca, V.; Romano, M. [INFN, Napoli (Italy)]|[Dipt. di Scienze Fisiche, Univ. Federico II, Napoli (Italy); Straniero, O. [Osservatorio Astronomico di Collurania, Teramo (Italy)
1998-06-01
Accurate determinations of reaction rates at astrophysical energies are very important in stellar structure and evolution studies. The cases of two key reactions, namely {sup 7}Be(p,{gamma}){sup 8}B and {sup 12}C({alpha},{gamma}){sup 16}O are discussed, both from the point of view of their astrophysical interest and of the experimental difficulties in the measurement of their cross section. (orig.)
Perturbation theory in the catalytic rate constant of the Henri-Michaelis-Menten enzymatic reaction.
Bakalis, Evangelos; Kosmas, Marios; Papamichael, Emmanouel M
2012-11-01
The Henry-Michaelis-Menten (HMM) mechanism of enzymatic reaction is studied by means of perturbation theory in the reaction rate constant k (2) of product formation. We present analytical solutions that provide the concentrations of the enzyme (E), the substrate (S), as well as those of the enzyme-substrate complex (C), and the product (P) as functions of time. For k (2) small compared to k (-1), we properly describe the entire enzymatic activity from the beginning of the reaction up to longer times without imposing extra conditions on the initial concentrations E ( o ) and S ( o ), which can be comparable or much different.
Taniguchi, Miki; Nishiyama, Akio; Sasauchi, Kenichi; Ito, Yusuke; Akamatsu, Fumiteru
In order to develop a small-scale gasifier in which biomass can be converted to energy with high efficiency, we planned a gasification process that consists of two parts: pyrolysis part (rotary kiln) and gasification part (downdraft gasifier). We performed fundamental experiments on gasification part and discussed the appropriate conditions such as air supply location, air ratio, air temperature and hearth load. We considered the results by calculating reaction rates of representative reactions on char gasification part and found that water gas reaction is dominant in the reduction area and its behavior gives important information to decide the adequate length of the char layer.
Combustion of Bimodal Nano/Micro Aluminum Suspension with New Reaction Rate Model
M. Bidabadi; N. Moallemi; I. Shafieenejad; M. Jadidi
2008-01-01
In this study a mathematical model for combustion of bimodal particle in lean flow was developed. The difference between structure of flame in this work and previous ones was that, in those flame was divided by five zones and reaction rate was considered to be constant in reaction zones and also zero in post flame zone. In reality it was obvious with respect to shape and size of different particles in dust, reaction didn't end suddenly. In the present research the heat loss term, which was as...
Rate constants for chemical reactions in high-temperature nonequilibrium air
Jaffe, R. L.
1986-01-01
In the nonequilibrium atmospheric chemistry regime that will be encountered by the proposed Aeroassisted Orbital Transfer Vehicle in the upper atmosphere, where air density is too low for thermal and chemical equilibrium to be maintained, the detailed high temperature air chemistry plays a critical role in defining radiative and convective heating loads. Although vibrational and electronic temperatures remain low (less than 15,000 K), rotational and translational temperatures may reach 50,000 K. Attention is presently given to the effects of multiple temperatures on the magnitudes of various chemical reaction rate constants, for the cases of both bimolecular exchange reactions and collisional excitation and dissociation reactions.
Comparison of mass loss rate in reaction of silica with carbon from different investigation results
J. Węgrzyn
2015-07-01
Full Text Available In the process of carbothermic reaction of SiO2 + mC, key reactions appear on the surfaces of both SiO2 and C grains. However, the values of these surfaces are not known. Assuming the simplest case, quartzite and carbon grains are spheres, total surfaces of reaction were calculated for grains of carbon and quartzite respectively. This enabled to determine the rate of weight loss referred to the unit area of C and SiO2.
Mineral/solution reaction rates in a mixed flow reactor: Wollastonite hydrolysis
Rimstidt, J. Donald; Dove, Patricia M.
1986-11-01
A newly developed mixed flow reactor was used to measure the rate of hydrolysis of wollastonite over the pH range of 3 to 8. This design avoids abrasion of the solid sample by confining it within a nylon mesh while the reacting solution is circulated over it by a stirrer. The rate of reaction was determined from the difference of the compositions of the input and output solutions following the methods used by chemical engineers for the analysis of mixed flow reactors, also called continuously stirred tank reactors (CSTR). This apparatus, constructed from easily obtainable parts, avoids many of the problems inherent in studying mineral/solution reaction kinetics in batch reactors. The hydrolysis of wollastonite CaSiO3 + 2 H+ + H2O = Ca2+ + H4SiO4 can be fit to a rate law of the form: dnH+/ dt = kadKH+mH+/(1.0 + KH+mH+) where kad = 9.80 × 10 -8molm-2sec-1 and KH+ = 2.08 × 10 5. Over the pH range of 4 to 7, the data also may fit a simple linear form: dnH+/ dt = - Ak+( aH+) 0.40 where k+ = 3.80 × 10 -6 sec -1 at 25°C. The presence of calcium ion in the solution at concentrations up to 1.0 mol kg -1 produces only a minor reduction of the reaction rate. The activation energy for this reaction is 79.2 kJ mol -1. Examination of the surfaces of the reacted grains showed no evidence of incongruent reaction leading to a product layer but did show the extensive development of etch pits leading to a rapid increase in the specific surface area. At large extents of reaction at low pH, diffusion of ions into or from these deep etch pits may limit the reaction rate.
The Influence of Reaction Rates on the Final p-Abundances
Rapp, W; Schatz, H; Käppeler, F K
2004-01-01
The astrophysical p-process is responsible for the origin of the proton rich nuclei,which are heavier than iron. A huge network involving thousands of reaction rates is necessary to calculate the final p-abundances. But not all rates included in the network have a strong influence on the p-nuclei abundances. The p-process was investigated using a full nuclear reaction network for a type II supernovae explosion when the shock front passes through the O/Ne layer. Calculations were done with a multi-layer model adopting the seed of a pre-explosion evolution of a 25 mass star. In extensive simulations we investigated the impact of single reaction rates on the final p-abundances. The results are important for the strategy of future experiments in this field.
Sensitivity of Type I X-Ray Bursts to rp-Process Reaction Rates
Amthor, A M; Heger, A; Sakharuk, A; Schatz, H; Smith, K; Galaviz, Daniel; Heger, Alexander; Sakharuk, Alexander; Schatz, Hendrik; Smith, Karl
2006-01-01
First steps have been taken in a more comprehensive study of the dependence of observables in Type I X-ray bursts on uncertain (p,gamma) reaction rates along the rp-process path. We use the multizone hydrodynamics code KEPLER which implicitly couples a full nuclear reaction network of more than 1000 isotopes, as needed, to follow structure and evolution of the X-ray burst layer and its ashes. This allows us to incorporate the full rp-process network, including all relevant nuclear reactions, and individually study changes in the X-ray burst light curves when modifying selected key nuclear reaction rates. In this work we considered all possible proton captures to nuclei with 10 < Z < 28 and N <= Z. When varying individual reaction rates within a symmetric full width uncertainty of a factor of 10000, early results for some rates show changes in the burst light curve as large as 10 percent of peak luminosity. This is very large compared to the current sensitivity of X-ray observations. More precise reac...
Ab-Initio Based Computation of Rate Constants for Spin Forbidden Metalloprotein-Substrate Reactions
Ozkanlar, Abdullah; Rodriguez, Jorge H.
2007-03-01
Some chemical and biochemical reactions are non-adiabatic processes whereby the total spin angular momentum, before and after the reaction, is not conserved. These are named spin- forbidden reactions. The application of ab-initio methods, such as spin density functional theory (SDFT), to the prediction of rate constants is a challenging task of fundamental and practical importance. We apply non-adiabatic transition state theory (NA-TST) in conjuntion with SDFT to predict the rate constant of the spin- forbidden recombination of carbon monoxide with iron tetracarbonyl. To model the surface hopping probability between singlet and triplet states, the Landau-Zener formalism is used. The lowest energy point for singlet-triplet crossing, known as minimum energy crossing point (MECP), was located and used to compute, in a semi-quantum approach, reaction rate constants at 300 K. The predicted rates are in very good agreement with experiment. In addition, we present results for the spin- forbidden ligand binding reactions of iron-containing heme proteins such as myoglobin.
Shizgal, Bernie D.
2016-12-01
There has been intense interest for several decades by different research groups to accurately model the temperature dependence of a large number of nuclear reaction rate coefficients for both light and heavy nuclides. The rate coefficient, k(T) , is given by the Maxwellian average of the reactive cross section expressed in terms of the astrophysical factor, S(E) , which for nonresonant reactions is generally written as a power series in the relative energy E. A computationally efficient algorithm for the temperature dependence of nuclear reaction rate coefficients is required for fusion reactor research and for models of nucleosynthesis and stellar evolution. In this paper, an accurate analytical expression for the temperature dependence of nuclear reaction rate coefficients is provided in terms of τ = 3(b / 2) 2/3 or equivalently, T - 1/3 , where b = B /√{kB T }, B is the Gamow factor and kB is the Boltzmann constant. The methodology is appropriate for all nonresonant nuclear reactions for which S(E) can be represented as a power series in E. The explicit expression for the rate coefficient versus temperature is derived with the asymptotic expansions of the moments of w(E) = exp(- E /kB T - B /√{ E }) in terms of τ. The zeroth order moment is the familiar Gaussian approximation to the rate coefficient. Results are reported for the representative reactions D(d, p)T, D(d, n)3He and 7Li(p, α) α and compared with several different fitting procedures reported in the literature.
Nurlaela, Ela
2016-01-25
The present work compares oxygen evolution reaction (OER) in electrocatalysis and photocatalysis in aqueous solutions using nanostructured NiFeOx as catalysts. The impacts of pH and reaction temperature on the electrocatalytic and photocatalytic OER kinetics were investigated. For electrocatalysis, a NiFeOx catalyst was hydrothermally decorated on Ni foam. In 1 M KOH solution, the NiFeOx electrocatalyst achieved 10 mA cm-2 at an overpotential of 260 mV. The same catalyst was decorated on the surface of Ta3N5 photocatalyst powder. The reaction was conducted in the presence of 0.1 M Na2S2O8 as a strong electron scavenger, thus likely leading to the OER being kinetically relevant. When compared with the bare Ta3N5, NiFeOx/Ta3N5 demonstrated a 5-fold improvement in photocatalytic activity in the OER under visible light irradiation, achieving a quantum efficiency of 24 % at 480 nm. Under the conditions investigated, a strong correlation between the electrocatalytic and photocatalytic performances was identified: an improvement in electrocatalysis corresponded with an improvement in photocatalysis without altering the identity of the materials. The rate change at different pH was likely associated with electrocatalytic kinetics that accordingly influenced the photocatalytic rates. The sensitivity of the reaction rates with respective to the reaction temperature resulted in an apparent activation energy of 25 kJ mol-1 in electrocatalysis, whereas that in photocatalysis was 16 kJ mol-1. The origin of the difference in these activation energy values is likely attributed to the possible effects of temperature on the individual thermodynamic and kinetic parameters of the reaction process. The work described herein demonstrates a method of “transferring the knowledge of electrocatalysis to photocatalysis” as a strong tool to rationally and quantitatively understand the complex reaction schemes involved in photocatalytic reactions.
Observation of double pygmy resonances in $^{195,196}$Pt and enhanced astrophysical reaction rates
Giacoppo, F; Eriksen, T K; Görgen, A; Guttormsen, M; Hagen, T W; Larsen, A C; Kheswa, B V; Klintefjord, M; Koehler, P E; Nyhus, H T; Renstr\\om, T; Sahin, E; Siem, S; Tornyi, T G
2014-01-01
Our measurements of $^{195,196}$Pt $\\gamma$-strength functions show a double-humped enhancement in the $E_{\\gamma}= 4-8$ MeV region. For the first time, the detailed shape of these resonances is revealed for excitation energies in the quasicontinuum. We demonstrate that the corresponding neutron-capture cross sections and astrophysical reaction rates are increased by up to a factor of 2 when these newly observed pygmy resonances are included. These results lend credence to theoretical predictions of enhanced reaction rates due to such pygmy resonances and hence are important for a better understanding of r-process nucleosynthesis.
Effect of macromolecular crowding on the rate of diffusion-limited enzymatic reaction
Manish Agrawal; S B Santra; Rajat Anand; Rajaram Swaminathan
2008-08-01
The cytoplasm of a living cell is crowded with several macromolecules of different shapes and sizes. Molecular diffusion in such a medium becomes anomalous due to the presence of macromolecules and diffusivity is expected to decrease with increase in macromolecular crowding. Moreover, many cellular processes are dependent on molecular diffusion in the cell cytosol. The enzymatic reaction rate has been shown to be affected by the presence of such macromolecules. A simple numerical model is proposed here based on percolation and diffusion in disordered systems to study the effect of macromolecular crowding on the enzymatic reaction rates. The model qualitatively explains some of the experimental observations.
Lee, Sang-Yong; Ortega, Antonio
2000-04-01
We address the problem of online rate control in digital cameras, where the goal is to achieve near-constant distortion for each image. Digital cameras usually have a pre-determined number of images that can be stored for the given memory size and require limited time delay and constant quality for each image. Due to time delay restrictions, each image should be stored before the next image is received. Therefore, we need to define an online rate control that is based on the amount of memory used by previously stored images, the current image, and the estimated rate of future images. In this paper, we propose an algorithm for online rate control, in which an adaptive reference, a 'buffer-like' constraint, and a minimax criterion (as a distortion metric to achieve near-constant quality) are used. The adaptive reference is used to estimate future images and the 'buffer-like' constraint is required to keep enough memory for future images. We show that using our algorithm to select online bit allocation for each image in a randomly given set of images provides near constant quality. Also, we show that our result is near optimal when a minimax criterion is used, i.e., it achieves a performance close to that obtained by applying an off-line rate control that assumes exact knowledge of the images. Suboptimal behavior is only observed in situations where the distribution of images is not truly random (e.g., if most of the 'complex' images are captured at the end of the sequence.) Finally, we propose a T- step delay rate control algorithm and using the result of 1- step delay rate control algorithm, we show that this algorithm removes the suboptimal behavior.
Reaction rate of H atoms with N2O in hot water
Sargent, Leanne; Sterniczuk, Marcin; Bartels, David M.
2017-06-01
The rate constant of H• atoms with N2O in water has been measured by a competition method up to 300 °C. Radiolysis with 2.5 MeV electrons generated H• atoms, and the HD product from their reaction with deuterated tetrahydrofuran (THF-d8) was measured with mass spectroscopy. The concentration of THF-d8 was changed by an order of magnitude in the presence of 25 mM N2O to obtain the ratio of rate constants. To determine the rate constant of H• with THF-d8, a similar competition vs. 0.2 mM OH- ion was also measured. The reaction rate of H• with OH- has been accurately determined vs. temperature in previous work, allowing the two unknown rate constants to be deduced. Rate constant of H• with THF-d8 follows the Arrhenius law ln(k/M-1s-1)=27.33 - (32.30 kJ/mol)/RT. Rate constant of H• with N2O follows the Arrhenius law ln(k/M-1s-1)=24.50 - (30.42 kJ/mol)/RT. In all likelihood, the N2O reaction proceeds via cis-HNNO• radical intermediate as in the gas phase, but with participation of a bridging water molecule in the 1,3 hydrogen shift to form N2 and •OH products.
2010-01-01
... 9 Animals and Animal Products 2 2010-01-01 2010-01-01 false Young chicken and squab slaughter... INSPECTION REGULATIONS Operating Procedures § 381.67 Young chicken and squab slaughter inspection rate... inspector per minute under the traditional inspection procedure for the different young chicken and...
Examining the reaction of monetary policy to exchange rate changes: A nonlinear ARDL approach
Manogaran, Lavaneesvari; Sek, Siok Kun
2017-04-01
Previous studies showed the exchange rate changes can have significant impacts on macroeconomic performance. Over fluctuation of exchange rate may lead to economic instability. Hence, monetary policy rule tends to react to exchange rate changes. Especially, in emerging economies where the policy-maker tends to limit the exchange rate movement through interventions. In this study, we seek to investigate how the monetary policy rule reacts to exchange rate changes. The nonlinear autoregressive distributed lag (NARDL) model is applied to capture the asymmetric effect of exchange rate changes on monetary policy reaction function (interest rate). We focus the study in ASEAN5 countries (Indonesia, Malaysia, Philippines, Thailand and Singapore). The results indicated the existence of asymmetric effect of exchange rates changes on the monetary reaction function for all ASEAN5 countries in the long-run. Where, in majority of the cases the monetary policy is reacting to the appreciation and depreciation of exchange rate by raising the policy rate. This affirms the intervention of policymakers with the `fear of floating' behavior.
Bartsch, Sebastian; Bornscheuer, Uwe T
2010-12-01
Phenylalanine ammonia lyases (PAL) catalyze the reversible, non-reductive amination of trans-cinnamic acid to l-phenylalanine in the presence of high ammonia concentrations. Since neither cofactor recycling nor other additives are needed and by this asymmetric synthesis theoretical yields of 100% can be reached, it is an interesting reaction for industrial processes. In this study we demonstrate the superior properties of p-nitro-cinnamic acid (p-n-CA) in the amination reaction using the PAL from Petroselinum crispum (pcPAL). By focused-directed evolution, three mutants were identified showing increased reaction rates and decreased substrate inhibition. Together, the F137V mutant with p-n-CA showed a 15-fold increased reaction rate compared with the pcPAL WT with the natural cinnamic acid. The high reaction rates were also proven in preparative scale experiments. Activities towards other p-substituted cinnamic acids showing different electronic effects of the substituent were analyzed. Focused-directed evolution around the carboxylic acid- and amine-binding site always decreased PAL activity, due to a sensitive H-bond network.
Rate constant for the reaction of atomic oxygen with phosphine at 298 K
Stief, L. J.; Payne, W. A.; Nava, D. F.
1987-01-01
The rate constant for the reaction of atomic oxygen with phosphine has been measured at 298 K using flash photolysis combined with time-resolved detection of O(3P) via resonance fluorescence. Atomic oxygen was produced by flash photolysis of N2O or NO highly diluted in argon. The results were shown to be independent of (PH3), (O), total pressure and the source of O(3P). The mean value of all the experiments is k1 = (3.6 + or -0.8) x 10 to the -11th cu cm/s (1 sigma). Two previous measurements of k1 differed by more than an order of magnitude, and the results support the higher value obtained in a discharge flow-mass spectrometry study. A comparison with rate data for other atomic and free radical reactions with phosphine is presented, and the role of these reactions in the aeronomy or photochemistry of Jupiter and Saturn is briefly considered.
The rate constant for the CO + H2O2 reaction
Glarborg, Peter; Marshall, Paul
2009-01-01
The rate constant for the reaction CO + H2O2 -> HOCO + OH (R1) at 713 K is determined based on the batch reactor experiments of Baldwin et al. [ R. R. Baldwin, R. W. Walker, S. J. Webster, Combust. Flame 15 (1970) 167] on decomposition of H2O2 sensitized by CO. The value, k(1) (713 K) = 8.1 x 10...... in combustion. The present analysis reconciles the batch reactor data of Baldwin et al. with recent high-level theoretical work on the CO + HO2 reaction.......(2) cm(3) mol(-1) s(-1), is consistent with spin-unrestricted density functional theory. Extrapolation to a wider temperature range through ab initio calculations yields the rate constant k(1) = 3.6 x 10(4)T(2.5) exp(-14425[K]/T) cm(3) mol(-1) s(-1). The reaction is probably of minor importance...
Reaction Rates and Kinetic Isotope Effects of H$_2$ + OH $\\rightarrow$ H$_2$O + H
Meisner, Jan
2016-01-01
We calculated reaction rate constants including atom tunneling of the reaction of dihydrogen with the hydroxy radical down to a temperature of 50 K. Instanton theory and canonical variational theory with microcanonical optimized multidimensional tunneling (CVT/$\\mu$OMT) were applied using a fitted potential energy surface [J. Chem. Phys. 138, 154301 (2013)]. All possible protium/deuterium isotopologues were considered. Atom tunneling increases at about 250 K (200 K for deuterium transfer). Even at 50 K the rate constants of all isotopologues remain in the interval $ 4 \\cdot 10^{-20}$ to $4 \\cdot 10^{-17}$ cm$^3$ s$^{-1}$ , demonstrating that even deuterated versions of the title reaction are possibly relevant to astrochemical processes in molecular clouds. The transferred hydrogen atom dominates the kinetic isotope effect at all temperatures.
Investigating rare events with nonequilibrium work measurements. II. Transition and reaction rates.
Moradi, Mahmoud; Sagui, Celeste; Roland, Christopher
2014-01-21
We present a formalism for investigating transition pathways and transition probabilities for rare events in biomolecular systems. The formalism is based on combining Transition Path Theory with the results of nonequilibrium work relations, and shows that the equilibrium and nonequilibrium transition rates are in fact related. Aside from its fundamental importance, this allows for the calculation of relative equilibrium reaction rates with driven nonequilibrium simulations such as Steered Molecular Dynamics. The workings of the formalism are illustrated with a few typical numerical examples.
Favorite, Jeffrey A. [Los Alamos National Lab. (LANL), Los Alamos, NM (United States)
2016-11-21
SENSMG is a tool for computing first-order sensitivities of neutron reaction rates, reaction-rate ratios, leakage, k_{eff}, and α using the PARTISN multigroup discrete-ordinates code. SENSMG computes sensitivities to all of the transport cross sections and data (total, fission, nu, chi, and all scattering moments), two edit cross sections (absorption and capture), and the density for every isotope and energy group. It also computes sensitivities to the mass density for every material and derivatives with respect to all interface locations. The tool can be used for one-dimensional spherical (r) and two-dimensional cylindrical (r-z) geometries. The tool can be used for fixed-source and eigenvalue problems. The tool implements Generalized Perturbation Theory (GPT) as discussed by Williams and Stacey. Section II of this report describes the theory behind adjoint-based sensitivities, gives the equations that SENSMG solves, and defines the sensitivities that are output. Section III describes the user interface, including the input file and command line options. Section IV describes the output. Section V gives some notes about the coding that may be of interest. Section VI discusses verification, which is ongoing. Section VII lists needs and ideas for future work. Appendix A lists all of the input files whose results are presented in Sec. VI.
Efficient Computation of Transition State Resonances and Reaction Rates from a Quantum Normal Form
Schubert, Roman; Waalkens, Holger; Wiggins, Stephen
2006-01-01
A quantum version of a recent formulation of transition state theory in phase space is presented. The theory developed provides an algorithm to compute quantum reaction rates and the associated Gamov-Siegert resonances with very high accuracy. The algorithm is especially efficient for multi-degree-o
Modified landfill gas generation rate model of first-order kinetics and two-stage reaction
Jiajun CHEN; Hao WANG; Na ZHANG
2009-01-01
This investigation was carried out to establish a new domestic landfill gas (LFG) generation rate model that takes into account the impact ofleachate recirculation. The first-order kinetics and two-stage reaction (FKTSR) model of the LFG generation rate includes mechanisms of the nutrient balance for biochemical reaction in two main stages. In this study, the FKTSR model was modified by the introduction of the outflow function and the organic acid conversion coefficient in order to represent the in-situ condition of nutrient loss through leachate. Laboratory experiments were carried out to simulate the impact of leachate recirculation and verify the modified FKTSR model. The model calibration was then calculated by using the experimental data. The results suggested that the new model was in line with the experimental data. The main parameters of the modified FKTSR model, including the LFG production potential (L0), the reaction rate constant in the first stage (K1), and the reaction rate constant in the second stage (K2) of 64.746 L, 0.202 d-1, and 0.338 d-1,respectively, were comparable to the old ones of 42.069 L,0.231 d-1, and 0.231 d-1. The new model is better able to explain the mechanisms involved in LFG generation.
Should Thermostatted Ring Polymer Molecular Dynamics be used to calculate reaction rates?
Hele, Timothy J H
2015-01-01
We apply Thermostatted Ring Polymer Molecular Dynamics (TRPMD), a recently-proposed approximate quantum dynamics method, to the computation of thermal reaction rates. Its short-time Transition-State Theory (TST) limit is identical to rigorous Quantum Transition-State Theory, and we find that its long-time limit is independent of the location of the dividing surface. TRPMD rate theory is then applied to one-dimensional model systems, the atom-diatom bimolecular reactions H+H$_2$, D+MuH and F+H$_2$, and the prototypical polyatomic reaction H+CH$_4$. Above the crossover temperature, the TRPMD rate is virtually invariant to the strength of the friction applied to the internal ring-polymer normal modes, and beneath the crossover temperature the TRPMD rate generally decreases with increasing friction, in agreement with the predictions of Kramers theory. We therefore find that TRPMD is less accurate than Ring Polymer Molecular Dynamics (RPMD) for symmetric reactions, and in certain asymmetric systems closer to the q...
Dependence of X-Ray Burst Models on Nuclear Reaction Rates
Cyburt, R H; Heger, A; Johnson, E; Keek, L; Meisel, Z; Schatz, H; Smith, K
2016-01-01
X-ray bursts are thermonuclear flashes on the surface of accreting neutron stars and reliable burst models are needed to interpret observations in terms of properties of the neutron star and the binary system. We investigate the dependence of X-ray burst models on uncertainties in (p,$\\gamma$), ($\\alpha$,$\\gamma$), and ($\\alpha$,p) nuclear reaction rates using fully self-consistent burst models that account for the feedbacks between changes in nuclear energy generation and changes in astrophysical conditions. A two-step approach first identified sensitive nuclear reaction rates in a single-zone model with ignition conditions chosen to match calculations with a state-of-the-art 1D multi-zone model based on the {\\Kepler} stellar evolution code. All relevant reaction rates on neutron deficient isotopes up to mass 106 were individually varied by a factor of 100 up and down. Calculations of the 84 highest impact reaction rate changes were then repeated in the 1D multi-zone model. We find a number of uncertain reac...
The influence of SPS heating rates on the synthesis reaction of tantalum diboride
Jolanta Laszkiewicz-Łukasik
2016-07-01
Full Text Available TaB2 is a material from the Ultra High Temperature Ceramics group and is rather unexplored because it is difficult to procure the raw materials and to densify TaB2. Using SPS technique to realize reactive sintering processes of powders mixture according to the reaction Ta + 2B → TaB2 makes it possible to achieve TaB2 in one technological step. The aim of the study was to determine the influence of heating rates on the synthesis reaction and on the multistage densification mechanisms during SPS processes. The mixture was sintered at constant parameters of 2200 °C, 48 MPa for 5 min with the usage of heating rates from 50 °C/min up to 400 °C/min. The densification processes were studied through analyzing the shrinkage of powder compacts during SPS (Spark Plasma Sintering processes. The comparison of the densification curves indicates that the reactions do not proceed completely at slow heating rates. Namely, too low heating rates contribute to the sintering of tantalum before the synthesis reaction and demonstrate the presence of boron in liquid state. The best material obtained in this study has Young's modulus 571 GPa, Vickers hardness 20.7 GPa (HV1 and indentation fracture toughness KIC 4.7 MPa m1/2.
Should thermostatted ring polymer molecular dynamics be used to calculate thermal reaction rates?
Hele, Timothy J. H., E-mail: tjhh2@cam.ac.uk [Department of Chemistry, University of Cambridge, Lensfield Road, Cambridge CB2 1EW (United Kingdom); Suleimanov, Yury V. [Computation-based Science and Technology Research Center, Cyprus Institute, 20 Kavafi St., Nicosia 2121 (Cyprus); Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Ave., Cambridge, Massachusetts 02139 (United States)
2015-08-21
We apply Thermostatted Ring Polymer Molecular Dynamics (TRPMD), a recently proposed approximate quantum dynamics method, to the computation of thermal reaction rates. Its short-time transition-state theory limit is identical to rigorous quantum transition-state theory, and we find that its long-time limit is independent of the location of the dividing surface. TRPMD rate theory is then applied to one-dimensional model systems, the atom-diatom bimolecular reactions H + H{sub 2}, D + MuH, and F + H{sub 2}, and the prototypical polyatomic reaction H + CH{sub 4}. Above the crossover temperature, the TRPMD rate is virtually invariant to the strength of the friction applied to the internal ring-polymer normal modes, and beneath the crossover temperature the TRPMD rate generally decreases with increasing friction, in agreement with the predictions of Kramers theory. We therefore find that TRPMD is approximately equal to, or less accurate than, ring polymer molecular dynamics for symmetric reactions, and for certain asymmetric systems and friction parameters closer to the quantum result, providing a basis for further assessment of the accuracy of this method.
Effect of Conceptual Change Approach on Students' Understanding of Reaction Rate Concepts
Kingir, Sevgi; Geban, Omer
2012-01-01
The purpose of the present study was to investigate the effect of conceptual change text oriented instruction compared to traditional instruction on 10th grade students' understanding of reaction rate concepts. 45 students from two classes of the same teacher in a public high school participated in this study. Students in the experimental group…
The Effect of Conceptual Change Pedagogy on Students' Conceptions of Rate of Reaction
Calik, Muammer; Kolomuc, Ali; Karagolge, Zafer
2010-01-01
This paper reports on an investigation of the effect of conceptual change pedagogy on students' conceptions of "rate of reaction" concepts. The study used a pre-test/post-test non-equivalent comparison group design approach and the sample consisted of 72 Turkish grade-11 students (aged 16-18 years) selected from two intact classrooms.…
Generalization of the Activated Complex Theory of Reaction Rates. II. Classical Mechanical Treatment
Marcus, R. A.
1964-01-01
In its usual classical form activated complex theory assumes a particular expression for the kinetic energy of the reacting system -- one associated with a rectilinear motion along the reaction coordinate. The derivation of the rate expression given in the present paper is based on the general kinetic energy expression.
Probing the Rate-Determining Step of the Claisen-Schmidt Condensation by Competition Reactions
Mak, Kendrew K. W.; Chan, Wing-Fat; Lung, Ka-Ying; Lam, Wai-Yee; Ng, Weng-Cheong; Lee, Siu-Fung
2007-01-01
Competition experiments are a useful tool for preliminary study of the linear free energy relationship of organic reactions. This article describes a physical organic experiment for upper-level undergraduates to identify the rate-determining step of the Claisen-Schmidt condensation of benzaldehyde and acetophenone by studying the linear free…
Automated Prediction of Catalytic Mechanism and Rate Law Using Graph-Based Reaction Path Sampling.
Habershon, Scott
2016-04-12
In a recent article [ J. Chem. Phys. 2015 , 143 , 094106 ], we introduced a novel graph-based sampling scheme which can be used to generate chemical reaction paths in many-atom systems in an efficient and highly automated manner. The main goal of this work is to demonstrate how this approach, when combined with direct kinetic modeling, can be used to determine the mechanism and phenomenological rate law of a complex catalytic cycle, namely cobalt-catalyzed hydroformylation of ethene. Our graph-based sampling scheme generates 31 unique chemical products and 32 unique chemical reaction pathways; these sampled structures and reaction paths enable automated construction of a kinetic network model of the catalytic system when combined with density functional theory (DFT) calculations of free energies and resultant transition-state theory rate constants. Direct simulations of this kinetic network across a range of initial reactant concentrations enables determination of both the reaction mechanism and the associated rate law in an automated fashion, without the need for either presupposing a mechanism or making steady-state approximations in kinetic analysis. Most importantly, we find that the reaction mechanism which emerges from these simulations is exactly that originally proposed by Heck and Breslow; furthermore, the simulated rate law is also consistent with previous experimental and computational studies, exhibiting a complex dependence on carbon monoxide pressure. While the inherent errors of using DFT simulations to model chemical reactivity limit the quantitative accuracy of our calculated rates, this work confirms that our automated simulation strategy enables direct analysis of catalytic mechanisms from first principles.
Gray, Patrick J. [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States); Department of Chemistry, The Ohio State University, 120 18th Avenue, Columbus, OH 43210 (United States); Olesik, John W., E-mail: olesik.2@osu.edu [Trace Element Research Laboratory, School of Earth Sciences, The Ohio State University, 125 S. Oval Mall, Columbus, OH 43210 (United States)
2015-03-01
Reaction gas flow rate dependent Ar{sub 2}{sup +} and Ar{sup +} signals are correlated to fundamental kinetic rate coefficients. A simple calculation, assuming that gas exits the reaction cell due only to effusion, is described to estimate the gas pressure in the reaction cell. The value of the product of the kinetic rate constant and the ion residence time in the reaction cell can be determined from experimental measurement of the decrease in an ion signal as a function of reaction gas flow rate. New kinetic rate constants are determined for the reaction of CH{sub 3}F with Ar{sup +} and Ar{sub 2}{sup +}. - Highlights: • How to determine pressure and the product of the kinetic rate constant times the ion residence time in reaction cell • Relate measured ICP-DRC-MS signals versus gas flow rate to kinetic rate constants measured previously using SIFT-MS • Describe how to determine previously unmeasured kinetic rate constants using ICP-DRC-MS.
Astrophysical reaction rate for alpha(alpha n,gamma) sup 9 Be by photodisintegration
Sumiyoshi, K; Goko, S; Kajino, T
2002-01-01
We study the astrophysical reaction rate for the formation of sup 9 Be through the three body reaction alpha(alpha n,gamma). This reaction is one of the key reactions which could bridge the mass gap at A=8 nuclear systems to produce intermediate-to-heavy mass elements in alpha- and neutron-rich environments such as r-process nucleosynthesis in supernova explosions, s-process nucleosynthesis in asymptotic giant branch (AGB) stars, and primordial nucleosynthesis in baryon inhomogeneous cosmological models. To calculate the thermonuclear reaction rate in a wide range of temperatures, we numerically integrate the thermal average of cross sections assuming a two-steps formation through a metastable sup 8 Be, alpha+alpha[rlhar2] sup 8 Be(n,gamma) sup 9 Be. Off-resonant and on-resonant contributions from the ground state in sup 8 Be are taken into account. As input cross section, we adopt the latest experimental data by photodisintegration of sup 9 Be with laser-electron photon beams, which covers all relevant reson...
A randomised controlled trial of two infusion rates to decrease reactions to antivenom.
Geoffrey K Isbister
Full Text Available BACKGROUND: Snake envenoming is a major clinical problem in Sri Lanka, with an estimated 40,000 bites annually. Antivenom is only available from India and there is a high rate of systemic hypersensitivity reactions. This study aimed to investigate whether the rate of infusion of antivenom reduced the frequency of severe systemic hypersensitivity reactions. METHODS AND FINDINGS: This was a randomized comparison trial of two infusion rates of antivenom for treatment of non-pregnant adult patients (>14 y with snake envenoming in Sri Lanka. Snake identification was by patient or hospital examination of dead snakes when available and confirmed by enzyme-immunoassay for Russell's viper envenoming. Patients were blindly allocated in a 11 randomisation schedule to receive antivenom either as a 20 minute infusion (rapid or a two hour infusion (slow. The primary outcome was the proportion with severe systemic hypersensitivity reactions (grade 3 by Brown grading system within 4 hours of commencement of antivenom. Secondary outcomes included the proportion with mild/moderate hypersensitivity reactions and repeat antivenom doses. Of 1004 patients with suspected snakebites, 247 patients received antivenom. 49 patients were excluded or not recruited leaving 104 patients allocated to the rapid antivenom infusion and 94 to the slow antivenom infusion. The median actual duration of antivenom infusion in the rapid group was 20 min (Interquartile range[IQR]:20-25 min versus 120 min (IQR:75-120 min in the slow group. There was no difference in severe systemic hypersensitivity reactions between those given rapid and slow infusions (32% vs. 35%; difference 3%; 95%CI:-10% to +17%;p = 0.65. The frequency of mild/moderate reactions was also similar. Similar numbers of patients in each arm received further doses of antivenom (30/104 vs. 23/94. CONCLUSIONS: A slower infusion rate would not reduce the rate of severe systemic hypersensitivity reactions from current high
α-Terpineol reactions with the nitrate radical: Rate constant and gas-phase products
Jones, Brian T.; Ham, Jason E.
The bimolecular rate constant of k rad +α-terpineol (16 ± 4) × 10 -12 cm 3 molecule -1 s -1 was measured using the relative rate technique for the reaction of the nitrate radical (NO 3rad ) with α-terpineol (2-(4-methyl-1-cyclohex-3-enyl)propan-2-ol) at 297 ± 3 K and 1 atmosphere total pressure. To more clearly define part of α-terpineol's indoor environment degradation mechanism, the products of α-terpineol + NO 3rad reaction were investigated. The identified reaction products were: acetone, glyoxal (HC( dbnd O)C( dbnd O)H), and methylglyoxal (CH 3C( dbnd O)C( dbnd O)H). The use of derivatizing agents O-(2,3,4,5,6-pentafluorobenzyl)hydroxylamine (PFBHA) and N, O-bis(trimethylsilyl) trifluoroacetamide (BSTFA) were used to propose the other major reaction products: 6-hydroxyhept-5-en-2-one, 4-(1-hydroxy-1-methylethyl)-1-methyl-2-oxocyclohexyl nitrate, 5-(1-hydroxy-1-methylethyl)-2-oxocyclohexyl nitrate, 1-formyl-5-hydroxy-4-(hydroxymethyl)-1,5-dimethylhexyl nitrate, and 1,4-diformyl-5-hydroxy-1,5-dimethylhexyl nitrate. The elucidation of these products was facilitated by mass spectrometry of the derivatized reaction products coupled with plausible α-terpineol + NO 3rad reaction mechanisms based on previously published volatile organic compound + NO 3rad gas-phase mechanisms. The additional gas-phase products (2,6,6-trimethyltetrahydro-2 H-pyran-2,5-dicarbaldehyde and 2,2-dimethylcyclohexane-1,4-dicarbaldehyde) are proposed to be the result of cyclization through a reaction intermediate.
Quantum three-body calculation of the nonresonant triple-\\alpha reaction rate at low temperatures
Ogata, Kazuyuki; Kamimura, Masayasu
2009-01-01
The triple-\\alpha reaction rate is re-evaluated by directly solving the three-body Schroedinger equation. The resonant and nonresonant processes are treated on the same footing using the continuum-discretized coupled-channels method for three-body scattering. Accurate description of the \\alpha-\\alpha nonresonant states significantly quenches the Coulomb barrier between the two-\\alpha's and the third \\alpha particle. Consequently, the \\alpha-\\alpha nonresonant continuum states below the resonance at 92.04 keV, i.e., the ground state of 8Be, give markedly larger contribution at low temperatures than in foregoing studies. We find about 20 orders-of-magnitude enhancement of the triple-\\alpha reaction rate around 10^7 K compared to the rate of the NACRE compilation.
Reaction rates for the s-process neutron source 22Ne+{\\alpha}
Longland, Richard; Karakas, Amanda I
2012-01-01
The 22Ne({\\alpha},n)25Mg reaction is an important source of neutrons for the s-process. In massive stars responsible for the weak component of the s-process, 22Ne({\\alpha},n)25Mg is the dominant source of neutrons, both during core helium burning and in shell carbon burning. For the main s-process component produced in Asymptotic Giant Branch (AGB) stars, the 13C({\\alpha},n)16O reaction is the dominant source of neutrons operating during the interpulse period, with the 22Ne+{\\alpha} source affecting mainly the s-process branchings during a thermal pulse. Rate uncertainties in the competing 22Ne({\\alpha},n)25Mg and 22Ne({\\alpha},{\\gamma})26Mg reactions result in large variations of s-process nucleosynthesis. Here, we present up-to-date and statistically rigorous 22Ne+{\\alpha} reaction rates using recent experimental results and Monte Carlo sampling. Our new rates are used in post-processing nucleosynthesis calculations both for massive stars and AGB stars. We demonstrate that the nucleosynthesis uncertainties ...
Reevaluation of thermonuclear reaction rate of 50Fe(p,gamma)51Co
Zhang, L P; Chai, W D; Hou, S Q; Zhang, L Y
2016-01-01
The thermonuclear rate of the 50Fe(p,gamma)51Co reaction in the Type I X-ray bursts (XRBs) temperature range has been reevaluated based on a recent precise mass measurement at CSRe lanzhou, where the proton separation energy Sp=142+/-77 keV has been determined firstly for the 51Co nucleus. Comparing to the previous theoretical predictions, the experimental Sp value has much smaller uncertainty. Based on the nuclear shell model and mirror nuclear structure information, we have calculated two sets of thermonuclear rates for the 50Fe(p,gamma)51Co reaction by utilizing the experimental Sp value. It shows that the statistical-model calculations are not ideally applicable for this reaction primarily because of the low density of low-lying excited states in 51Co. In this work, we recommend that a set of new reaction rate based on the mirror structure of 51Cr should be incorporated in the future astrophysical network calculations.
Dang, Cuong Cao; Le, Vinh Sy; Gascuel, Olivier; Hazes, Bart; Le, Quang Si
2014-10-24
Amino acid replacement rate matrices are a crucial component of many protein analysis systems such as sequence similarity search, sequence alignment, and phylogenetic inference. Ideally, the rate matrix reflects the mutational behavior of the actual data under study; however, estimating amino acid replacement rate matrices requires large protein alignments and is computationally expensive and complex. As a compromise, sub-optimal pre-calculated generic matrices are typically used for protein-based phylogeny. Sequence availability has now grown to a point where problem-specific rate matrices can often be calculated if the computational cost can be controlled. The most time consuming step in estimating rate matrices by maximum likelihood is building maximum likelihood phylogenetic trees from protein alignments. We propose a new procedure, called FastMG, to overcome this obstacle. The key innovation is the alignment-splitting algorithm that splits alignments with many sequences into non-overlapping sub-alignments prior to estimating amino acid replacement rates. Experiments with different large data sets showed that the FastMG procedure was an order of magnitude faster than without splitting. Importantly, there was no apparent loss in matrix quality if an appropriate splitting procedure is used. FastMG is a simple, fast and accurate procedure to estimate amino acid replacement rate matrices from large data sets. It enables researchers to study the evolutionary relationships for specific groups of proteins or taxa with optimized, data-specific amino acid replacement rate matrices. The programs, data sets, and the new mammalian mitochondrial protein rate matrix are available at http://fastmg.codeplex.com.
Mishra, Manish Kumar; Mukherjee, Arijit; Ramamurty, Upadrasta; Desiraju, Gautam R
2015-11-01
A new monoclinic polymorph, form II (P21/c, Z = 4), has been isolated for 3,4-dimethoxycinnamic acid (DMCA). Its solid-state 2 + 2 photoreaction to the corresponding α-truxillic acid is different from that of the first polymorph, the triclinic form I ([Formula: see text], Z = 4) that was reported in 1984. The crystal structures of the two forms are rather different. The two polymorphs also exhibit different photomechanical properties. Form I exhibits photosalient behavior but this effect is absent in form II. These properties can be explained on the basis of the crystal packing in the two forms. The nanoindentation technique is used to shed further insights into these structure-property relationships. A faster photoreaction in form I and a higher yield in form II are rationalized on the basis of the mechanical properties of the individual crystal forms. It is suggested that both Schmidt-type and Kaupp-type topochemistry are applicable for the solid-state trans-cinnamic acid photodimerization reaction. Form I of DMCA is more plastic and seems to react under Kaupp-type conditions with maximum molecular movements. Form II is more brittle, and its interlocked structure seems to favor Schmidt-type topochemistry with minimum molecular movement.
Nuclear Reaction Rates in a Plasma The Effect of Highly Damped Modes
Opher, M; Opher, Merav; Opher, Reuven
2000-01-01
The fluctuation-dissipation theorem is used to evaluate the screening factor of nuclear reactions due to the electromagnetic fluctuations in a plasma. We show that the commonly used Saltpeter factor is obtained if only fluctuations near the plasma eigenfrequency are assumed to be important (\\omega \\sim \\omega_{pe}\\ll T (\\hbar=k_{B}=1)). By taking into account all the fluctuations, the highly damped ones, with \\omega >\\omega_{pe}, as well as those with \\omega\\leq\\omega_{pe}, we find that nuclear reaction rates are higher than those obtained using the Saltpeter factor, for many interesting plasmas.
Beretta, G. P.; Al-Abbasi, Omar; von Spakovsky, M. R.
2017-04-01
The steepest entropy ascent (SEA) dynamical principle provides a general framework for modeling the dynamics of nonequilibrium (NE) phenomena at any level of description, including the atomistic one. It has recently been shown to provide a precise implementation and meaning to the maximum entropy production principle and to encompass many well-established theories of nonequilibrium thermodynamics into a single unifying geometrical framework. Its original formulation in the framework of quantum thermodynamics (QT) assumes the simplest and most natural Fisher-Rao metric to geometrize from a dynamical standpoint the manifold of density operators, which represent the thermodynamic NE states of the system. This simplest SEAQT formulation is used here to develop a general mathematical framework for modeling the NE time evolution of the quantum state of a chemically reactive mixture at an atomistic level. The method is illustrated for a simple two-reaction kinetic scheme of the overall reaction F +H2⇔HF +F in an isolated tank of fixed volume. However, the general formalism is developed for a reactive system subject to multiple reaction mechanisms. To explicitly implement the SEAQT nonlinear law of evolution for the density operator, both the energy and the particle number eigenvalue problems are set up and solved analytically under the dilute gas approximation. The system-level energy and particle number eigenvalues and eigenstates are used in the SEAQT equation of motion to determine the time evolution of the density operator, thus effectively describing the overall kinetics of the reacting system as it relaxes toward stable chemical equilibrium. The predicted time evolution in the near-equilibrium limit is compared to the reaction rates given by a standard detailed kinetic model so as to extract the single time constant needed by the present SEA model.
Beretta, G P; Al-Abbasi, Omar; von Spakovsky, M R
2017-04-01
The steepest entropy ascent (SEA) dynamical principle provides a general framework for modeling the dynamics of nonequilibrium (NE) phenomena at any level of description, including the atomistic one. It has recently been shown to provide a precise implementation and meaning to the maximum entropy production principle and to encompass many well-established theories of nonequilibrium thermodynamics into a single unifying geometrical framework. Its original formulation in the framework of quantum thermodynamics (QT) assumes the simplest and most natural Fisher-Rao metric to geometrize from a dynamical standpoint the manifold of density operators, which represent the thermodynamic NE states of the system. This simplest SEAQT formulation is used here to develop a general mathematical framework for modeling the NE time evolution of the quantum state of a chemically reactive mixture at an atomistic level. The method is illustrated for a simple two-reaction kinetic scheme of the overall reaction F+H_{2}⇔HF+F in an isolated tank of fixed volume. However, the general formalism is developed for a reactive system subject to multiple reaction mechanisms. To explicitly implement the SEAQT nonlinear law of evolution for the density operator, both the energy and the particle number eigenvalue problems are set up and solved analytically under the dilute gas approximation. The system-level energy and particle number eigenvalues and eigenstates are used in the SEAQT equation of motion to determine the time evolution of the density operator, thus effectively describing the overall kinetics of the reacting system as it relaxes toward stable chemical equilibrium. The predicted time evolution in the near-equilibrium limit is compared to the reaction rates given by a standard detailed kinetic model so as to extract the single time constant needed by the present SEA model.
Rauscher, T
2008-01-01
Nucleosynthesis processes involve reactions on several thousand nuclei, both close to and far off stability. The preparation of reaction rates to be used in astrophysical investigations requires experimental and theoretical input. In this context, two interesting aspects are discussed: (i) the relevant gamma transition energies in astrophysical capture reactions, and (ii) the newly discovered Coulomb suppression of the stellar enhancement factor. The latter makes a number of reactions with negative Q value more favorable for experimental investigation than their inverse reactions, contrary to common belief.
S.L. Butarbutar
2013-08-01
Full Text Available It has been a longstanding issue in the radiation chemistry of water that, even though H2 is a molecular product, its “escape” yield g(H2 increases with increasing temperature. A main source of H2 is the bimolecular reaction of two hydrated electrons (eaq. The temperature dependence of the rate constant of this reaction (k1, measured under alkaline conditions, reveals that the rate constant drops abruptly above ~150°C. Recently, it has been suggested that this temperature dependence should be regarded as being independent of pH and used in high-temperature modeling of near-neutral water radiolysis. However, when this drop in the eaq self-reaction rate constant is included in low (isolated spurs and high (cylindrical tracks linear energy transfer (LET modeling calculations, g(H2 shows a marked downward discontinuity at ~150°C which is not observed experimentally. The consequences of the presence of this discontinuity in g(H2 for both low and high LET radiation are briefly discussed in this communication. It is concluded that the applicability of the sudden drop in k1 observed at ~150°C in alkaline water to near-neutral water is questionable and that further measurements of the rate constant in pure water are highly desirable.
Formulation of a universal first-order rate constant for enzymatic reactions.
Imoto, Taiji
2013-01-01
It is a common practice to employ k(cat)[E]₀/K(m) as a first-order rate constant for the analysis of an enzymatic reaction, where [E]₀ is the total enzyme concentration. I describe in this report a serious shortcoming in analyzing enzymatic reactions when kcat[E]₀/K(m) is employed and show that k(cat)[E]₀/K(m) can only be applied under very limited conditions. I consequently propose the use of a more universal first-order rate constant, k(cat)[ES](K)/[S]₀, where [ES](K) is the initial equilibrium concentration of the ES-complex derived from [E]₀, [S]₀ and K(m). Employing k(cat)[ES](K)/[S]₀ as the first-order rate constant enables all enzymatic reactions to be reasonably simulated under a wide range of conditions, and the catalytic and binding contributions to the rate constant of any enzyme can be determined under any and all conditions.
Rate constant for the reaction SO + BrO yields SO2 + Br
Brunning, J.; Stief, L.
1986-01-01
The rate of the radical-radical reaction SO + BrO yields SO2 + Br has been determined at 298 K in a discharge flow system near 1 torr pressure with detection of SO and BrO via collision-free sampling mass spectrometry. The rate constant was determined using two different methods: measuring the decay of SO radicals in the presence of an excess of BrO and measuring the decay of BrO radicals in excess SO. The results from the two methods are in reasonable agreement and the simple mean of the two values gives the recommended rate constant at 298 K, k = (5.7 + or - 2.0) x 10 to the -11th cu cm/s. This represents the first determination of this rate constant and it is consistent with a previously derived lower limit based on SO2 formation. Comparison is made with other radical-radical reactions involving SO or BrO. The reaction SO + BrO yields SO2 + Br is of interest for models of the upper atmosphere of the earth and provides a potential coupling between atmospheric sulfur and bromine chemistry.
Wu, Junjun
2017-08-03
We report a systematic chemical kinetics study of the H-atom abstractions from ethyl formate (EF) by H, O(3P), CH3, OH, and HO2 radicals. The geometry optimization and frequency calculation of all the species were conducted using the M06 method and the cc-pVTZ basis set. The one-dimensional hindered rotor treatment of the reactants and transition states and the intrinsic reaction coordinate analysis were also performed at the M06/cc-pVTZ level of theory. The relative electronic energies were calculated at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory and further extrapolated to the complete basis set limit. Rate constants for the tittle reactions were calculated over the temperature range of 500‒2500 K by the transition state theory (TST) in conjunction with asymmetric Eckart tunneling effect. In addition, the rate constants of H-abstraction by hydroxyl radical were measured in shock tube experiments at 900‒1321 K and 1.4‒2.0 atm. Our theoretical rate constants of OH + EF → Products agree well with the experimental results within 15% over the experimental temperature range of 900‒1321 K. Branching ratios for the five types of H-abstraction reactions were also determined from their individual site-specific rate constants.
Iftimie, R; Schofield, J P; Iftimie, Radu; Salahub, Dennis; Schofield, Jeremy
2003-01-01
In this article, we propose an efficient method for sampling the relevant state space in condensed phase reactions. In the present method, the reaction is described by solving the electronic Schr\\"{o}dinger equation for the solute atoms in the presence of explicit solvent molecules. The sampling algorithm uses a molecular mechanics guiding potential in combination with simulated tempering ideas and allows thorough exploration of the solvent state space in the context of an ab initio calculation even when the dielectric relaxation time of the solvent is long. The method is applied to the study of the double proton transfer reaction that takes place between a molecule of acetic acid and a molecule of methanol in tetrahydrofuran. It is demonstrated that calculations of rates of chemical transformations occurring in solvents of medium polarity can be performed with an increase in the cpu time of factors ranging from 4 to 15 with respect to gas-phase calculations.
Lamia, L. [Dipartimento di Fisica e Astronomia, Università degli Studi di Catania, Catania (Italy); Spitaleri, C. [Dipartimento di Fisica e Astronomia, Università degli Studi di Catania, Catania, Italy and INFN-Laboratori Nazionali del Sud, Catania (Italy); La Cognata, M.; Palmerini, S.; Sergi, M. L. [INFN-Laboratori Nazionali del Sud, Catania (Italy); Puglia, S. M. R. [INFN-Laboratori Nazionali del Sud, Catania, Italy and Dipartimento di Fisica e Astronomia, Università degli Studi di Catania, Catania (Italy)
2015-02-24
Experimental nuclear astrophysics aims at determining the reaction rates for astrophysically relevant reactions at their Gamow energies. For charged-particle induced reactions, the access to these energies is usually hindered, in direct measurements, by the presence of the Coulomb barrier between the interacting particles or by electron screening effects, which make hard the determination of the bare-nucleus S(E)-factor of interest for astrophysical codes. The use of the Trojan Horse Method (THM) appears as one of the most suitable tools for investigating nuclear processes of interest for astrophysics. Here, in view of the recent TH measurements, the main destruction channels for deuterium ({sup 2}H), for the two lithium {sup 6,7}Li isotopes, for the {sup 9}Be and the one for the two boron {sup 10,11}B isotopes will be discussed.
Reaction Rate Distributions and Ratios in FR0 Assemblies 1, 2 and 3
Andersson, T.L.
1966-06-15
The spatial distribution of different reaction rates and reaction ratios in Assemblies 1, 2 and 3 of the fast reactor FR0 was measured by fission chamber scans and foil activation technique. Assemblies 1 and 2 had cores of undiluted fuel (uranium metal enriched to 20 % U{sup 235}) while the core of Assembly 3 was diluted with about 30 vol. % graphite. All the systems had a thick copper reflector, The experimental results were compared with calculated values obtained from DSN and TDC multigroup spectra and group cross-section sets for the reactions. Good agreement between experiment and calculations is generally obtained in the core region but in the reflector the neutron spectrum is calculated too hard.
Ge, Hao; Qian, Hong
2017-01-01
This paper studies a mathematical formalism of nonequilibrium thermodynamics for chemical reaction models with N species, M reactions, and general rate law. We establish a mathematical basis for J. W. Gibbs' macroscopic chemical thermodynamics under G. N. Lewis' kinetic law of entire equilibrium (detailed balance in nonlinear chemical kinetics). In doing so, the equilibrium thermodynamics is then naturally generalized to nonequilibrium settings without detailed balance. The kinetic models are represented by a Markovian jumping process. A generalized macroscopic chemical free energy function and its associated balance equation with nonnegative source and sink are the major discoveries. The proof is based on the large deviation principle of this type of Markov processes. A general fluctuation dissipation theorem for stochastic reaction kinetics is also proved. The mathematical theory illustrates how a novel macroscopic dynamic law can emerges from the mesoscopic kinetics in a multi-scale system.
Electron capture rates in stars studied with heavy ion charge exchange reactions
Bertulani, C A
2015-01-01
Indirect methods using nucleus-nucleus reactions at high energies (here, high energies mean $\\sim$ 50 MeV/nucleon and higher) are now routinely used to extract information of interest for nuclear astrophysics. This is of extreme relevance as many of the nuclei involved in stellar evolution are short-lived. Therefore, indirect methods became the focus of recent studies carried out in major nuclear physics facilities. Among such methods, heavy ion charge exchange is thought to be a useful tool to infer Gamow-Teller matrix elements needed to describe electron capture rates in stars and also double beta-decay experiments. In this short review, I provide a theoretical guidance based on a simple reaction model for charge exchange reactions.
Learned cardiac control with heart rate biofeedback transfers to emotional reactions.
Nathalie Peira
Full Text Available Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could decrease heart rate reactivity when later exposed to negative arousing pictures without biofeedback. These findings suggest that (i short lasting biofeedback training improves heart rate regulation and (ii the learned ability transfers to emotion challenging situations without biofeedback. Thus, heart rate biofeedback training may enable regulation of bodily aspects of emotion also when feedback is not available.
Learned cardiac control with heart rate biofeedback transfers to emotional reactions.
Peira, Nathalie; Pourtois, Gilles; Fredrikson, Mats
2013-01-01
Emotions involve subjective feelings, action tendencies and physiological reactions. Earlier findings suggest that biofeedback might provide a way to regulate the physiological components of emotions. The present study investigates if learned heart rate regulation with biofeedback transfers to emotional situations without biofeedback. First, participants learned to decrease heart rate using biofeedback. Then, inter-individual differences in the acquired skill predicted how well they could decrease heart rate reactivity when later exposed to negative arousing pictures without biofeedback. These findings suggest that (i) short lasting biofeedback training improves heart rate regulation and (ii) the learned ability transfers to emotion challenging situations without biofeedback. Thus, heart rate biofeedback training may enable regulation of bodily aspects of emotion also when feedback is not available.
Atchley, Adam L; Navarre-Sitchler, Alexis K; Maxwell, Reed M
2014-09-01
The role of coupled physical and geochemical heterogeneities in hydro-geochemical transport is investigated by simulating three-dimensional transport in a heterogeneous system with kinetic mineral reactions. Ensembles of 100 physically heterogeneous realizations were simulated for three geochemical conditions: 1) spatially homogeneous reactive mineral surface area, 2) reactive surface area positively correlated to hydraulic heterogeneity, and 3) reactive surface area negatively correlated to hydraulic heterogeneity. Groundwater chemistry and the corresponding effective reaction rates were calculated at three transverse planes to quantify differences in plume evolution due to heterogeneity in mineral reaction rates and solute residence time (τ). The model is based on a hypothetical CO2 intrusion into groundwater from a carbon capture utilization and storage (CCUS) operation where CO2 dissolution and formation of carbonic acid created geochemical dis-equilibrium between fluids and the mineral galena that resulted in increased aqueous lead (Pb(2+)) concentrations. Calcite dissolution buffered the pH change and created conditions of galena oversaturation, which then reduced lead concentrations along the flow path. Near the leak kinetic geochemical reactions control the release of solutes into the fluid, but further along the flow path mineral solubility controls solute concentrations. Simulation results demonstrate the impact of heterogeneous distribution of geochemical reactive surface area in coordination with physical heterogeneity on the effective reaction rate (Krxn,eff) and Pb(2+) concentrations within the plume. Dissimilarities between ensemble Pb(2+) concentration and Krxn,eff are attributed to how geochemical heterogeneity affects the time (τeq) and therefore advection distance (Leq) required for the system to re-establish geochemical equilibrium. Only after geochemical equilibrium is re-established, Krxn,eff and Pb(2+) concentrations are the same for all
Rate parameters for the reaction of atomic hydrogen with dimethyl ether and dimethyl sulfide
Lee, J. H.; Machen, R. C.; Nava, D. F.; Stief, L. J.
1981-03-01
Absolute rate constants for the reaction of atomic hydrogen with dimethyl ether (DME) and dimethyl sulfide (DMS) were obtained using the flash photolysis-resonance fluorescence technique. Under conditions where secondary reactions are avoided, rate constants for the H+DME reaction over the temperature range 273-426 K are well represented by the Arrhenius expression k1=(4.38±0.59)×10-12 exp(-1956±43/T) cm3 molecule-1 s-1. The corresponding Arrhenius expression for the H+DMS reaction over the temperature range 212-500 K is k2=(1.30±0.43)×10-11exp(-1118±81/T) cm3 molecule-1 s-1. The Arrhenius plot for k2 shows signs of curvature, however, and separate Arrhenius expressions are derived for the data above and below room temperature. These results are discussed and comparisons are made with previous determinations which employed flow discharge and product analysis techniques.
Transition path sampling with quantum/classical mechanics for reaction rates.
Gräter, Frauke; Li, Wenjin
2015-01-01
Predicting rates of biochemical reactions through molecular simulations poses a particular challenge for two reasons. First, the process involves bond formation and/or cleavage and thus requires a quantum mechanical (QM) treatment of the reaction center, which can be combined with a more efficient molecular mechanical (MM) description for the remainder of the system, resulting in a QM/MM approach. Second, reaction time scales are typically many orders of magnitude larger than the (sub-)nanosecond scale accessible by QM/MM simulations. Transition path sampling (TPS) allows to efficiently sample the space of dynamic trajectories from the reactant to the product state without an additional biasing potential. We outline here the application of TPS and QM/MM to calculate rates for biochemical reactions, by means of a simple toy system. In a step-by-step protocol, we specifically refer to our implementation within the MD suite Gromacs, which we have made available to the research community, and include practical advice on the choice of parameters.
Greene, Samuel M; Shan, Xiao; Clary, David C
2016-06-28
Semiclassical Transition State Theory (SCTST), a method for calculating rate constants of chemical reactions, offers gains in computational efficiency relative to more accurate quantum scattering methods. In full-dimensional (FD) SCTST, reaction probabilities are calculated from third and fourth potential derivatives along all vibrational degrees of freedom. However, the computational cost of FD SCTST scales unfavorably with system size, which prohibits its application to larger systems. In this study, the accuracy and efficiency of 1-D SCTST, in which only third and fourth derivatives along the reaction mode are used, are investigated in comparison to those of FD SCTST. Potential derivatives are obtained from numerical ab initio Hessian matrix calculations at the MP2/cc-pVTZ level of theory, and Richardson extrapolation is applied to improve the accuracy of these derivatives. Reaction barriers are calculated at the CCSD(T)/cc-pVTZ level. Results from FD SCTST agree with results from previous theoretical and experimental studies when Richardson extrapolation is applied. Results from our implementation of 1-D SCTST, which uses only 4 single-point MP2/cc-pVTZ energy calculations in addition to those for conventional TST, agree with FD results to within a factor of 5 at 250 K. This degree of agreement and the efficiency of the 1-D method suggest its potential as a means of approximating rate constants for systems too large for existing quantum scattering methods.
Badra, Jihad
2014-01-01
Reaction rate constants of the reaction of four large ketones with hydroxyl (OH) are investigated behind reflected shock waves using OH laser absorption. The studied ketones are isomers of hexanone and include 2-hexanone, 3-hexanone, 3-methyl-2-pentanone, and 4-methl-2-pentanone. Rate constants are measured under pseudo-first-order kinetics at temperatures ranging from 866 K to 1375 K and pressures near 1.5 atm. The reported high-temperature rate constant measurements are the first direct measurements for these ketones under combustion-relevant conditions. The effects of the position of the carbonyl group (CO) and methyl (CH3) branching on the overall rate constant with OH are examined. Using previously published data, rate constant expressions covering, low-to-high temperatures, are developed for acetone, 2-butanone, 3-pentanone, and the hexanone isomers studied here. These Arrhenius expressions are used to devise rate rules for H-abstraction from various sites. Specifically, the current scheme is applied with good success to H-abstraction by OH from a series of n-ketones. Finally, general expressions for primary and secondary site-specific H-abstraction by OH from ketones are proposed as follows (the subscript numbers indicate the number of carbon atoms bonded to the next-nearest-neighbor carbon atom, the subscript CO indicates that the abstraction is from a site next to the carbonyl group (CO), and the prime is used to differentiate different neighboring environments of a methylene group):P1,CO = 7.38 × 10-14 exp(-274 K/T) + 9.17 × 10-12 exp(-2499 K/T) (285-1355 K)S10,CO = 1.20 × 10-11 exp(-2046 K/T) + 2.20 × 10-13 exp(160 K/T) (222-1464 K)S11,CO = 4.50 × 10-11 exp(-3000 K/T) + 8.50 × 10-15 exp(1440 K/T) (248-1302 K)S11′,CO = 3.80 × 10-11 exp(-2500 K/T) + 8.50 × 10-15 exp(1550 K/T) (263-1370 K)S 21,CO = 5.00 × 10-11 exp(-2500 K/T) + 4.00 × 10-13 exp(775 K/T) (297-1376 K) © 2014 the Partner Organisations.
Kim, Daesang
2013-11-01
We have extended reactive flow simulation in pore-network models to include geometric changes in the medium from dissolution effects. These effects include changes in pore volume and reactive surface area, as well as topological changes that open new connections. The computed changes were based upon a mineral map from an X-ray computed tomography image of a sandstone core. We studied the effect of these changes on upscaled (pore-scale to core-scale) reaction rates and compared against the predictions of a continuum model. Specifically, we modeled anorthite and kaolinite reactions under acidic flow conditions during which the anorthite reactions remain far from equilibrium (dissolution only), while the kaolinite reactions can be near-equilibrium. Under dissolution changes, core-scale reaction rates continuously and nonlinearly evolved in time. At higher injection rates, agreement with predictions of the continuum model degraded significantly. For the far-from-equilibrium reaction, our results indicate that the ability to correctly capture the heterogeneity in dissolution changes in the reactive mineral surface area is critical to accurately predict upscaled reaction rates. For the near-equilibrium reaction, the ability to correctly capture the heterogeneity in the saturation state remains critical. Inclusion of a Nernst-Planck term to ensure neutral ionic currents under differential diffusion resulted in at most a 9% correction in upscaled rates.
Gonzalez-Lopezlira, Rosa A; Kroupa, Pavel
2012-01-01
We analyze the relationship between maximum cluster mass, M_max, and surface densities of total gas (Sigma_gas), molecular gas (Sigma_H2) and star formation rate (Sigma_SFR) in the flocculent galaxy M33, using published gas data and a catalog of more than 600 young star clusters in its disk. By comparing the radial distributions of gas and most massive cluster masses, we find that M_max is proportional to Sigma_gas^4.7, M_max is proportional Sigma_H2^1.3, and M_max is proportional to Sigma_SFR^1.0. We rule out that these correlations result from the size of sample; hence, the change of the maximum cluster mass must be due to physical causes.
Hunt, Allen G; Ghanbarian, Behzad
2013-01-01
We apply our theory of conservative solute transport, based on concepts from percolation theory, directly and without modification to reactive solute transport. This theory has previously been shown to predict the observed range of dispersivity values for conservative solute transport over ten orders of magnitude of length scale. We now show that the temporal dependence derived for the solute velocity accurately predicts the time-dependence for the weathering of silicate minerals over nine orders of magnitude of time scale, while its predicted length dependence agrees with data obtained for reaction rates over five orders of magnitude of length scale. In both cases, it is possible to unify lab and field results. Thus, net reaction rates appear to be limited by solute transport velocities. We suggest the possible relevance of our results to landscape evolution of the earth's terrestrial surface.
Reacting gas mixtures in the state-to-state approach: The chemical reaction rates
Kustova, Elena V. [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr., 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M. [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)
2014-12-09
In this work chemically reacting mixtures of viscous flows are analyzed within the framework of Boltzmann equation. By applying a modified Chapman-Enskog method to the system of Boltzmann equations general expressions for the rates of chemical reactions and vibrational energy transitions are determined as functions of two thermodynamic forces: the velocity divergence and the affinity. As an application chemically reacting mixtures of N{sub 2} across a shock wave are studied, where the first lowest vibrational states are taken into account. Here we consider only the contributions from the first four single quantum vibrational-translational energy transitions. It is shown that the contribution to the chemical reaction rate related to the affinity is much larger than that of the velocity divergence.
Reacting gas mixtures in the state-to-state approach: The chemical reaction rates
Kustova, Elena V.; Kremer, Gilberto M.
2014-12-01
In this work chemically reacting mixtures of viscous flows are analyzed within the framework of Boltzmann equation. By applying a modified Chapman-Enskog method to the system of Boltzmann equations general expressions for the rates of chemical reactions and vibrational energy transitions are determined as functions of two thermodynamic forces: the velocity divergence and the affinity. As an application chemically reacting mixtures of N2 across a shock wave are studied, where the first lowest vibrational states are taken into account. Here we consider only the contributions from the first four single quantum vibrational-translational energy transitions. It is shown that the contribution to the chemical reaction rate related to the affinity is much larger than that of the velocity divergence.
Kirkpatrick, Iain; Worrall, David R; Williams, Siân L; Buck, Craig J T; Meseguer, Rafael G
2012-10-01
In this study we have compared energy and electron transfer reactions in termolecular systems using a nanosecond diffuse reflectance laser flash photolysis technique. We have previously investigated these processes on silica gel surfaces for bimolecular systems and electron transfer in termolecular systems. The latter systems involved electron transfer between three arene molecules with azulene acting as a molecular shuttle. In this study we present an alternative electron transfer system using trans β-carotene as an electron donor in order to effectively immobilise all species except the shuttle, providing the first unambiguous evidence for radical ion mobility. In the energy transfer system we use naphthalene, a structural isomer of azulene, as the shuttle, facilitating energy transfer from a selectively excited benzophenone sensitiser to 9-cyanoanthracene. Bimolecular rate constants for all of these processes have been measured and new insights into the factors determining the rates of these reactions on silica gel have been obtained.
Usami, S.; Suzuoki, Z.; Deshimaru, T. [Monju Construction Office, Japan Nuclear Cycle Development Institute, Fukui-ken (Japan); Nakashima, F. [Tsuruga head Office, Japan Nuclear Cycle Development Institute, Fukui-ken (Japan)
2001-07-01
Monju is a prototype fast breeder reactor designed to have an output of 280 MW (714 MWt), fueled with mixed oxides of plutonium and uranium and cooled by liquid sodium. The principal data on plant design and performance are shown in Table 1. Monju attained initial criticality in April 1994 and the reactor physics tests were carried out from May through November 1994. The reaction rate distribution measurement by the foil activation method was one of these tests and was carried out in order to verify the core performance and to contribute to the development of the core design methods. On the basis of the reaction rate measurement data, the Monju initial core breeding ratio and the power distribution were evaluated. (author)
The 23Na({\\alpha},p) 26Mg reaction rate at astrophysically relevant energies
Howard, A M; Fynbo, H O U; Kirsebom, O S; Laursen, K L; Diget, C Aa; Hubbard, N J
2015-01-01
The production of 26 Al in massive stars is sensitive to the 23 Na(a,p) 26 Mg cross section. Recent experimental data suggest the currently recommended cross sections are underestimated by a factor of 40. We present here differential cross sections for the 23 Na(a,p) 26 Mg reaction measured in the energy range E c.m. = 1.7 - 2.5 MeV. Concurrent measurements of Rutherford scattering provide absolute normalisations which are independent of variations in target properties. Angular distributions were measured for both p 0 and p 1 permitting the determination of total cross sections. The results show no significant deviation from the statistical model calculations upon which the recommended rates are based. We therefore retain the previous recommendation without the increase in cross section and resulting stellar reaction rates of a factor of 40, impacting on the 26 Al yield from massive stars by more than a factor of three.
Rate of diffusion-limited reactions for a fractal aggregate of reactive spheres
Tseng, Chin-Yao; Tsao, Heng-Kwong
2002-08-01
We study the reaction rate for a fractal cluster of perfectly absorbing, stationary spherical sinks in a medium containing a mobile reactant. The effectiveness factor eta, which is defined as the ratio of the total reaction rate of the cluster to that without diffusional interactions, is calculated. The scaling behavior of eta is derived for arbitrary fractal dimension based on the Kirkwood-Riseman approximation. The asymptotic as well as the finite size scaling of eta are confirmed numerically by the method of multipole expansion, which has been proven to be an excellent approximation. The fractal assembly is made of N spheres with its dimension varying from D1, eta][approx(ln N)-1 for D=1, and eta][approxN0 for D1 the screening effect of diffusive interactions grows with the size, for Ddecays with decreasing D. The conclusion is also applicable to transport phenomena like dissolution, heat conduction, and sedimentation.
Pattison, D I; Davies, Michael Jonathan
2001-01-01
, absolute second-order rate constants for the reactions of HOCl with protein side chains, model compounds, and backbone amide (peptide) bonds have been determined at physiological pH values. The reactivity of HOCl with potential reactive sites in proteins is summarized by the series: Met (3.8 x 10(7) M(-1......) x s(-1)) > backbone amides (10-10(-3) M(-1) x s(-1)) > Gln(0.03 M(-1) x s(-1)) approximately Asn (0.03 M(-1) x s(-1)). The rate constants for reaction of HOCl with backbone amides (peptide bonds) vary by 4 orders of magnitude with uncharged peptide bonds reacting more readily with HOCl than those...
Reactivity and reaction rate studies on the fourth loading of ZENITH
Cameron, I.R.; Freemantle, R.G.; Reed, D.L.; Wilson, D.J. [General Reactor Physics Division, Atomic Energy Establishment, Winfrith, Dorchester, Dorset (United Kingdom)] (and others)
1963-08-15
The determination of the excess reactivity, control rod worths, prompt neutron lifetime, flux fine structure, and reaction rates of various nuclides for the fourth loading of the heated zero energy reactor ZENITH is described. The core contains 7.76 kg of U235, giving a carbon/U235 atom ratio of 7578, and forms the most dilute of the range studied. Comparisons of the experimental results with calculations using multigroup diffusion codes are presented. (author)
Gian Paolo Beretta
2008-08-01
Full Text Available A rate equation for a discrete probability distribution is discussed as a route to describe smooth relaxation towards the maximum entropy distribution compatible at all times with one or more linear constraints. The resulting dynamics follows the path of steepest entropy ascent compatible with the constraints. The rate equation is consistent with the Onsager theorem of reciprocity and the fluctuation-dissipation theorem. The mathematical formalism was originally developed to obtain a quantum theoretical unification of mechanics and thermodinamics. It is presented here in a general, non-quantal formulation as a part of an effort to develop tools for the phenomenological treatment of non-equilibrium problems with applications in engineering, biology, sociology, and economics. The rate equation is also extended to include the case of assigned time-dependences of the constraints and the entropy, such as for modeling non-equilibrium energy and entropy exchanges.
Beretta, Gian P.
2008-09-01
A rate equation for a discrete probability distribution is discussed as a route to describe smooth relaxation towards the maximum entropy distribution compatible at all times with one or more linear constraints. The resulting dynamics follows the path of steepest entropy ascent compatible with the constraints. The rate equation is consistent with the Onsager theorem of reciprocity and the fluctuation-dissipation theorem. The mathematical formalism was originally developed to obtain a quantum theoretical unification of mechanics and thermodinamics. It is presented here in a general, non-quantal formulation as a part of an effort to develop tools for the phenomenological treatment of non-equilibrium problems with applications in engineering, biology, sociology, and economics. The rate equation is also extended to include the case of assigned time-dependences of the constraints and the entropy, such as for modeling non-equilibrium energy and entropy exchanges.
Sutiani, Ani; Silitonga, Mei Y.
2017-08-01
This research focused on the effect of learning models and emotional intelligence in students' chemistry learning outcomes on reaction rate teaching topic. In order to achieve the objectives of the research, with 2x2 factorial research design was used. There were two factors tested, namely: the learning models (factor A), and emotional intelligence (factor B) factors. Then, two learning models were used; problem-based learning/PBL (A1), and project-based learning/PjBL (A2). While, the emotional intelligence was divided into higher and lower types. The number of population was six classes containing 243 grade X students of SMAN 10 Medan, Indonesia. There were 15 students of each class were chosen as the sample of the research by applying purposive sampling technique. The data were analyzed by applying two-ways analysis of variance (2X2) at the level of significant α = 0.05. Based on hypothesis testing, there was the interaction between learning models and emotional intelligence in students' chemistry learning outcomes. Then, the finding of the research showed that students' learning outcomes in reaction rate taught by using PBL with higher emotional intelligence is higher than those who were taught by using PjBL. There was no significant effect between students with lower emotional intelligence taught by using both PBL and PjBL in reaction rate topic. Based on the finding, the students with lower emotional intelligence were quite hard to get in touch with other students in group discussion.
Experimental results for studies of the 40Ca(α,γ)44Ti reaction rates
Robertson, Daniel; Becker, Hans-Werner; Bowers, Matt; Collon, Philippe; Goerres, Joachim; Lu, Wenting; Schmitt, Chris; Wiescher, Michael
2011-10-01
Observational studies of galactic γ emitters such as 44Ti have highlighted their use in nucleosynthesis studies of massive stars in their late stage stellar evolution and final explosive demise in core collapse supernova events. Models used in the simulation of such γ emitters rely heavily upon reliable reaction rates for both the creation and annihilation of these isotopes over large temperature ranges. The production of 44Ti mainly through the 40Ca(α,γ)44Ti reaction is thought to take place primarily in the α-rich freeze out phase of a core collapse supernova. However, current supernova models predict lower 44Ti to 56Ni ratios than observed, creating a need for more information about its production mechanism. A number of previous studies include prompt γ-ray measurements, recoil mass separator experiments and the use of AMS, all giving greatly different reaction rates. Aiding in the refinement of these needed rates, the results of experiments at the DTL, Bochum and NSL, Notre Dame will be presented against the backdrop of these previous measurements. Work supported by grant # 0758100 and # 0822648.
Quantum Tunneling Rates of Gas-Phase Reactions from On-the-Fly Instanton Calculations.
Beyer, Adrian N; Richardson, Jeremy O; Knowles, Peter J; Rommel, Judith; Althorpe, Stuart C
2016-11-03
The instanton method obtains approximate tunneling rates from the minimum-action path (known as the instanton) linking reactants to the products at a given temperature. An efficient way to find the instanton is to search for saddle-points on the ring-polymer potential surface, which is obtained by expressing the quantum Boltzmann operator as a discrete path-integral. Here we report a practical implementation of this ring-polymer form of instanton theory into the Molpro electronic-structure package, which allows the rates to be computed on-the-fly, without the need for a fitted analytic potential-energy surface. As a test case, we compute tunneling rates for the benchmark H + CH4 reaction, showing how the efficiency of the instanton method allows the user systematically to converge the tunneling rate with respect to the level of electronic-structure theory.
Reaction Rate Theory in Coordination Number Space: An Application to Ion Solvation
Roy, Santanu; Baer, Marcel D.; Mundy, Christopher J.; Schenter, Gregory K.
2016-04-14
Understanding reaction mechanisms in many chemical and biological processes require application of rare event theories. In these theories, an effective choice of a reaction coordinate to describe a reaction pathway is essential. To this end, we study ion solvation in water using molecular dynamics simulations and explore the utility of coordination number (n = number of water molecules in the first solvation shell) as the reaction coordinate. Here we compute the potential of mean force (W(n)) using umbrella sampling, predicting multiple metastable n-states for both cations and anions. We find with increasing ionic size, these states become more stable and structured for cations when compared to anions. We have extended transition state theory (TST) to calculate transition rates between n-states. TST overestimates the rate constant due to solvent-induced barrier recrossings that are not accounted for. We correct the TST rates by calculating transmission coefficients using the reactive flux method. This approach enables a new way of understanding rare events involving coordination complexes. We gratefully acknowledge Liem Dang and Panos Stinis for useful discussion. This research used resources of the National Energy Research Scientific Computing Center, a DOE Office of Science User Facility supported by the Office of Science of the U.S. Department of Energy under Contract No. DE-AC02-05CH11231. SR, CJM, and GKS were supported by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences, and Biosciences. MDB was supported by MS3 (Materials Synthesis and Simulation Across Scales) Initiative, a Laboratory Directed Research and Development Program at Pacific Northwest National Laboratory (PNNL). PNNL is a multiprogram national laboratory operated by Battelle for the U.S. Department of Energy.
Lovell, Dale I; Cuneo, Ross; Gass, Greg C
2010-06-01
This study examined the effect of strength training (ST) and short-term detraining on maximum force and rate of force development (RFD) in previously sedentary, healthy older men. Twenty-four older men (70-80 years) were randomly assigned to a ST group (n = 12) and C group (control, n = 12). Training consisted of three sets of six to ten repetitions on an incline squat at 70-90% of one repetition maximum three times per week for 16 weeks followed by 4 weeks of detraining. Regional muscle mass was assessed before and after training by dual-energy X-ray absorptiometry. Training increased RFD, maximum bilateral isometric force, and force in 500 ms, upper leg muscle mass and strength above pre-training values (14, 25, 22, 7, 90%, respectively; P force and RFD of older men. However, older individuals may lose some neuromuscular performance after a period of short-term detraining and that resistance exercise should be performed on a regular basis to maintain training adaptations.
Miles, A. M.
1982-01-01
The effectiveness of powdered semiconductor materials in photocatalyzing candidate redox reactions was investigated. The rate of the photocatalyzed oxidation of cyanide at platinized TiO2 was studied. The extent of the cyanide reaction was followed directly using an electroanalytical method (i.e. differential pulse polarography). Experiments were performed in natural or artificial light. A comparison was made of kinetic data obtained for photocatalysis at platinized powders with rate data for nonplatinized powders.
Christensen, H.; Kiil, Søren; Dam-Johansen, Kim;
2006-01-01
The Buchwald-Hartwig amination reaction between p-bromotoluene and piperazine in the presence of the homogeneous catalytic system Pd(dba)(2)/(+/-)-BINAP and the base NaO-t-Bu was investigated in two different classes of solvents: aprotic, nonpolar and aprotic, polar. The reaction was carried out...... solvent for the Buchwald-Hartwig amination reaction under the conditions applied was m-xylene....
Nuclear halo effect on nucleon capture reaction rates at stellar energies
Liu Zu-Hua; Zhou Hong-Yu
2005-01-01
The capture cross sections at stellar energies are very difficult to measure directly. Hence, data are usually evaluated by using indirect methods or extrapolations from the experimental data obtained at the lowest possible energies. The asymptotic normalization coefficient (ANC) approach of the transfer reactions provides a reliable way for the determination of the capture cross sections at stellar energies. By virtue of its reliability, we have calculated the capture cross sections of the 10Be(n,γ)11Be reaction by using nuclear ANC method. 11Be is a well-known neutron halo nucleus with two weakly bound states. As a typical example, we have shown that the radiative cross sections for a nucleon captured into a halo state are obviously enhanced. The enormous enhancement of the capture cross section is just due to the large overlap of the incident neutron wave with the extended tail of the halo. The 10Be(n,γ)11Be capture reaction is involved in the inhomogeneous big-bang nucleosynthesis. We have evaluated its reaction rates at stellar energies with the nuclear ANC method.
Naine, Tarun Bharath; Gundawar, Manoj Kumar
2017-09-01
We demonstrate a very powerful correlation between the discrete probability of distances of neighboring cells and thermal wave propagation rate, for a system of cells spread on a one-dimensional chain. A gamma distribution is employed to model the distances of neighboring cells. In the absence of an analytical solution and the differences in ignition times of adjacent reaction cells following non-Markovian statistics, invariably the solution for thermal wave propagation rate for a one-dimensional system with randomly distributed cells is obtained by numerical simulations. However, such simulations which are based on Monte-Carlo methods require several iterations of calculations for different realizations of distribution of adjacent cells. For several one-dimensional systems, differing in the value of shaping parameter of the gamma distribution, we show that the average reaction front propagation rates obtained by a discrete probability between two limits, shows excellent agreement with those obtained numerically. With the upper limit at 1.3, the lower limit depends on the non-dimensional ignition temperature. Additionally, this approach also facilitates the prediction of burning limits of heterogeneous thermal mixtures. The proposed method completely eliminates the need for laborious, time intensive numerical calculations where the thermal wave propagation rates can now be calculated based only on macroscopic entity of discrete probability.
Liao, Fei; Zhu, Xiao-Yun; Wang, Yong-Mei; Zuo, Yu-Ping
2005-01-31
The estimation of enzyme kinetic parameters by nonlinear fitting reaction curve to the integrated Michaelis-Menten rate equation ln(S(0)/S)+(S(0)-S)/K(m)=(V(m)/K(m))xt was investigated and compared to that by fitting to (S(0)-S)/t=V(m)-K(m)x[ln(S(0)/S)/t] (Atkins GL, Nimmo IA. The reliability of Michaelis-Menten constants and maximum velocities estimated by using the integrated Michaelis-Menten equation. Biochem J 1973;135:779-84) with uricase as the model. Uricase reaction curve was simulated with random absorbance error of 0.001 at 0.075 mmol/l uric acid. Experimental reaction curve was monitored by absorbance at 293 nm. For both CV and deviation kinetic parameters and applicable for the characterization of enzyme inhibitors.
Astrophysical reaction rates from a symmetry-informed first-principles perspective
Dreyfuss, Alison; Launey, Kristina; Baker, Robert; Draayer, Jerry; Dytrych, Tomas
2017-01-01
With a view toward a new unified formalism for studying bound and continuum states in nuclei, to understand stellar nucleosynthesis from a fully ab initio perspective, we studied the nature of surface α-clustering in 20Ne by considering the overlap of symplectic states with cluster-like states. We compute the spectroscopic amplitudes and factors, α-decay width, and absolute resonance strength - characterizing major contributions to the astrophysical reaction rate through a low-lying 1- resonant state in 20Ne. As a next step, we consider a fully microscopic treatment for the n+4 He system, based on the successful first-principles No-Core Shell Model/Resonating Group Method (NCSM/RGM) for light nuclei, but with the capability to reach intermediate-mass nuclei. The new model takes advantage of the symmetry-based concept central to the Symmetry-Adapted No-Core Shell Model (SA-NCSM) to reduce computational complexity in physically-informed and methodical way, with sights toward first-principles calculations of rates for important astrophysical reactions, such as the 23 Al(p , γ) 24 Si reaction, believed to have a strong influence on X-ray burst light curves. Supported by the U.S. NSF (OCI-0904874, ACI -1516338) and the U.S. DOE (DE-SC0005248), and benefitted from computing resources provided by Blue Waters and the LSU Center for Computation & Technology.
Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Iron
American Society for Testing and Materials. Philadelphia
2009-01-01
DESIG: E 263 09 ^TITLE: Standard Test Method for Measuring Fast-Neutron Reaction Rates by Radioactivation of Iron ^SIGNUSE: Refer to Guide E 844 for guidance on the selection, irradiation, and quality control of neutron dosimeters. Refer to Practice E 261 for a general discussion of the determination of fast-neutron fluence rate with threshold detectors. Pure iron in the form of foil or wire is readily available and easily handled. Fig. 1 shows a plot of cross section as a function of neutron energy for the fast-neutron reaction 54Fe(n,p)54Mn (1). This figure is for illustrative purposes only to indicate the range of response of the 54Fe(n,p)54Mn reaction. Refer to Guide E 1018 for descriptions of recommended tabulated dosimetry cross sections. 54Mn has a half-life of 312.13 days (3) (2) and emits a gamma ray with an energy of 834.845 keV (5). (2) Interfering activities generated by neutron activation arising from thermal or fast neutron interactions are 2.57878 (46)-h 56Mn, 44.95-d (8) 59Fe, and 5.27...
Malekifarsani, A; Skachek, M A
2009-10-01
shown that the concentrations of the following radionuclides are limited by solubility and precipitate around the waste and buffer: U, Np, Ra, Sm, Zr, Se, Tc, and Pd. The Sensitivity of maximum release rates in case precipitation shows that some nuclides such as Cs-135, Nb-94, Nb-93 m, Zr-93, Sn-126, Th-230, Pu-240, Pu-242, Pu-239, Cm-245, Am-243, Cm-245, U-233, Ac-227, Pb-210, Pa-231 and Th-229 are very little changed in case the maximum release rate from EBS corresponding to eliminate precipitation in buffer material. Some nuclides such as Se-79, Tc-99, Pd-107, Th-232, U-236, U-233, Ra-226, Np-237 U-235, U-234, and U-238 are virtually changed in the maximum release rate compared to case that taking account precipitation. In Sensitivity of maximum release rates in case to taking account stable isotopes (according to the table of inventory) there are only some nuclides with their stable isotopes in the vitrified waste. And calculation shows that Pd-107 and Se-79 are very increase in case eliminate stable isotope. The Sensitivity of maximum release rates in case retardation with sorption shows that some nuclides such as Pu-240, Pu-241, Pu-239, Cm-245, Am-241, Cm-246, and Am-243 are increased in some time in case maximum release rate from EBS corresponding to eliminate retardation in buffer material. Some nuclides such as U-235, U-233 and U-236 have a little decrease in case maximum release because their parents have short live and before decay to their daughter will released from the EBS. If the characteristic time taken for a nuclide to diffuse across the buffer exceeds its half-life, then the release rate of that nuclide from the EBS will be attenuated by radioactive decay. Thus, the retardation of the diffusion process due to sorption tends to reduce the release rates of short-lived nuclides more effectively than for the long-lived ones. For example, release rates of Pu-240, Cm-246 and Am-241, which are relatively short-lived and strongly sorbing, are very small
Arnould, M.; Goriely, S.; Jorissen, A.
1999-07-01
The abundances of the isotopes of the elements from C to Al produced by the non-explosive CNO, NeNa and MgAl modes of hydrogen burning, as well as by helium burning, are calculated with the thermonuclear rates recommended by the European compilation of reaction rates for astrophysics (NACRE). The impact of nuclear physics uncertainties on the derived abundances is discussed in the framework of a simple parametric astrophysical model. These calculations have the virtue of being a guide in the selection of the nuclear uncertainties that have to be duly analyzed in detailed model stars, particularly in order to perform meaningful confrontations between abundance observations and predictions. They are also hoped to help nuclear astrophysicists pinpointing the rate uncertainties that have to be reduced most urgently. An electronic version of this paper, with colour figures, is available at {\\it http://astro.ulb.ac.be}
A reaction-diffusion-based coding rate control mechanism for camera sensor networks.
Yamamoto, Hiroshi; Hyodo, Katsuya; Wakamiya, Naoki; Murata, Masayuki
2010-01-01
A wireless camera sensor network is useful for surveillance and monitoring for its visibility and easy deployment. However, it suffers from the limited capacity of wireless communication and a network is easily overflown with a considerable amount of video traffic. In this paper, we propose an autonomous video coding rate control mechanism where each camera sensor node can autonomously determine its coding rate in accordance with the location and velocity of target objects. For this purpose, we adopted a biological model, i.e., reaction-diffusion model, inspired by the similarity of biological spatial patterns and the spatial distribution of video coding rate. Through simulation and practical experiments, we verify the effectiveness of our proposal.
Luis Eduardo Cruz-Martínez
2014-10-01
Full Text Available Background. The formulas to predict maximum heart rate have been used for many years in different populations. Objective. To verify the significance and the association of formulas of Tanaka and 220-age when compared to real maximum heart rate. Materials and methods. 30 subjects -22 men, 8 women- between 18 and 30 years of age were evaluated on a cycle ergometer and their real MHR values were statistically compared with the values of formulas currently used to predict MHR. Results. The results demonstrate that both Tanaka p=0.0026 and 220-age p=0.000003 do not predict real MHR, nor does a linear association exist between them. Conclusions. Due to the overestimation with respect to real MHR value that these formulas make, we suggest a correction of 6 bpm to the final result. This value represents the median of the difference between the Tanaka value and the real MHR. Both Tanaka (r=0.272 and 220-age (r=0.276 are not adequate predictors of MHR during exercise at the elevation of Bogotá in subjects of 18 to 30 years of age, although more study with a larger sample size is suggested.
Li, Wenjiao; Xue, Yongqiang, E-mail: xyqlw@126.com; Cui, Zixiang
2016-08-15
Surface thermodynamic properties are the fundamental properties of nanomaterials, and these properties depend on the size of nanoparticles. In this paper, relations of molar surface thermodynamic properties and surface heat capacity at constant pressure of nanoparticles with particle size were derived theoretically, and the method of obtaining the surface thermodynamic properties by reaction rate constant was put forward. The reaction of nano-MgO with sodium bisulfate solution was taken as a research system. The influence regularities of the particle size on the surface thermodynamic properties were discussed theoretically and experimentally, which show that the experimental regularities are in accordance with the corresponding theoretical relations. With the decreasing of nanoparticle size, the molar surface thermodynamic properties increase, while the surface heat capacity decreases (the absolute value increases). In addition, the surface thermodynamic properties are linearly related to the reciprocal of nanoparticle diameter, respectively.
Temperature dependence of the absolute rate constant for the reaction of ozone with dimethyl sulfide
WANG Hai-tao; ZHANG Yu-jie; MU Yu-jing
2007-01-01
Absolute rate constants for the reaction of ozone with dimethyl sulfide (DMS) were measured in a 200-L Teflon chamber over the temperature range of 283-353 K. Measurements were carried out using DMS in large excess over ozone of 10 to 1 or greater. Over the indicated temperature range,the data could be fit to the simple Arrhenius expression as KDMS = (9.96±3.61)×10-11exp(-(7309.7±1098.2)/T)cm3/(molecule·s). A compared investigation of the reaction between ozone and ethene had a kc2H4 value of(1.35±0.11)×10-18 cm3/(molecule·s) at room temperature.
Measurement of absolute reaction rates in Be,Pb and Fe spherical systems
LiuRong; ChenYuan; 等
1998-01-01
The absolute reaction rates in Be,Pb and Fe have been measured by using the activation foil technique with different reaction energy thresholds.Thicknesses of Be,Pb and Fe spheres were 5.3,19.1 and 31.9cm.respectively,Eight kinds of activation folis were used for Fe,and four kinds each for Be and Pb,The total experimental er5ror was about 5-7%.The measured results were compared to the values calculated with the 1-D ANISN code and the ENDF/B-VI library data.The average ratio of the experimental to the calculational is less than 7% for Be and Pb,about 5-30% for Fe.
Shaw, A; Takács, I; Pagilla, K R; Murthy, S
2013-10-15
The Monod equation is often used to describe biological treatment processes and is the foundation for many activated sludge models. The Monod equation includes a "half-saturation coefficient" to describe the effect of substrate limitations on the process rate and it is customary to consider this parameter to be a constant for a given system. The purpose of this study was to develop a methodology, and its use to show that the half-saturation coefficient for denitrification is not constant but is in fact a function of the maximum denitrification rate. A 4-step procedure is developed to investigate the dependency of half-saturation coefficients on the maximum rate and two different models are used to describe this dependency: (a) an empirical linear model and (b) a deterministic model based on Fick's law of diffusion. Both models are proved better for describing denitrification kinetics than assuming a fixed K(NO3) at low nitrate concentrations. The empirical model is more utilitarian whereas the model based on Fick's law has a fundamental basis that enables the intrinsic K(NO3) to be estimated. In this study data was analyzed from 56 denitrification rate tests and it was found that the extant K(NO3) varied between 0.07 mgN/L and 1.47 mgN/L (5th and 95th percentile respectively) with an average of 0.47 mgN/L. In contrast to this, the intrinsic K(NO3) estimated for the diffusion model was 0.01 mgN/L which indicates that the extant K(NO3) is greatly influenced by, and mostly describes, diffusion limitations.
High-precision (p,t) reaction measurement to determine Ne-18(alpha,p)Na-21 reaction rates
Matic, A.; van den Berg, A. M.; Harakeh, M. N.; Wörtche, H. J.; Berg, G. P. A.; Couder, M.; Fisker, J. L.; Goerres, J.; LeBlanc, P.; O'Brien, S.; Wiescher, M.; Fujita, K.; Hatanaka, K.; Sakemi, Y.; Shimizu, Y.; Tameshige, Y.; Tamii, A.; Yosoi, M.; Adachi, T.; Fujita, Y.; Shimbara, Y.; Fujita, H.; Wakasa, T.; Hess, P. O.; Brown, B. A.; Schatz, H.
2009-01-01
x-ray bursts are identified as thermonuclear explosions in the outer atmosphere of accreting neutron stars. The thermonuclear runaway is fueled by the alpha p process that describes a sequence of (alpha,p) reactions triggered by the Ne-18(alpha,p)Na-21 breakout reaction from the hot CNO cycles. We
Accurate quantum thermal rate constants for the three-dimensional H+H2 reaction
Park, Tae Jun; Light, J. C.
1989-07-01
The rate constants for the three-dimensional H+H2 reaction on the Liu-Siegbahn-Truhlar-Horowitz (LSTH) surface are calculated using Pack-Parker hyperspherical (APH) coordinates and a C2v symmetry adapted direct product discrete variable representation (DVR). The C2v symmetry decomposition and the parity decoupling on the basis are performed for the internal coordinate χ. The symmetry decomposition results in a block diagonal representation of the flux and Hamiltonian operators. The multisurface flux is introduced to represent the multichannel reactive flux. The eigenvalues and eigenvectors of the J=0 internal Hamiltonian are obtained by sequential diagonalization and truncation. The individual symmetry blocks of the flux operator are propagated by the corresponding blocks of the Hamiltonian, and the J=0 rate constant k0(T) is obtained as a sum of the rate constants calculated for each block. k0(T) is compared with the exact k0(T) obtained from thermal averaging of the J=0 reaction probabilities; the errors are within 5%-20% up to T=1500 K. The sequential diagonalization-truncation method reduces the size of the Hamiltonian greatly, but the resulting Hamiltonian matrix still describes the time evolution very accurately. For the J≠0 rate constant calculations, the truncated internal Hamiltonian eigenvector basis is used to construct reduced (JKJ) blocks of the Hamiltonian. The individual (JKJ) blocks are diagonalized neglecting Coriolis coupling and treating the off-diagonal KJ±2 couplings by second order perturbation theory. The full wave function is parity decoupled. The rate constant is obtained as a sum over J of (2J+1)kJ(T). The time evolution of the flux for J≠0 is again very accurately described to give a well converged rate constant.
Structural and dynamical control of the reaction rate in protein electron transfer
Balabin, Ilya A.
Electron transfer (ET) reactions in proteins are key steps in many vital bioenergetic processes, and the reaction rate is known to be highly sensitive to the protein structure in some cases. For most bioenergetic reactions, as described by the Fermi Golden rule, the rate is proportional to a product of the average square of the effective electronic donor to acceptor coupling and a Franck-Condon factor, which accounts for the nuclear control of the energy gap. The nuclear factor is reasonably well described in Marcus theory and its modifications, and this work is focused on the mechanisms that control the effective coupling. About ten years ago, the Pathways model described for the first time how protein environment may control the effective coupling. In this work, a novel theoretical approach is developed to explore the mechanisms of structural and dynamical control beyond the qualitative level of the Pathways model. In Chapter 1, the assumptions of the Pathways model, its limitations and effects of the structure and the electronic Hamiltonian are investigated for model chain-like bridges using the Dyson's equations. In Chapter II, the framework to explore the sensitivity of the effective coupling to quality of the electronic Hamiltonian, the interference among the dominant pathways and the bridge dynamics is presented. This analysis employs the Green's function technique and includes combined molecular dynamics and electronic structure calculations. Finally, in Chapter III, this framework is tested on the bacterial photosynthetic reaction center, and the mechanisms of the structural and dynamical control for different ET steps are discussed.
Gallis, Michael A; Bond, Ryan B; Torczynski, John R
2009-09-28
Recently proposed molecular-level chemistry models that predict equilibrium and nonequilibrium reaction rates using only kinetic theory and fundamental molecular properties (i.e., no macroscopic reaction-rate information) are investigated for chemical reactions occurring in upper-atmosphere hypersonic flows. The new models are in good agreement with the measured Arrhenius rates for near-equilibrium conditions and with both measured rates and other theoretical models for far-from-equilibrium conditions. Additionally, the new models are applied to representative combustion and ionization reactions and are in good agreement with available measurements and theoretical models. Thus, molecular-level chemistry modeling provides an accurate method for predicting equilibrium and nonequilibrium chemical-reaction rates in gases.
Kinkhabwala, Ali
2013-01-01
The most fundamental problem in statistics is the inference of an unknown probability distribution from a finite number of samples. For a specific observed data set, answers to the following questions would be desirable: (1) Estimation: Which candidate distribution provides the best fit to the observed data?, (2) Goodness-of-fit: How concordant is this distribution with the observed data?, and (3) Uncertainty: How concordant are other candidate distributions with the observed data? A simple unified approach for univariate data that addresses these traditionally distinct statistical notions is presented called "maximum fidelity". Maximum fidelity is a strict frequentist approach that is fundamentally based on model concordance with the observed data. The fidelity statistic is a general information measure based on the coordinate-independent cumulative distribution and critical yet previously neglected symmetry considerations. An approximation for the null distribution of the fidelity allows its direct conversi...
New reaction rates for improved primordial D /H calculation and the cosmic evolution of deuterium
Coc, Alain; Petitjean, Patrick; Uzan, Jean-Philippe; Vangioni, Elisabeth; Descouvemont, Pierre; Iliadis, Christian; Longland, Richard
2015-12-01
Primordial or big bang nucleosynthesis (BBN) is one of the three historically strong evidences for the big bang model. Standard BBN is now a parameter-free theory, since the baryonic density of the Universe has been deduced with an unprecedented precision from observations of the anisotropies of the cosmic microwave background radiation. There is a good agreement between the primordial abundances of 4He, D, 3He, and 7Li deduced from observations and from primordial nucleosynthesis calculations. However, the 7Li calculated abundance is significantly higher than the one deduced from spectroscopic observations and remains an open problem. In addition, recent deuterium observations have drastically reduced the uncertainty on D /H , to reach a value of 1.6%. It needs to be matched by BBN predictions whose precision is now limited by thermonuclear reaction rate uncertainties. This is especially important as many attempts to reconcile Li observations with models lead to an increased D prediction. Here, we reevaluate the d (p ,γ )3He, d (d ,n ) 3H3, and d (d ,p ) 3H reaction rates that govern deuterium destruction, incorporating new experimental data and carefully accounting for systematic uncertainties. Contrary to previous evaluations, we use theoretical ab initio models for the energy dependence of the S factors. As a result, these rates increase at BBN temperatures, leading to a reduced value of D /H =(2.45 ±0.10 )×10-5 (2 σ ), in agreement with observations.
Arnould, M; Jorissen, A
1999-01-01
The abundances of the isotopes of the elements from C to Al produced by the non-explosive CNO, NeNa and MgAl modes of hydrogen burning, as well as by helium burning, are calculated with the thermonuclear rates recommended by the European compilation of reaction rates for astrophysics (NACRE: details about NACRE may be found at http://astro.ulb.ac.be. This electronic address provides many data of nuclear astrophysics interest and also offers the possibility of generating interactively tables of reaction rates for networks and temperature grids selected by the user). The impact of nuclear physics uncertainties on the derived abundances is discussed in the framework of a simple parametric astrophysical model. These calculations have the virtue of being a guide in the selection of the nuclear uncertainties that have to be duly analyzed in detailed model stars, particularly in order to perform meaningful confrontations between abundance observations and predictions. They are also hoped to help nuclear astrophysici...
Shock tube measurements of the rate constant for the reaction ethanol + OH.
Stranic, Ivo; Pang, Genny A; Hanson, Ronald K; Golden, David M; Bowman, Craig T
2014-02-06
The overall rate constant for the reaction ethanol + OH → products was determined experimentally from 900 to 1270 K behind reflected shock waves. Ethan(18)ol was utilized for these measurements in order to avoid the recycling of OH radicals following H-atom abstraction at the β-site of ethanol. Similar experiments were also performed with unlabeled ethan(16)ol in order to infer the rate constant that excludes reactivity at the β-site. The two data sets were used to directly infer the branching ratio for the reaction at the β-site. Experimental data in the current study and in previous low-temperature studies for the overall rate constant are best fit by the expression koverall = 5.07 × 10(5) T[K](2.31) exp(608/T[K]) cm(3) mol(-1) s(-1), valid from 300 to 1300 K. Measurements indicate that the branching ratio of the β-site is between 20 and 25% at the conditions studied. Pseudo-first-order reaction conditions were generated using tert-butylhydroperoxide (TBHP) as a fast source of (16)OH with ethanol in excess. (16)OH mole fraction time-histories were measured using narrow-line width laser absorption near 307 nm. Measurements were performed at the linecenter of the R22(5.5) transition in the A-X(0,0) band of (16)OH that does not overlap with any absorption features of (18)OH, thus producing a measurement of the (16)OH mole fraction that is insensitive to the presence of (18)OH.
Frank Seebacher
2017-08-01
Full Text Available Endotherms regulate their core body temperature by adjusting metabolic heat production and insulation. Endothermic body temperatures are therefore relatively stable compared to external temperatures. The thermal sensitivity of biochemical reaction rates is thought to have co-evolved with body temperature regulation so that optimal reaction rates occur at the regulated body temperature. However, recent data show that core body temperatures even of non-torpid endotherms fluctuate considerably. Additionally, peripheral temperatures can be considerably lower and more variable than core body temperatures. Here we discuss whether published data support the hypothesis that thermal performance curves of physiological reaction rates are plastic so that performance is maintained despite variable body temperatures within active (non-torpid endotherms, and we explore mechanisms that confer plasticity. There is evidence that thermal performance curves in tissues that experience thermal fluctuations can be plastic, although this question remains relatively unexplored for endotherms. Mechanisms that alter thermal responses locally at the tissue level include transient potential receptor ion channels (TRPV and TRPM and the AMP-activated protein kinase (AMPK both of which can influence metabolism and energy expenditure. Additionally, the thermal sensitivity of processes that cause post-transcriptional RNA degradation can promote the relative expression of cold-responsive genes. Endotherms can respond to environmental fluctuations similarly to ectotherms, and thermal plasticity complements core body temperature regulation to increase whole-organism performance. Thermal plasticity is ancestral to endothermic thermoregulation, but it has not lost its selective advantage so that modern endotherms are a physiological composite of ancestral ectothermic and derived endothermic traits.
Unimolecular reaction rate constants of NO{sub 2} just above D{sub 0}
Bezel, I.; Stolyarov, D.; Wittig, C.
1999-12-09
Photoinitiated unimolecular decomposition on a barrierless potential energy surface (PES) has been studied for the reaction NO{sub 2} {yields} O({sup 3}P{sub 2}) + NO(X{sup 2}{Pi}{sub 1/2}, {nu} = 0) for excess energies up to approximately 17 cm{sup {minus}1} above the dissociation threshold (i.e., D{sub 0} for nonrotating molecules) by using expansion-cooled samples and the time-resolved pump-probe technique. To examine the threshold region with enough energy resolution to discern abrupt changes in the rate constant, should they occur, a pump-probe cross-correlation temporal width of {approximately}25 ps and a pump line width {le}2 cm{sup {minus}1} has been used. These are the first direct observations of the reaction rate constants in this energy regime. The rate constant was found to increase by an order of magnitude, varying from {approximately}2 x 10{sup 10} s{sup {minus}1} to {ge}10{sup 11} s{sup {minus}1}, the latter being a rough lower bound imposed by the experimental arrangement. The rate constant does not display the energy dependence predicted by using phase space theory, at least in detail. Rather, it appears to reflect the highly complex nature of the levels and the multiple PESs that are believed to be responsible for the anomalously high vibronic level density which has been observed just below D{sub 0}. These results bridge the gap between spectroscopic studies which have been carried out at energies just above D{sub 0} and ultrafast experiments which have measured rate constants in this energy region with pump laser spectral widths of {approximately}30 cm{sup {minus}1}.
Chemical reaction rates using the semiclassical Van-Vleck initialvalue representation
Venkataraman, Charulatha; Miller, William H.
2006-11-29
A semiclassical IVR formulation using the Van-Vleck propagator has been used to calculate the flux correlation function and thereby reaction rate constants. This Van-Vleck formulation of the flux-flux correlation function is computationally as simple as the classical Wigner model. However unlike the latter, it has the ability to capture quantum interference/coherence effects. Classical trajectories are evolved starting from the dividing surface that separates reactants and products, and are evolved negatively in time. This formulation has been tested on model problems ranging from the Eckart barrier, double well to the collinear H + H{sub 2}.
Rates of reaction and process design data for the Hydrocarb Process
Steinberg, M.; Kobayashi, Atsushi [Brookhaven National Lab., Upton, NY (United States); Tung, Yuanki [Hydrocarb Corp., New York, NY (United States)
1992-08-01
In support of studies for developing the coprocessing of fossil fuels with biomass by the Hydrocarb Process, experimental and process design data are reported. The experimental work includes the hydropryolysis of biomass and the thermal decomposition of methane in a tubular reactor. The rates of reaction and conversion were obtained at temperature and pressure conditions pertaining to a Hydrocarb Process design. A Process Simulation Computer Model was used to design the process and obtain complete energy and mass balances. Multiple feedstocks including biomass with natural gas and biomass with coal were evaluated. Additional feedstocks including green waste, sewage sludge and digester gas were also evaluated for a pilot plant unit.
Shock tube/laser absorption measurements of the reaction rates of OH with ethylene and propene.
Vasu, Subith S; Hong, Zekai; Davidson, David F; Hanson, Ronald K; Golden, David M
2010-11-04
Reaction rates of hydroxyl (OH) radicals with ethylene (C₂H₄) and propene (C₃H₆) were studied behind reflected shock waves. OH + ethylene → products (rxn 1) rate measurements were conducted in the temperature range 973-1438 K, for pressures from 2 to 10 atm, and for initial concentrations of ethylene of 500, 751, and 1000 ppm. OH + propene → products (rxn 2) rate measurements spanned temperatures of 890-1366 K, pressures near 2.3 atm, and initial propene concentrations near 300 ppm. OH radicals were produced by shock-heating tert-butyl hydroperoxide, (CH₃)₃-CO-OH, and monitored by laser absorption near 306.7 nm. Rate constants for the reactions of OH with ethylene and propene were extracted by matching modeled and measured OH concentration time-histories in the reflected shock region. Current data are in excellent agreement with previous studies and extend the temperature range of OH + propene data. Transition state theory calculations using recent ab initio results give excellent agreement with our measurements and other data outside our temperature range. Fits (in units of cm³/mol/s) to the abstraction channels of OH + ethylene and OH + propene are k₁ = 2.23 × 10⁴ (T)(2.745) exp(-1115 K/T) for 600-2000 K and k₂ = 1.94 × 10⁶ (T)(2.229) exp(-540 K/T) for 700-1500 K, respectively. A rate constant determination for the reaction TBHP → products (rxn 3) was also obtained in the range 745-1014 K using OH data from behind both incident and reflected shock waves. These high-temperature measurements were fit with previous low-temperature data, and the following rate expression (0.6-2.6 atm), applicable over the temperature range 400-1050 K, was obtained: k₃ (1/s) = 8.13 × 10⁻¹² (T)(7.83) exp(-14598 K/T).
Ross, A.B.
1975-06-01
A compilation of rates of reactions of hydrated electrons with other transients and with organic and inorganic solutes in aqueous solution appeared in NSRDS-NBS 43, and covered the literature up to early 1971. This supplement includes additional rates which have been published through July 1973.
Rosewarne, P J; Wilson, J M; Svendsen, J C
2016-01-01
Metabolic rate is one of the most widely measured physiological traits in animals and may be influenced by both endogenous (e.g. body mass) and exogenous factors (e.g. oxygen availability and temperature). Standard metabolic rate (SMR) and maximum metabolic rate (MMR) are two fundamental physiological variables providing the floor and ceiling in aerobic energy metabolism. The total amount of energy available between these two variables constitutes the aerobic metabolic scope (AMS). A laboratory exercise aimed at an undergraduate level physiology class, which details the appropriate data acquisition methods and calculations to measure oxygen consumption rates in rainbow trout Oncorhynchus mykiss, is presented here. Specifically, the teaching exercise employs intermittent flow respirometry to measure SMR and MMR, derives AMS from the measurements and demonstrates how AMS is affected by environmental oxygen. Students' results typically reveal a decline in AMS in response to environmental hypoxia. The same techniques can be applied to investigate the influence of other key factors on metabolic rate (e.g. temperature and body mass). Discussion of the results develops students' understanding of the mechanisms underlying these fundamental physiological traits and the influence of exogenous factors. More generally, the teaching exercise outlines essential laboratory concepts in addition to metabolic rate calculations, data acquisition and unit conversions that enhance competency in quantitative analysis and reasoning. Finally, the described procedures are generally applicable to other fish species or aquatic breathers such as crustaceans (e.g. crayfish) and provide an alternative to using higher (or more derived) animals to investigate questions related to metabolic physiology.
Lansdown, K.; Heppell, C. M.; Trimmer, M.; Binley, A.; Heathwaite, A. L.; Byrne, P.; Zhang, H.
2015-06-01
Anthropogenic nitrogen fixation and subsequent use of this nitrogen as fertilizer have greatly disturbed the global nitrogen cycle. Rivers are recognized hot spots of nitrogen removal in the landscape as interaction between surface water and sediments creates heterogeneous redox environments conducive for nitrogen transformations. Our understanding of riverbed nitrogen dynamics to date comes mainly from shallow sediments or hyporheic exchange flow pathways with comparatively little attention paid to groundwater-fed, gaining reaches. We have used 15N techniques to quantify in situ rates of nitrate removal to 1 m depth within a groundwater-fed riverbed where subsurface hydrology ranged from strong upwelling to predominantly horizontal water fluxes. We combine these rates with detailed hydrologic measurements to investigate the interplay between biogeochemical activity and water transport in controlling nitrogen attenuation along upwelling flow pathways. Nitrate attenuation occurred via denitrification rather than dissimilatory nitrate reduction to ammonium or anammox (range = 12 to >17,000 nmol 15N L-1 h-1). Overall, nitrate removal within the upwelling groundwater was controlled by water flux rather than reaction rate (i.e., Damköhler numbers rates of denitrification and short water residence time close to the riverbed surface balanced by slower rates of denitrification and water flux at depth. Within this permeable riverbed >80% of nitrate removal occurs within sediments not exposed to hyporheic exchange flows under base flow conditions, illustrating the importance of deep sediments as nitrate sinks in upwelling systems.
Elementary reaction rate measurements at high temperatures by tunable-laser flash-absorption
Hessler, J.P. [Argonne National Laboratory, IL (United States)
1993-12-01
The major objective of this program is to measure thermal rate coefficients and branching ratios of elementary reactions. To perform these measurements, the authors constructed an ultrahigh-purity shock tube to generate temperatures between 1000 and 5500 K. The tunable-laser flash-absorption technique is used to measure the rate of change of the concentration of species which absorb below 50,000 cm{sup {minus}1} e.g.: OH, CH, and CH{sub 3}. This technique is being extended into the vacuum-ultraviolet spectral region where one can measure atomic species e.g.: H, D, C, O, and N; and diatomic species e.g.: O{sub 2}, CO, and OH.
Rate Constant and Branching Fraction for the NH2 + NO2 Reaction
Klippenstein, Stephen J.; Harding, Lawrence B.; Glarborg, Peter
2013-01-01
The NH2 + NO2 reaction has been studied experimentally and theoretically. On the basis of laser photolysis/LIF experiments, the total rate constant was determined over the temperature range 295–625 K as k1,exp(T) = 9.5 × 10–7(T/K)−2.05 exp(−404 K/T) cm3 molecule–1 s–1. This value is in the upper...... may facilitate a small flux between the adducts. High- and low-pressure limit rate coefficients for the various product channels of NH2 + NO2 are determined from the ab initio TST-based master equation calculations for the temperature range 300–2000 K. The theoretical predictions are in good agreement...
Gilbert, J L; Smith, S M; Lautenschlager, E P
1993-11-01
The Scanning Electrochemical Microscope (SECM) is a nonoptical scanning microscopic instrument capable of imaging highly localized electrical currents associated with charge transfer reactions on metallic biomaterials surfaces. The SECM operates as an aqueous electrochemical cell under bipotentiostatic control with a microelectrode and sample independently biased as working electrodes. Microelectrode current and position is recorded as it is scanned very near a metallurgically polished planar sample surface. To date, the SECM has imaged metallic biomaterials surfaces in oxygen reaction rate imaging (ORRI) and ion release and deposition imaging (IRDI) modes. In ORRI, sample and microelectrode are biased at sufficiently negative potentials to reduce absorbed oxygen. As the microelectrode scans areas of active oxygen reduction, localized diffusion fields with decreased oxygen solution concentrations are encountered and resultant decrements in microelectrode current are observed. In IRDI mode the sample is positively biased and the microelectrode is negatively biased. The microelectrode detects anodic dissolution products with highest currents being observed over the most active areas. Performance of the SECM has been evaluated on Ni minigrids, gamma-1 Hg-Ag dental amalgam crystals, and sintered beads of Co-Cr-Mo alloy which represent significantly different geometries and corrosion processes to help demonstrate the potential of this instrument. The SECM is a valuable tool for imaging microelectrochemical processes on the surfaces of metallurgically polished metallic biomaterials samples and a wide variety of other surfaces of biological interest where charge transfer reactions occur. The SECM allows selective biasing of metallic biomaterials surfaces and Faradaic reactions can be selectively imaged while the surface is in the active, passive, or transpassive state.
Ma, Jingxing; Mungoni, Lucy Jubeki; Verstraete, Willy; Carballa, Marta
2009-07-01
The maximum propionic acid (HPr) removal rate (R(HPr)) was investigated in two lab-scale Upflow Anaerobic Sludge Bed (UASB) reactors. Two feeding strategies were applied by modifying the hydraulic retention time (HRT) in the UASB(HRT) and the influent HPr concentration in the UASB(HPr), respectively. The experiment was divided into three main phases: phase 1, influent with only HPr; phase 2, HPr with macro-nutrients supplementation and phase 3, HPr with macro- and micro-nutrients supplementation. During phase 1, the maximum R(HPr) achieved was less than 3 g HPr-CODL(-1)d(-1) in both reactors. However, the subsequent supplementation of macro- and micro-nutrients during phases 2 and 3 allowed to increase the R(HPr) up to 18.1 and 32.8 g HPr-CODL(-1)d(-1), respectively, corresponding with an HRT of 0.5h in the UASB(HRT) and an influent HPr concentration of 10.5 g HPr-CODL(-1) in the UASB(HPr). Therefore, the high operational capacity of these reactor systems, specifically converting HPr with high throughput and high influent HPr level, was demonstrated. Moreover, the presence of macro- and micro-nutrients is clearly essential for stable and high HPr removal in anaerobic digestion.
Gonzalez-Lopezlira, Rosa A; Kroupa, Pavel
2013-01-01
We analyze the relationship between maximum cluster mass, and surface densities of total gas (Sigma_gas), molecular gas (Sigma_H_2), neutral gas (Sigma_HI) and star formation rate (Sigma_SFR) in the grand design galaxy M51, using published gas data and a catalog of masses, ages, and reddenings of more than 1800 star clusters in its disk, of which 223 are above the cluster mass distribution function completeness limit. We find for clusters older than 25 Myr that M_3rd, the median of the 5 most massive clusters, is proportional to Sigma_HI^0.4. There is no correlation with Sigma_gas, Sigma_H2, or Sigma_SFR. For clusters younger than 10 Myr, M_3rd is proportional to Sigma_HI^0.6, M_3rd is proportional to Sigma_gas^0.5; there is no correlation with either Sigma_H_2 or Sigma_SFR. The results could hardly be more different than those found for clusters younger than 25 Myr in M33. For the flocculent galaxy M33, there is no correlation between maximum cluster mass and neutral gas, but M_3rd is proportional to Sigma_g...
Reaction rate uncertainties and 26Al in AGB silicon carbide stardust
van Raai, M A; Karakas, A I; Iliadis, C
2007-01-01
Stardust is a class of presolar grains each of which presents an ideally uncontaminated stellar sample. Mainstream silicon carbide (SiC) stardust formed in the extended envelopes of carbon-rich asymptotic giant branch (AGB) stars and incorporated the radioactive nucleus 26Al as a trace element. The aim of this paper is to analyse in detail the effect of nuclear uncertainties, in particular the large uncertainties of up to four orders of magnitude related to the 26Al_g+(p,gamma)27Si reaction rate, on the production of 26Al in AGB stars and compare model predictions to data obtained from laboratory analysis of SiC stardust grains. Stellar uncertainties are also briefly discussed. We use a detailed nucleosynthesis postprocessing code to calculate the 26Al/27Al ratios at the surface of AGB stars of different masses (M = 1.75, 3, and 5 M_sun) and metallicities (Z = 0.02, 0.012, and 0.008). For the lower limit and recommended value of the 26Al_g(p,gamma)27Si reaction rate, the predicted 26Al/27Al ratios replicate t...
Deep Mixing in Evolved Stars: I. The Effect of Reaction Rate Revisions from C to Al
Palmerini, S; Cristallo, S; Busso, M
2010-01-01
We present computations of nucleosynthesis in low-mass red-giant-branch and asymptotic-giant-branch stars of Population I experiencing extended mixing. We adopt the updated version of the FRANEC evolutionary model, a new post-process code for non-convective mixing and the most recent revisions for solar abundances. In this framework, we discuss the effects of recent improvements in relevant reaction rates for proton captures on intermediate-mass nuclei (from carbon to aluminum). For each nucleus we briefly discuss the new choices and their motivations. The calculations are then performed on the basis of a parameterized circulation, where the effects of the new nuclear inputs are best compared to previous works. We find that the new rates (and notably the one for the 14N(p,g)15O reaction) imply considerable modifications in the composition of post-main sequence stars. In particular, the slight temperature changes due to the reduced efficiency of proton captures on 14N induce abundance variations at the first d...
Yi, Jian-Hua; Zhao, Feng-Qi; Wang, Bo-Zhou; Liu, Qian; Zhou, Cheng; Hu, Rong-Zu; Ren, Ying-Hui; Xu, Si-Yu; Xu, Kang-Zhen; Ren, Xiao-Ning
2010-09-15
The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f(alpha)=(1-alpha)(2), and the kinetic equations are dalpha/dt = 10(19.24)(1-alpha)(2)e(-2.32x10(4)/T) and dalpha/dt = 10(20.32)(1-alpha)(2)e(-2.32x10(4)/T). The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa.
Yi Jianhua [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Zhao Fengqi, E-mail: yiren@nwu.edu.cn [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Wang Bozhou; Liu Qian; Zhou Cheng; Hu Rongzu [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Ren Yinghui [School of Chemical Engineering, Northwest University, Xi' an 710069 (China); Xu Siyu [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China); Xu, Kang-Zhen [School of Chemical Engineering, Northwest University, Xi' an 710069 (China); Ren Xiaoning [Xi' an Modern Chemistry Research Institute, Xi' an 710065 (China)
2010-09-15
The composite modified double base (CMDB) propellants (nos. RB0601 and RB0602) containing 3,6-bis (1H-1,2,3,4-tetrazol-5-yl-amino)-1,2,4,5-tetrazine (BTATz) without and with the ballistic modifier were prepared and their thermal behaviors, nonisothermal decomposition reaction kinetics, thermal safety and burning rates were investigated. The results show that there are three mass-loss stages in TG curve and two exothermic peaks in DSC curve for the BTATz-CMDB propellant. The first two mass-loss stages occur in succession and the temperature ranges are near apart, and the decomposition peaks of the two stages overlap each other, inducing only one visible exothermic peak appear in DSC curve during 350-550 K. The reaction mechanisms of the main exothermal decomposition processes of RB0601 and RB0602 are all classified as chemical reaction, the mechanism functions are f({alpha}) = (1 - {alpha}){sup 2}, and the kinetic equations are d{alpha}/dt=10{sup 19.24}(1-{alpha}){sup 2}e{sup -2.32x10{sup 4/T}} and d{alpha}/dt=10{sup 20.32}(1-{alpha}){sup 2}e{sup -2.43x10{sup 4/T}}. The thermal safety evaluation on the BTATz-CMDB propellants was obtained. With the substitution of 26% RDX by BTATz and with the help of the ballistic modifier in the CMDB propellant formulation, the burning rate can be improved by 89.0% at 8 MPa and 47.1% at 22 MPa, the pressure exponent can be reduced to 0.353 at 14-20 MPa.
Syed Imran A. Shah
2012-01-01
Full Text Available Competitive-consecutive and competitive-parallel reactions are both mixing sensitive reactions where the yield of desired product depends on how fast the reactants are brought together. Recent experimental results have suggested that the magnitude of the mixing effect may depend strongly on the stoichiometry of the reactions. To investigate this, a 1D, dimensionless, reaction-diffusion model was developed at the micromixing scale, yielding a single general Damköhler number. Dimensionless reaction rate ratios were derived for both reaction schemes. A detailed investigation of the effects of initial mixing condition (striation thickness, dimensionless reaction rate ratio, and reaction stoichiometry on the yield of desired product showed that the stoichiometry has a considerable effect on yield. All three variables were found to interact strongly. Model results for 12 stoichiometries are used to determine the mixing scale and relative rate ratio needed to achieve a specified yield for each reaction scheme. The results show that all three variables need to be considered when specifying reactors for mixing sensitive reactions.
Comfort, Paul; Allen, Mark; Graham-Smith, Phillip
2011-05-01
The aim of this investigation was to determine the differences in vertical ground reaction forces and rate of force development (RFD) during variations of the power clean. Elite rugby league players (n = 11; age 21 ± 1.63 years; height 181.56 ± 2.61 cm; body mass 93.65 ± 6.84 kg) performed 1 set of 3 repetitions of the power clean, hang-power clean, midthigh power clean, or midthigh clean pull, using 60% of 1-repetition maximum power clean, in a randomized order, while standing on a force platform. Differences in peak vertical ground reaction forces (F(z)) and instantaneous RFD between lifts were analyzed via 1-way analysis of variance and Bonferroni post hoc analysis. Statistical analysis revealed a significantly (p < 0.001) greater peak F(z) during the midthigh power clean (2,801.7 ± 195.4 N) and the midthigh clean pull (2,880.2 ± 236.2 N) compared to both the power clean (2,306.24 ± 240.47 N) and the hang-power clean (2,442.9 ± 293.2 N). The midthigh power clean (14,655.8 ± 4,535.1 N·s⁻¹) and the midthigh clean pull (15,320.6 ± 3,533.3 N·s⁻¹) also demonstrated significantly (p < 0.001) greater instantaneous RFD when compared to both the power clean (8,839.7 ± 2,940.4 N·s⁻¹) and the hang-power clean (9,768.9 ± 4,012.4 N·s⁻¹). From the findings of this study, when training to maximize peak F(z) and RFD the midthigh power clean and midthigh clean pull appear to be the most advantageous variations of the power clean to perform.
Sunil Kwon; Hyunbae Dong; Sang-Yup Lee
2010-01-01
An investigation was carried out about the gold nanotube synthesis via a galvanic replacement reaction. The progress of the gold nanotube synthesis was investigated using electron microscopy and UV-Vis spectroscopy. In addition, the reaction rates of gold nanotube formation in the early stage of the reaction were studied. The chlorine ion concentration linearly increased with the gold precursor concentration but deviated from the stoichiometric amounts. This deviation was probably due to AgCl...
Stress-associated cardiovascular reaction masks heart rate dependence on physical load in mice.
Andreev-Andrievskiy, A A; Popova, A S; Borovik, A S; Dolgov, O N; Tsvirkun, D V; Custaud, M; Vinogradova, O L
2014-06-10
When tested on the treadmill mice do not display a graded increase of heart rate (HR), but rather a sharp shift of cardiovascular indices to high levels at the onset of locomotion. We hypothesized that under test conditions cardiovascular reaction to physical load in mice is masked with stress-associated HR increase. To test this hypothesis we monitored mean arterial pressure (MAP) and heart rate in C57BL/6 mice after exposure to stressful stimuli, during spontaneous locomotion in the open-field test, treadmill running or running in a wheel installed in the home cage. Mice were treated with β1-adrenoblocker atenolol (2mg/kg ip, A), cholinolytic ipratropium bromide (2mg/kg ip, I), combination of blockers (A+I), anxiolytic diazepam (5mg/kg ip, D) or saline (control trials, SAL). MAP and HR in mice increased sharply after handling, despite 3weeks of habituation to the procedure. Under stressful conditions of open field test cardiovascular parameters in mice were elevated and did not depend on movement speed. HR values did not differ in I and SAL groups and were reduced with A or A+I. HR was lower at rest in D pretreated mice. In the treadmill test HR increase over speeds of 6, 12 and 18m/min was roughly 1/7-1/10 of HR increase observed after placing the mice on the treadmill. HR could not be increased with cholinolytic (I), but was reduced after sympatholytic (A) or A+I treatment. Anxiolytic (D) reduced heart rate at lower speeds of movement and its overall effect was to unmask the dependency of HR on running speed. During voluntary running in non-stressful conditions of the home cage HR in mice linearly increased with increasing running speeds. We conclude that in test situations cardiovascular reactions in mice are governed predominantly by stress-associated sympathetic activation, rendering efforts to evaluate HR and MAP reactions to workload unreliable. Copyright © 2014 Elsevier Inc. All rights reserved.
Yao, Qian; Sun, Xiao-Hui; Li, Ze-Rong; Chen, Fang-Fang; Li, Xiang-Yuan
2017-04-27
Intramolecular H-migration reaction of hydroperoxyalkylperoxy radicals ((•)O2QOOH) is one of the most important reaction families in the low-temperature oxidation of hydrocarbon fuels. This reaction family is first divided into classes depending upon H atom transfer from -OOH bonded carbon or non-OOH bonded carbon, and then the two classes are further divided depending upon the ring size of the transition states and the types of the carbons from which the H atom is transferred. High pressure limit rate rules and pressure-dependent rate rules for each class are derived from the rate constants of a representative set of reactions within each class using electronic structure calculations performed at the CBS-QB3 level of theory. For the intramolecular H-migration reactions of (•)O2QOOH radicals for abstraction from an -OOH substituted carbon atom (-OOH bonded case), the result shows that it is acceptable to derive the rate rules by taking the average of the rate constants from a representative set of reactions with different sizes of the substitutes. For the abstraction from a non-OOH substituted carbon atom (non-OOH bonded case), rate rules for each class are also derived and it is shown that the difference between the rate constants calculated by CBS-QB3 method and rate constants estimated from the rate rules may be large; therefore, to get more reliable results for the low-temperature combustion modeling of alkanes, it is better to assign each reaction its CBS-QB3 calculated rate constants, instead of assigning the same values for the same reaction class according to rate rules. The intramolecular H-migration reactions of (•)O2QOOH radicals (a thermally equilibrated system) are pressure-dependent, and the pressure-dependent rate constants of these reactions are calculated by using the Rice-Ramsberger-Kassel-Marcus/master-equation theory at pressures varying from 0.01 to 100 atm. The impact of molecular size on the pressure-dependent rate constants of the
Beckingham, L. E.; Zhang, S.; Mitnick, E.; Cole, D. R.; Yang, L.; Anovitz, L. M.; Sheets, J.; Swift, A.; Kneafsey, T. J.; Landrot, G.; Mito, S.; Xue, Z.; Steefel, C. I.; DePaolo, D. J.; Ajo Franklin, J. B.
2014-12-01
Geologic sequestration of CO2 in deep sedimentary formations is a promising means of mitigating carbon emissions from coal-fired power plants but the long-term fate of injected CO2 is challenging to predict. Reactive transport models are used to gain insight over long times but rely on laboratory determined mineral reaction rates that have been difficult to extrapolate to field systems. This, in part, is due to a lack of understanding of mineral reactive surface area. Many models use an arbitrary approximation of reactive surface area, applying orders of magnitude scaling factors to measured BET or geometric surface areas. Recently, a few more sophisticated approaches have used 2D and 3D image analyses to determine mineral-specific reactive surface areas that account for the accessibility of minerals. However, the ability of these advanced surface area estimates to improve predictions of mineral reaction rates has yet to be determined. In this study, we fuse X-ray microCT, SEM QEMSCAN, XRD, SANS, and SEM-FIB analysis to determine mineral-specific accessible reactive surface areas for a core sample from the Nagaoka pilot CO2 injection site (Japan). This sample is primarily quartz, plagioclase, smectite, K-feldspar, and pyroxene. SEM imaging shows abundant smectite cement and grain coatings that decrease the fluid accessibility of other minerals. However, analysis of FIB-SEM images reveals that smectite nano-pores are well connected such that access to underlying minerals is not occluded by smectite coatings. Mineral-specific accessible surfaces are determined, accounting for the connectivity of the pore space with and without connected smectite nano-pores. The large-scale impact of variations in accessibility and dissolution rates are then determined through continuum scale modeling using grid-cell specific information on accessible surface areas. This approach will be compared with a traditional continuum scale model using mineral abundances and common surface area
van Harrevelt, Rob; Honkala, Johanna Karoliina; Nørskov, Jens Kehlet
2005-01-01
Quantum-mechanical calculations of the reaction rate for dissociative adsorption of N-2 on stepped Ru(0001) are presented. Converged six-dimensional quantum calculations for this heavy-atom reaction have been performed using the multiconfiguration time-dependent Hartree method. A potential...
Zaylaa, Amira; Oudjemia, Souad; Charara, Jamal; Girault, Jean-Marc
2015-09-01
This paper presents two new concepts for discrimination of signals of different complexity. The first focused initially on solving the problem of setting entropy descriptors by varying the pattern size instead of the tolerance. This led to the search for the optimal pattern size that maximized the similarity entropy. The second paradigm was based on the n-order similarity entropy that encompasses the 1-order similarity entropy. To improve the statistical stability, n-order fuzzy similarity entropy was proposed. Fractional Brownian motion was simulated to validate the different methods proposed, and fetal heart rate signals were used to discriminate normal from abnormal fetuses. In all cases, it was found that it was possible to discriminate time series of different complexity such as fractional Brownian motion and fetal heart rate signals. The best levels of performance in terms of sensitivity (90%) and specificity (90%) were obtained with the n-order fuzzy similarity entropy. However, it was shown that the optimal pattern size and the maximum similarity measurement were related to intrinsic features of the time series.
1993-07-01
This document provides an analysis of the potential impacts associated with the proposed action, which is continued operation of Naval Petroleum Reserve No. I (NPR-1) at the Maximum Efficient Rate (MER) as authorized by Public law 94-258, the Naval Petroleum Reserves Production Act of 1976 (Act). The document also provides a similar analysis of alternatives to the proposed action, which also involve continued operations, but under lower development scenarios and lower rates of production. NPR-1 is a large oil and gas field jointly owned and operated by the federal government and Chevron U.SA Inc. (CUSA) pursuant to a Unit Plan Contract that became effective in 1944; the government`s interest is approximately 78% and CUSA`s interest is approximately 22%. The government`s interest is under the jurisdiction of the United States Department of Energy (DOE). The facility is approximately 17,409 acres (74 square miles), and it is located in Kern County, California, about 25 miles southwest of Bakersfield and 100 miles north of Los Angeles in the south central portion of the state. The environmental analysis presented herein is a supplement to the NPR-1 Final Environmental Impact Statement of that was issued by DOE in 1979 (1979 EIS). As such, this document is a Supplemental Environmental Impact Statement (SEIS).
Abdel-Latif A. Seoud
2010-01-01
Full Text Available Problem statement: For chemical reactions, the determination of the rate constants is both very difficult and a time consuming process. The aim of this research was to develop computer programs for determining the rate constants for the general form of any complex reaction at a certain temperature. The development of such program can be very helpful in the control of industrial processes as well as in the study of the reaction mechanisms. Determination of the accurate values of the rate constants would help in establishing the optimum conditions of reactor design including pressure, temperature and other parameters of the chemical reaction. Approach: From the experimental concentration-time data, initial values of rate constants were calculated. Experimental data encountered several types of errors, including temperature variation, impurities in the reactants and human errors. Simulations of a second order consecutive irreversible chemical reaction of the saponification of diethyl ester were presented as an example of the complex reactions. The rate equations (system of simultaneous differential equations of the reaction were solved to get the analytical concentration versus time profiles. The simulation results were compared with experimental results at each measured point. All deviations between experimental and calculated values were squared and summed up to form a new function. This function was fed into a minimizer routine that gave the optimal rate constants. Two optimization techniques were developed using FORTRAN and MATLAB for accurately determining the rate constants of the reaction at certain temperature from the experimental data. Results: Results showed that the two proposed programs were very efficient, fast and accurate tools to determine the true rate constants of the reaction with less 1% error. The use of the MATLAB embedded subroutines for simultaneously solving the differential equations and minimization of the error function
Analysis of turbulent free jet hydrogen-air diffusion flames with finite chemical reaction rates
Sislian, J. P.
1978-01-01
The nonequilibrium flow field resulting from the turbulent mixing and combustion of a supersonic axisymmetric hydrogen jet in a supersonic parallel coflowing air stream is analyzed. Effective turbulent transport properties are determined using the (K-epsilon) model. The finite-rate chemistry model considers eight reactions between six chemical species, H, O, H2O, OH, O2, and H2. The governing set of nonlinear partial differential equations is solved by an implicit finite-difference procedure. Radial distributions are obtained at two downstream locations of variables such as turbulent kinetic energy, turbulent dissipation rate, turbulent scale length, and viscosity. The results show that these variables attain peak values at the axis of symmetry. Computed distributions of velocity, temperature, and mass fraction are also given. A direct analytical approach to account for the effect of species concentration fluctuations on the mean production rate of species (the phenomenon of unmixedness) is also presented. However, the use of the method does not seem justified in view of the excessive computer time required to solve the resulting system of equations.
Jesudason, C G
2006-01-01
The rates or formation and concentration distributions of a dimer reaction showing hysteresis behavior are examined in an ab initio chemical reaction designed as elementary and where the hysteresis structure precludes the formation of transition states (TS) with pre-equilibrium and internal sub-reactions. It was discovered that the the reactivity coefficients, defined as a measure of departure from the zero density rate constant for the forward and backward steps had a ratio that was equal to the activity coefficient ratio for the product and reactant species. From the above observations, a theory is developed with the aid of some proven elementary theorems in thermodynamics, and expressions are derived whereby a feasible experimental and computational method for determining the activity coefficients from the rate constants may be obtained The theory developed is applied to ionic reactions where the standard Bronsted-Bjerrum rate equation and exceptions to this are rationalized, and by viewing ion association...
Monte carlo simulations of Yttrium reaction rates in Quinta uranium target
Suchopár M.
2017-01-01
Full Text Available The international collaboration Energy and Transmutation of Radioactive Waste (E&T RAW performed intensive studies of several simple accelerator-driven system (ADS setups consisting of lead, uranium and graphite which were irradiated by relativistic proton and deuteron beams in the past years at the Joint Institute for Nuclear Research (JINR in Dubna, Russia. The most recent setup called Quinta, consisting of natural uranium target-blanket and lead shielding, was irradiated by deuteron beams in the energy range between 1 and 8 GeV in three accelerator runs at JINR Nuclotron in 2011 and 2012 with yttrium samples among others inserted inside the setup to measure the neutron flux in various places. Suitable activation detectors serve as one of possible tools for monitoring of proton and deuteron beams and for measurements of neutron field distribution in ADS studies. Yttrium is one of such suitable materials for monitoring of high energy neutrons. Various threshold reactions can be observed in yttrium samples. The yields of isotopes produced in the samples were determined using the activation method. Monte Carlo simulations of the reaction rates leading to production of different isotopes were performed in the MCNPX transport code and compared with the experimental results obtained from the yttrium samples.
Angulo, Gonzalo; Milkiewicz, Jadwiga; Kattnig, Daniel; Nejbauer, Michał; Stepanenko, Yuriy; Szczepanek, Jan; Radzewicz, Czesław; Wnuk, Paweł; Grampp, Günter
2017-02-22
The effect of multiple light excitation events on bimolecular photo-induced electron transfer reactions in liquid solution is studied experimentally. It is found that the decay of fluorescence can be up to 25% faster if a second photon is absorbed after a first cycle of quenching and recombination. A theoretical model is presented which ascribes this effect to the enrichment of the concentration of quenchers in the immediate vicinity of fluorophores that have been previously excited. Despite its simplicity, the model delivers a qualitative agreement with the observed experimental trends. The original theory by Burshtein and Igoshin (J. Chem. Phys., 2000, 112, 10930-10940) was created for continuous light excitation though. A qualitative extrapolation from the here presented pulse experiments to the continuous excitation conditions lead us to conclude that in the latter the order of magnitude of the increase of the quenching efficiency upon increasing the light intensity of excitation, must also be on the order of tens of percent. These results mean that the rate constant for photo-induced bimolecular reactions depends not only on the usual known factors, such as temperature, viscosity and other properties of the medium, but also on the intensity of the excitation light.
Origin of the Non-Arrhenius Behavior of the Rates of Enzymatic Reactions.
Roy, Subhendu; Schopf, Patrick; Warshel, Arieh
2017-07-13
The origin of the non-Arrhenius behavior of the rate constant for hydride transfer enzymatic reactions has been a puzzling problem since its initial observation. This effect has been used originally to support the idea that enzymes work by dynamical effects and more recently to suggest an entropy funnel model. Our analysis, however, has advanced the idea that the reason for the non-Arrhenius trend reflects the temperature dependence of the rearrangements of the protein polar groups in response to the change in the charge distribution of the reacting system during the transition from the ground state (GS) to the transition state (TS). Here we examine the validity of our early proposal by simulating the catalytic reaction of alcohol dehydrogenase (ADH) and determine the microscopic origin of the entropic and enthalpic contributions to the activation barrier. The corresponding analysis establishes the origin of the non-Arrhenius behaviors and quantifies our original suggestion that the classical effect is due to the entropic contributions of the environment. We also find that the quantum effects reflect in part the temperature dependence of the donor-acceptor distance.
Halász, Adám M; Lai, Hong-Jian; McCabe Pryor, Meghan; Radhakrishnan, Krishnan; Edwards, Jeremy S
2013-01-01
True steady states are a rare occurrence in living organisms, yet their knowledge is essential for quasi-steady-state approximations, multistability analysis, and other important tools in the investigation of chemical reaction networks (CRN) used to describe molecular processes on the cellular level. Here, we present an approach that can provide closed form steady-state solutions to complex systems, resulting from CRN with binary reactions and mass-action rate laws. We map the nonlinear algebraic problem of finding steady states onto a linear problem in a higher-dimensional space. We show that the linearized version of the steady-state equations obeys the linear conservation laws of the original CRN. We identify two classes of problems for which complete, minimally parameterized solutions may be obtained using only the machinery of linear systems and a judicious choice of the variables used as free parameters. We exemplify our method, providing explicit formulae, on CRN describing signal initiation of two important types of RTK receptor-ligand systems, VEGF and EGF-ErbB1.
Levay, B.; Mogensen, O. E.
1977-01-01
a correlation between the inhibition coefficient and the chemical rate constant of electrons with scavenger molecules. We found that the dependence of the inhibition coefficient on the work function (VOo)f electrons in different liquids shows a very unusual behavior, similar to that recently found...... for the chemical rate constants of quasifree electrons with the same scavenger molecules. The inhibition coefficient as a function of Vo had a maximum for C2HsBr, while it increased monotonously with decreasing V, for CC14. The inhibition coefficient for C2H5Br in a 1:l molar tetramethylsilane......-n-tetradecane mixture was found to be greater than in both of the pure components. The clear correlation found between electron scavenging rate constants and positronium inhibition constitutes the severest test to date of the spur reaction model of positronium formation. The importance of the positron annihilation...
Abadi, Ali Salehi Sahl; Mazlomi, Adel; Saraji, Gebraeil Nasl; Zeraati, Hojjat; Hadian, Mohammad Reza; Jafari, Amir Homayoun
2015-10-01
In spite of the widespread use of automation in industry, manual material handling (MMH) is still performed in many occupational settings. The emphasis on ergonomics in MMH tasks is due to the potential risks of workplace accidents and injuries. This study aimed to assess the effect of box size, frequency of lift, and height of lift on maximum acceptable weight of lift (MAWL) on the heart rates of male university students in Iran. This experimental study was conducted in 2015 with 15 male students recruited from Tehran University of Medical Sciences. Each participant performed 18 different lifting tasks that involved three lifting frequencies (1lift/min, 4.3 lifts/min and 6.67 lifts/min), three lifting heights (floor to knuckle, knuckle to shoulder, and shoulder to arm reach), and two box sizes. Each set of experiments was conducted during the 20 min work period using the free-style lifting technique. The working heart rates (WHR) were recorded for the entire duration. In this study, we used SPSS version 18 software and descriptive statistical methods, analysis of variance (ANOVA), and the t-test for data analysis. The results of the ANOVA showed that there was a significant difference between the mean of MAWL in terms of frequencies of lifts (p = 0.02). Tukey's post hoc test indicated that there was a significant difference between the frequencies of 1 lift/minute and 6.67 lifts/minute (p = 0. 01). There was a significant difference between the mean heart rates in terms of frequencies of lifts (p = 0.006), and Tukey's post hoc test indicated a significant difference between the frequencies of 1 lift/minute and 6.67 lifts/minute (p = 0.004). But, there was no significant difference between the mean of MAWL and the mean heart rate in terms of lifting heights (p > 0.05). The results of the t-test showed that there was a significant difference between the mean of MAWL and the mean heart rate in terms of the sizes of the two boxes (p = 0.000). Based on the results of
Nielsen, Jens Bredal
1997-01-01
Metabolic control analysis is a powerful technique for the evaluation of flux control within biochemical pathways. Its foundation is the elasticity coefficients and the flux control coefficients (FCCs). On the basis of a thermokinetic description of reaction rates it is here shown...... affinity. This parameter can often be determined from experiments in vitro. The methodology is applicable only to the analysis of simple two-step pathways, but in many cases larger pathways can be lumped into two overall conversions. In cases where this cannot be done it is necessary to apply an extension...... be much more widely applied, although it was originally based on linearized kinetics. The methodology of determining elasticity coefficients directly from pool levels is illustrated with an analysis of the first two steps of the biosynthetic pathway of penicillin. The results compare well with previous...
Toropov, A A; Toropova, A P; Rasulev, B F; Benfenati, E; Gini, G; Leszczynska, D; Leszczynski, J
2012-09-05
The rate constants (K(OH)) of reactions between 78 organic aromatic pollutants and hydroxyl radical were examined. Simplified molecular input line entry system was used as representation of the molecular structure of the pollutants. Quantitative structure-property relationships was developed using CORAL software (http://www.insilico.eu/CORAL) for four random splits of the data into the subtraining, calibration, and test sets. The obtained results reveal good predictive potential of the applied approach: correlation coefficients (r(2)) for the test sets of the four random splits are 0.75, 0.91, 0.84, and 0.80. Using the Monte Carlo method CORAL software generated the optimal descriptors for one-variable models. The reproducibility of each model was tested performing three runs of the Monte Carlo optimization. The current data were compared to previous results and discussed. Copyright © 2012 Wiley Periodicals, Inc.
Viglino, P; Scarpa, M; Rotilio, G; Rigo, A
1988-01-04
H2O2 was shown to reduce the copper ion of native bovine Cu,Zn superoxide dismutase (superoxide:superoxide oxidoreductase, EC 1.15.1.1) (ECu2+) and to oxidize the reduced enzyme (ECu+). The time-course of these processes was monitored by NMR measurement of the longitudinal relaxation rate of the water protons. A steady-state characterized by the same ratio [ECu2+]/[( EC2+] + [ECu+]) was obtained either by starting from the oxidized or the reduced enzyme. The kinetics of these processes appear to be quite complex, since different reactions between H2O2, or its reaction products, and the enzyme-bound copper control the reaction rate. The solution of the differential equations describing the kinetic processes showed that the oxidation and the reduction of the copper ion by H2O2 are first-order with respect to the copper ion itself only when these processes approach the steady-state. The rate constants of the reduction and oxidation reactions were calculated according to these equations and were found to have comparable values which are in the range 5-80 and 5-45 M-1.min-1, respectively, changing the pH from 5.6 to 7 at 0.21 M ionic strength. This result, together with the dependence of the reaction rates on pH and ionic strength, points to HO2- as the reactive species in both processes, and indicates that the electrostatic control of the access of the peroxide to the active site is the rate-determining step of the two redox reactions.
Usami, Shin; Suzuki, Takayuki; Sasaki, Kenji; Deshimaru, Takehide [Power Reactor and Nuclear Fuel Development Corp., Tsuruga, Fukui (Japan). Monju Construction Office; Nakashima, Fumiaki
1996-09-01
In MONJU, reaction rate distribution measurements were made by foil activation methods from May through September 1994. On the basis of the reaction rate measurement data, the MONJU initial core breeding ratio and the power distribution, etc. were evaluated. As a result, the evaluated values and the calculated values showed good agreement, and we confirmed that the core performance of MONJU and the method of core calculations were satisfactory. (author)
Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique
2017-03-01
This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d kinetics, where transport phenomena accelerate processes as the temperature increases; (ii) the sub-Arrhenius kinetics, where quantum mechanical tunnelling propitiates low-temperature reactivity; (iii) the anti-Arrhenius kinetics, where processes with no energetic obstacles are rate-limited by molecular reorientation requirements. Particular attention is given for case (i) to the treatment of diffusion and viscosity, for case (ii) to formulation of a transition rate theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature. This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'.
Watanabe, Y.; Morishita, K.; Nakasuji, T.; Ando, M.; Tanigawa, H.
2015-06-01
Reaction rate theory analysis has been conducted to investigate helium effects on the formation kinetics of interstitial type dislocation loops (I-loops) and helium bubbles in reduced-activation-ferritic/martensitic steel during irradiation, by focusing on the nucleation and growth processes of the defect clusters. The rate theory model employs the size and chemical composition dependence of thermal dissociation of point defects from defect clusters. In the calculations, the temperature and the production rate of Frenkel pairs are fixed to be T = 723 K and PV = 10-6 dpa/s, respectively. And then, only the production rate of helium atoms was changed into the following three cases: PHe = 0, 10-7 and 10-5 appm He/s. The calculation results show that helium effect on I-loop formation quite differs from that on bubble formation. As to I-loops, the loop formation hardly depends on the existence of helium, where the number density of I-loops is almost the same for the three cases of PHe. This is because helium atoms trapped in vacancies are easily emitted into the matrix due to the recombination between the vacancies and SIAs, which induces no pronounced increase or decrease of vacancies and SIAs in the matrix, leading to no remarkable impact on the I-loop nucleation. On the other hand, the bubble formation depends much on the existence of helium, in which the number density of bubbles for PHe = 10-7 and 10-5 appm He/s is much higher than that for PHe = 0. This is because helium atoms trapped in a bubble increase the vacancy binding energy, and suppress the vacancy dissociation from the bubble, resulting in a promotion of the bubble nucleation. And then, the helium effect on the promotion of bubble nucleation is very strong, even the number of helium atoms in a bubble is not so large.
Blok, Chris; Jackson, Brian E; Guo, Xianfeng; de Visser, Pieter H B; Marcelis, Leo F M
2017-01-01
Growing on rooting media other than soils in situ -i.e., substrate-based growing- allows for higher yields than soil-based growing as transport rates of water, nutrients, and oxygen in substrate surpass those in soil. Possibly water-based growing allows for even higher yields as transport rates of water and nutrients in water surpass those in substrate, even though the transport of oxygen may be more complex. Transport rates can only limit growth when they are below a rate corresponding to maximum plant uptake. Our first objective was to compare Chrysanthemum growth performance for three water-based growing systems with different irrigation. We compared; multi-point irrigation into a pond (DeepFlow); one-point irrigation resulting in a thin film of running water (NutrientFlow) and multi-point irrigation as droplets through air (Aeroponic). Second objective was to compare press pots as propagation medium with nutrient solution as propagation medium. The comparison included DeepFlow water-rooted cuttings with either the stem 1 cm into the nutrient solution or with the stem 1 cm above the nutrient solution. Measurements included fresh weight, dry weight, length, water supply, nutrient supply, and oxygen levels. To account for differences in radiation sum received, crop performance was evaluated with Radiation Use Efficiency (RUE) expressed as dry weight over sum of Photosynthetically Active Radiation. The reference, DeepFlow with substrate-based propagation, showed the highest RUE, even while the oxygen supply provided by irrigation was potentially growth limiting. DeepFlow with water-based propagation showed 15-17% lower RUEs than the reference. NutrientFlow showed 8% lower RUE than the reference, in combination with potentially limiting irrigation supply of nutrients and oxygen. Aeroponic showed RUE levels similar to the reference and Aeroponic had non-limiting irrigation supply of water, nutrients, and oxygen. Water-based propagation affected the subsequent
İ. Küçük; Ş. Çalışkan
2010-09-01
In understanding the nucleosynthesis of the elements in stars, one of the most important quantities is the reaction rate and it must be evaluated in terms of the stellar temperature , and its determination involves the knowledge of the excitation function () of the specific nuclear reaction leading to the final nucleus. In this paper, the effect of thermonuclear reaction rates to the pre-main sequence evolution of low mass stars having masses 0.7, 0.8, 0.9 and 1 M⊙ are studied by using our modified Stellar Evolutionary Program.
Evaluation of the reaction rate constants for the gas-phase Al-CH4-air combustion chemistry
Sharipov, A. S.; Titova, N. S.; Starik, A. M.
2012-10-01
The most likely reaction pathways and reaction products in the Al-CH4-O2-N2 system are investigated using density functional theory and ab initio calculations. The B3LYP functional with extended 6-311+G(3df,2p) basis set as well as the CBS-QB3 composite method are mainly utilised. Theoretical analysis of corresponding reaction rate constants is also performed with the use of simple theoretical models. A critical overview of current knowledge on combustion-relevant reactions with aluminium compounds is given. On the basis of critical comparison of available experimental kinetic data with theoretical calculations, the approximations for rate constants for 44 reversible elementary reactions involving Al-containing species are recommended for use in combustion issues.
Kustova, Elena V., E-mail: e.kustova@spbu.ru [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr. 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M., E-mail: kremer@fisica.ufpr.br [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)
2014-12-05
Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N{sub 2} flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.
New Determination of the 2H(d,p)3H and 2H(d,n)3He Reaction Rates at Astrophysical Energies
Tumino, A.; Spartà, R.; Spitaleri, C.; Mukhamedzhanov, A. M.; Typel, S.; Pizzone, R. G.; Tognelli, E.; Degl'Innocenti, S.; Burjan, V.; Kroha, V.; Hons, Z.; La Cognata, M.; Lamia, L.; Mrazek, J.; Piskor, S.; Prada Moroni, P. G.; Rapisarda, G. G.; Romano, S.; Sergi, M. L.
2014-04-01
The cross sections of the 2H(d,p)3H and 2H(d,n)3He reactions have been measured via the Trojan Horse method applied to the quasi-free 2H(3He,p 3H)1H and 2H(3He,n 3He)1H processes at 18 MeV off the proton in 3He. For the first time, the bare nucleus S(E) factors have been determined from 1.5 MeV, across the relevant region for standard Big Bang nucleosynthesis, down to the thermal energies of deuterium burning in the pre-main-sequence (PMS) phase of stellar evolution, as well as of future fusion reactors. Both the energy dependence and the absolute value of the S(E) factors deviate by more than 15% from the available direct data and existing fitting curves, with substantial variations in the electron screening by more than 50%. As a consequence, the reaction rates for astrophysics experience relevant changes, with a maximum increase of up to 20% at the temperatures of the PMS phase. From a recent primordial abundance sensitivity study, it turns out that the 2H(d,n)3He reaction is quite influential on 7Li, and the present change in the reaction rate leads to a decrease in its abundance by up to 10%. The present reaction rates have also been included in an updated version of the FRANEC evolutionary code to analyze their influence on the central deuterium abundance in PMS stars with different masses. The largest variation of about 10%-15% pertains to young stars (=1 M ⊙.
New Astrophysical Reaction Rates for 18F(p, α)15O and 18F(p, γ)19Ne
SHU Neng-Chuan(舒能川); D. W. Bardayan; J. C. Blackmon; CHEN Yong-Shou(陈永寿); R. L. Kozub; P. D. Parker; M. S. Smith
2003-01-01
The rates of the thermonuclear 18F(p, α)15O and 18F(p,γ)19Ne reactions in hot astrophysical environments are needed to understand gamma-ray emission from nova explosions. The rates for these reactions have been uncertain due to discrepancies in recent measurements, as well as to a lack of a comprehensive examination of the available structure information in the compound nucleus 19Ne. We have examined the latest experimental measurements with radioactive and stable beams, and made estimates of the unmeasured 19Ne nuclear level parameters, to generate new rates with uncertainties for these reactions. The rates are expressed as numerical values over the temperature range relevant for stellar explosions, as well as analytical expressions as functions of temperature in a format suitable for use in astrophysical simulations. Comparisons with the previous rate calculations are carried out, and the astrophysical implications are briefly discussed.
Sunil Kwon
2010-01-01
Full Text Available An investigation was carried out about the gold nanotube synthesis via a galvanic replacement reaction. The progress of the gold nanotube synthesis was investigated using electron microscopy and UV-Vis spectroscopy. In addition, the reaction rates of gold nanotube formation in the early stage of the reaction were studied. The chlorine ion concentration linearly increased with the gold precursor concentration but deviated from the stoichiometric amounts. This deviation was probably due to AgCl precipitates formed by the reaction of chlorine ions with dissolved silver ions. The replacement reaction was promoted with increased temperature and was nonlinearly proportional to the gold ion concentration. The outcomes of this research will enhance the current understanding of the galvanic replacement reaction.
D. K. Papoulias
2015-01-01
Full Text Available In this work, we explore ν-nucleus processes from a nuclear theory point of view and obtain results with high confidence level based on accurate nuclear structure cross sections calculations. Besides cross sections, the present study includes simulated signals expected to be recorded by nuclear detectors and differential event rates as well as total number of events predicted to be measured. Our original cross sections calculations are focused on measurable rates for the standard model process, but we also perform calculations for various channels of the nonstandard neutrino-nucleus reactions and come out with promising results within the current upper limits of the corresponding exotic parameters. We concentrate on the possibility of detecting (i supernova neutrinos by using massive detectors like those of the GERDA and SuperCDMS dark matter experiments and (ii laboratory neutrinos produced near the spallation neutron source facilities (at Oak Ridge National Lab by the COHERENT experiment. Our nuclear calculations take advantage of the relevant experimental sensitivity and employ the severe bounds extracted for the exotic parameters entering the Lagrangians of various particle physics models and specifically those resulting from the charged lepton flavour violating μ-→e- experiments (Mu2e and COMET experiments.
Aquilanti, Vincenzo; Coutinho, Nayara Dantas; Carvalho-Silva, Valter Henrique
2017-04-28
This article surveys the empirical information which originated both by laboratory experiments and by computational simulations, and expands previous understanding of the rates of chemical processes in the low-temperature range, where deviations from linearity of Arrhenius plots were revealed. The phenomenological two-parameter Arrhenius equation requires improvement for applications where interpolation or extrapolations are demanded in various areas of modern science. Based on Tolman's theorem, the dependence of the reciprocal of the apparent activation energy as a function of reciprocal absolute temperature permits the introduction of a deviation parameter d covering uniformly a variety of rate processes, from those where quantum mechanical tunnelling is significant and d 0, corresponding to the Pareto-Tsallis statistical weights: these generalize the Boltzmann-Gibbs weight, which is recovered for d = 0. It is shown here how the weights arise, relaxing the thermodynamic equilibrium limit, either for a binomial distribution if d > 0 or for a negative binomial distribution if d theory for chemical kinetics including quantum mechanical tunnelling, and for case (iii) to the stereodirectional specificity of the dynamics of reactions strongly hindered by the increase of temperature.This article is part of the themed issue 'Theoretical and computational studies of non-equilibrium and non-statistical dynamics in the gas phase, in the condensed phase and at interfaces'. © 2017 The Author(s).
Analysis of turbulent free-jet hydrogen-air diffusion flames with finite chemical reaction rates
Sislian, J. P.; Glass, I. I.; Evans, J. S.
1979-01-01
A numerical analysis is presented of the nonequilibrium flow field resulting from the turbulent mixing and combustion of an axisymmetric hydrogen jet in a supersonic parallel ambient air stream. The effective turbulent transport properties are determined by means of a two-equation model of turbulence. The finite-rate chemistry model considers eight elementary reactions among six chemical species: H, O, H2O, OH, O2 and H2. The governing set of nonlinear partial differential equations was solved by using an implicit finite-difference procedure. Radial distributions were obtained at two downstream locations for some important variables affecting the flow development, such as the turbulent kinetic energy and its dissipation rate. The results show that these variables attain their peak values on the axis of symmetry. The computed distribution of velocity, temperature, and mass fractions of the chemical species gives a complete description of the flow field. The numerical predictions were compared with two sets of experimental data. Good qualitative agreement was obtained.
Motola, Domenico; Vargiu, Antonio; Leone, Roberto; Conforti, Anita; Moretti, Ugo; Vaccheri, Alberto; Velo, Giampaolo; Montanaro, Nicola
2008-01-01
The reporting of adverse drug reactions (ADRs) is the mainstay of post-marketing surveillance systems. Under-reporting and selective reporting are considered the main limitations of a spontaneous reporting-based pharmacovigilance system. However, excessive reporting induced by external events may also impair signal detection by increasing the noise level. The aim of this study was to examine the influence of regulatory measures and other external factors on the rate of ADR reporting in Italy, focusing on four situations occurring in the last 10 years: ACE inhibitor-induced cough; HMG-CoA reductase inhibitors ('statins') and rhabdomyolysis; nimesulide and hepatic toxicity; and cyclo-oxygenase (COX)-2 selective inhibitors ('coxibs') and increase in cardiovascular risk. The study was based on data from spontaneous reporting in six Italian regions collected from January 1995 to December 2005. We analysed a 10-year period as a reasonable time interval around the four situations of interest, highlighting the influence of regulatory measures on the rate of ADR reporting (number of reports per million inhabitants). Chi-squared tests were used to assess the statistical significance of any changes in ADR reporting. Drug sales data were also studied to examine possible changes in drug use. Sales data were expressed as daily defined dose per 1000 inhabitants per day. ACE inhibitors: a 5-fold increase in the reporting rate of ACE inhibitor-induced cough was observed in 1998 and 1999 following a restriction on reimbursement for angiotensin receptor blockers introduced in 1998 and removed at the end of 1999. Statins: after the withdrawal of cerivastatin in 2001, the ADR reporting rate increased more than 4-fold, with musculoskeletal ADRs representing about 60% of all the ADRs reported in that year, and progressively decreased in the following years. Nimesulide: an increase in hepatic ADR reporting was observed after withdrawal of the drug from the Finnish and Spanish markets in
Sun, Cuihong; Xu, Baoen; Zhang, Shaowen
2014-05-22
Methacrolein is a major degradation product of isoprene, the reaction of methacrolein with Cl atoms may play some roles in the degradation of isoprene where these species are relatively abundant. However, the energetics and kinetics of this reaction, which govern the reaction branching, are still not well understood so far. In the present study, two-dimensional potential energy surfaces were constructed to analyze the minimum energy path of the barrierless addition process between Cl and the C═C double bond of methacrolein, which reveals that the terminal addition intermediate is directly formed from the addition reaction. The terminal addition intermediate can further yield different products among which the reaction paths abstracting the aldehyde hydrogen atom and the methyl hydrogen atom are dominant reaction exits. The minimum reaction path for the direct aldehydic hydrogen atom abstraction is also obtained. The reaction kinetics was calculated by the variational transition state theory in conjunction with the master equation method. From the theoretical model we predicted that the overall rate constant of the Cl + methacrolein reaction at 297 K and atmospheric pressure is koverall = 2.3× 10(-10) cm(3) molecule(-1) s(-1), and the branching ratio of the aldehydic hydrogen abstraction is about 12%. The reaction is pressure dependent at P pressure limit at about 100 Torr. The calculated results could well account for the experimental observations.
Walker, Anthony P.; Quaife, Tristan; Van Bodegom, Peter M.; De Kauwe, Martin G.; Keenan, Trevor F.; Joiner, Joanna; Lomas, Mark R.; MacBean, Natasha; Xu, Chongang; Yang, Xiaojuan;
2017-01-01
The maximum photosynthetic carboxylation rate (V (sub cmax)) is an influential plant trait that has multiple scaling hypotheses, which is a source of uncertainty in predictive understanding of global gross primary production (GPP). Four trait-scaling hypotheses (plant functional type, nutrient limitation, environmental filtering, and plant plasticity) with nine specific implementations were used to predict global V(sub cmax) distributions and their impact on global GPP in the Sheffield Dynamic Global Vegetation Model (SDGVM). Global GPP varied from 108.1 to 128.2 petagrams of Carbon (PgC) per year, 65 percent of the range of a recent model intercomparison of global GPP. The variation in GPP propagated through to a 27percent coefficient of variation in net biome productivity (NBP). All hypotheses produced global GPP that was highly correlated (r equals 0.85-0.91) with three proxies of global GPP. Plant functional type-based nutrient limitation, underpinned by a core SDGVM hypothesis that plant nitrogen (N) status is inversely related to increasing costs of N acquisition with increasing soil carbon, adequately reproduced global GPP distributions. Further improvement could be achieved with accurate representation of water sensitivity and agriculture in SDGVM. Mismatch between environmental filtering (the most data-driven hypothesis) and GPP suggested that greater effort is needed understand V(sub cmax) variation in the field, particularly in northern latitudes.
Modal dispersion, pulse broadening and maximum transmission rate in GRIN optical fibers encompass a central dip in the core index profile
El-Diasty, Fouad; El-Hennawi, H. A.; El-Ghandoor, H.; Soliman, Mona A.
2013-12-01
Intermodal and intramodal dispersions signify one of the problems in graded-index multi-mode optical fibers (GRIN) used for LAN communication systems and for sensing applications. A central index dip (depression) in the profile of core refractive-index may occur due to the CVD fabrication processes. The index dip may also be intentionally designed to broaden the fundamental mode field profile toward a plateau-like distribution, which have advantages for fiber-source connections, fiber amplifiers and self-imaging applications. Effect of core central index dip on the propagation parameters of GRIN fiber, such as intermodal dispersion, intramodal dispersion and root-mean-square broadening, is investigated. The conventional methods usually study optical signal propagation in optical fiber in terms of mode characteristics and the number of modes, but in this work multiple-beam Fizeau interferometry is proposed as an inductive but alternative methodology to afford a radial approach to determine dispersion, pulse broadening and maximum transmission rate in GRIN optical fiber having a central index dip.
Su, Yu-min; Makinia, Jacek; Pagilla, Krishna R
2008-04-01
The autotrophic maximum specific growth rate constant, muA,max, is the critical parameter for design and performance of nitrifying activated sludge systems. In literature reviews (i.e., Henze et al., 1987; Metcalf and Eddy, 1991), a wide range of muA,max values have been reported (0.25 to 3.0 days(-1)); however, recent data from several wastewater treatment plants across North America revealed that the estimated muA,max values remained in the narrow range 0.85 to 1.05 days(-1). In this study, long-term operation of a laboratory-scale sequencing batch reactor system was investigated for estimating this coefficient according to the low food-to-microorganism ratio bioassay and simulation methods, as recommended in the Water Environment Research Foundation (Alexandria, Virginia) report (Melcer et al., 2003). The estimated muA,max values using steady-state model calculations for four operating periods ranged from 0.83 to 0.99 day(-1). The International Water Association (London, United Kingdom) Activated Sludge Model No. 1 (ASM1) dynamic model simulations revealed that a single value of muA,max (1.2 days(-1)) could be used, despite variations in the measured specific nitrification rates. However, the average muA,max was gradually decreasing during the activated sludge chlorination tests, until it reached the value of 0.48 day(-1) at the dose of 5 mg chlorine/(g mixed liquor suspended solids x d). Significant discrepancies between the predicted XA/YA ratios were observed. In some cases, the ASM1 predictions were approximately two times higher than the steady-state model predictions. This implies that estimating this ratio from a complex activated sludge model and using it in simple steady-state model calculations should be accepted with great caution and requires further investigation.
A sensitivity study of s-process: the impact of uncertainties from nuclear reaction rates
Vinyoles, N.; Serenelli, A.
2016-01-01
The slow neutron capture process (s-process) is responsible for the production of about half the elements beyond the Fe-peak. The production sites and the conditions under which the different components of s-process occur are relatively well established. A detailed quantitative understanding of s-process nucleosynthesis may yield light in physical processes, e.g. convection and mixing, taking place in the production sites. For this, it is important that the impact of uncertainties in the nuclear physics is well understood. In this work we perform a study of the sensitivity of s-process nucleosynthesis, with particular emphasis in the main component, on the nuclear reaction rates. Our aims are: to quantify the current uncertainties in the production factors of s-process elements originating from nuclear physics and, to identify key nuclear reactions that require more precise experimental determinations. In this work we studied two different production sites in which s-process occurs with very different neutron exposures: 1) a low-mass extremely metal-poor star during the He-core flash (nn reaching up to values of ∼ 1014cm-3); 2) the TP-AGB phase of a M⊙, Z=0.01 model, the typical site of the main s-process component (nn up to 108 — 109cm-3). In the first case, the main variation in the production of s-process elements comes from the neutron poisons and with relative variations around 30%-50%. In the second, the neutron poison are not as important because of the higher metallicity of the star that actually acts as a seed and therefore, the final error of the abundances are much lower around 10%-25%.
Theoretical study of the mechanism and rate constant of the B + CO2 reaction.
Poully, Benjamin; Bergeat, Astrid; Hannachi, Yacine
2008-09-04
The different stationary points on the potential energy surface relative to the title reaction have been reinvestigated at the B3LYP/aug-cc-pVDZ level with relative energies computed at the CCSD(T)/aug-cc-pVTZ level with B3LYP/aug-cc-pVDZ optimized geometries and by using the G3B3 composite method. Two entrance channels have been identified. The first one corresponds to boron addition at one of the oxygen atoms of the CO 2 molecule leading to trans-BOCO, which is found to be about 27 kcal/mol exothermic with a potential energy barrier of 16.4 kcal/mol (G3B3). The second channel, which has not been identified in previous theoretical works, corresponds to a direct insertion of the boron atom into a CO bond and leads to OBCO. The B + CO 2 --> OBCO step is found to be about 84 kcal/mol exothermic and needs to overcome a potential energy barrier of only 3.6 kcal/mol (G3B3). The rate constant at 300 K of the insertion step, calculated by using TST theory with G3B3 calculated activation energy value, is 5.4 10 (-14) cm (3) molecule (-1) s (-1), in very good agreement with the experimental data ((7.0 +/- 2.8) 10 (-14) cm (3) molecule (-1) s (-1), DiGiuseppe, T. G.; Davidovits, P. J. Chem. Phys. 1981, 74, 3287). The one corresponding to the addition process is found to be several orders of magnitude smaller because of a much higher potential energy barrier. The addition channel would not contribute to the title reaction even at high temperature. A modified Arrhenius equation has been fitted in the 300-1000 K temperature range, which might be useful for chemical models.
Calcite Dissolution in Deionized Water from 50℃ to 250℃ at I0 MPa:Rate Equation and Reaction Order
GONG Qingjie; DENG Jun; WANG Qingfei; YANG Liqiang; SHE Min
2008-01-01
Carbonate minerals and water (or geofiuids) reactions are important for modeling of geochemical processes and have received considerable attention over the past decades. The calcite dissolution rates from 50℃ to 250℃ at 10 Mpa in deionized water with a flow rate varying from 0.2 to 5 mL/min were experimentally measured in a continuous flow column pressure vessel reactor. The dissolution began near the equilibrium with clceq > 0.3 and finally reached the equilibrium at 100℃-250℃, so the corresponding solubility was also determined as 1.87, 2.02, 2.02 and 1.88×10-4"mol/L at 100℃, 150℃, 200~C and 2500C respectively, which was first increasing and then switching to decreasing with temperature and the maximum value might occur between 150℃ and 200℃. The experimental dissolution rate not only increased with temperature, but also had a rapid increase between 150℃ and 200℃ at a constant flow rate of 4 mL/min. The measured dissolution rates can be described using rate equations of R = k(1-c/c) or R = kc. In these equations the reaction order n changed with temperature, which indicates that n was a variable rather than a constant, and the activation energy was 13.4 kJ/mol calculated with R = k(1-c/c) or 18.0 kJ/mol with R = kc, which is a little lower than the surface controlled values. The varied reaction order and lower activation energy indicates that calcite dissolution in this study is a complex interplay of diffusion controlled and surface controlled processes.
Morales, Sébastien B; Le Picard, Sébastien D; Canosa, André; Sims, Ian R
2010-01-01
The kinetics of the reactions of cyano radical, CN (X2sigma+) with three hydrocarbons, propane (CH3CH2CH3), propene (CH3CH=CH2) and 1-butyne (CH[triple band]CCH2CH3) have been studied over the temperature range of 23-298 K using a CRESU (Cinétique de Réaction en Ecoulement Supersonique Uniforme or Reaction Kinetics in Uniform Supersonic Flow) apparatus combined with the pulsed laser photolysis-laser induced fluorescence technique. These reactions are of interest for the cold atmospheres of Titan, Pluto and Triton, as they might participate in the formation of nitrogen and carbon bearing molecules, including nitriles, that are thought to play an important role in the formation of hazes and biological molecules. All three reactions are rapid with rate coefficients in excess of 10(-10) cm3 molecule(-1) s(-1) at the lowest temperatures of this study and show behaviour characteristic of barrierless reactions. Temperature dependences, different for each reaction, are compared to those used in the most recent photochemical models of Titan's atmosphere.
Mudunuru, M. K.; Nakshatrala, K. B.
2016-01-01
We present a robust computational framework for advective-diffusive-reactive systems that satisfies maximum principles, the non-negative constraint, and element-wise species balance property. The proposed methodology is valid on general computational grids, can handle heterogeneous anisotropic media, and provides accurate numerical solutions even for very high Péclet numbers. The significant contribution of this paper is to incorporate advection (which makes the spatial part of the differential operator non-self-adjoint) into the non-negative computational framework, and overcome numerical challenges associated with advection. We employ low-order mixed finite element formulations based on least-squares formalism, and enforce explicit constraints on the discrete problem to meet the desired properties. The resulting constrained discrete problem belongs to convex quadratic programming for which a unique solution exists. Maximum principles and the non-negative constraint give rise to bound constraints while element-wise species balance gives rise to equality constraints. The resulting convex quadratic programming problems are solved using an interior-point algorithm. Several numerical results pertaining to advection-dominated problems are presented to illustrate the robustness, convergence, and the overall performance of the proposed computational framework.
Petrowsky, Matt; Glatzhofer, Daniel T; Frech, Roger
2013-11-21
The dependence of the reaction rate on solvent dielectric constant is examined for the reaction of trihexylamine with 1-bromohexane in a series of 2-ketones over the temperature range 25-80 °C. The rate constant data are analyzed using the compensated Arrhenius formalism (CAF), where the rate constant assumes an Arrhenius-like equation that also contains a dielectric constant dependence in the exponential prefactor. The CAF activation energies are substantially higher than those obtained using the simple Arrhenius equation. A master curve of the data is observed by plotting the prefactors against the solvent dielectric constant. The master curve shows that the reaction rate has a weak dependence on dielectric constant for values approximately less than 10 and increases more rapidly for dielectric constant values greater than 10.
Dybeck, Eric Christopher; Plaisance, Craig Patrick; Neurock, Matthew
2017-02-14
A novel algorithm has been developed to achieve temporal acceleration during kinetic Monte Carlo (KMC) simulations of surface catalytic processes. This algorithm allows for the direct simulation of reaction networks containing kinetic processes occurring on vastly disparate timescales which computationally overburden standard KMC methods. Previously developed methods for temporal acceleration in KMC have been designed for specific systems and often require a priori information from the user such as identifying the fast and slow processes. In the approach presented herein, quasi-equilibrated processes are identified automatically based on previous executions of the forward and reverse reactions. Temporal acceleration is achieved by automatically scaling the intrinsic rate constants of the quasi-equilibrated processes, bringing their rates closer to the timescales of the slow kinetically relevant non-equilibrated processes. All reactions are still simulated directly, although with modified rate constants. Abrupt changes in the underlying dynamics of the reaction network are identified during the simulation and the reaction rate constants are rescaled accordingly. The algorithm has been utilized here to model the Fischer-Tropsch synthesis reaction over ruthenium nanoparticles. This reaction network has multiple timescale-disparate processes which would be intractable to simulate without the aid of temporal acceleration. The accelerated simulations are found to give reaction rates and selectivities indistinguishable from those calculated by an equivalent mean-field kinetic model. The computational savings of the algorithm can span many orders of magnitude in realistic systems and the computational cost is not limited by the magnitude of the timescale disparity in the system processes. Furthermore, the algorithm has been designed in a generic fashion and can easily be applied to other surface catalytic processes of interest.
Potier, Elise; Loubet, Benjamin; Durand, Brigitte; Flura, Dominique; Bourdat-Deschamps, Marjolaine; Ciuraru, Raluca; Ogée, Jérôme
2017-02-01
In this study we present results from a laboratory experiment designed to evaluate the first-order chemical reaction rate (k) of ozone in water films on plant leaves occurring during dew or rain events. Ozone deposition to wet cuticles is indeed known to be a significant pathway of ozone deposition, but the underlying processes are not yet well understood. Leaf infusions obtained by infusing plant leaves with water at room temperature were introduced into a wet effluent denuder fed with a flux of ozone-rich air. Ozone, water vapour concentrations and temperature were measured in both inlet and outlet airflows in order to compute ozone reaction rates kr using an ozone reaction-diffusion model in the water film. Ascorbate solutions were used to validate the set up and led to kr = 3.6 107 M-1 s-1 consistent with the literature. Ozone reaction rates were determined for wheat, beech, oak and pine leaves infusions at several developmental stages, as well as for rain samples. Leaf infusions reaction rates were between 240 s-1 and 3.4 105 s-1 depending on species and developmental stage, while k for rain water ranged from 130 to 830 s-1. Wheat leaves solutions showed significantly (P ascorbate and VOCs as well as the reaction products of ozone with these compounds.
Umesh S Joge
2013-01-01
Full Text Available Background: From the moment scientists identified Human Immunodeficiency Virus/Acquired Immunodeficiency Syndrome (HIV/AIDS, social responses of fear, denial, stigma, and discrimination have accompanied the epidemic. Aims: To assess the rate of disclosure of HIV serostatus, reactions by the HIV/AIDS patients and their spouse, and discrimination faced by the patients. Methods: The present cross-sectional study was conducted at Antiretroviral Therapy (ART center of a rural tertiary care hospital, situated in Marathawada region of Maharashtra state from November 2008 to October 2010. Totally, 801 HIV-positive patients coming to ART center for treatment were included after ensuring confidentiality and taking informed consent. A preformed questionnaire was used to enquire about reaction after diagnosis, disclosure, and discrimination faced by the patients. The data analyzed using descriptive statistics and Chi-square test. Results: The most common immediate reaction by the HIV patients after getting diagnosed as seropositive was fear (593, 74.03% followed by depression (385, 48.06% and suicidal thoughts (98, 12.25%. Out of 801 patients, 769 (96% had spouse and of these maximum number of patients (653, 84.92% had disclosed HIV status to their spouses. Most common immediate reaction by spouse after disclosure was crime (324, 42.13% followed by horror (294, 38.23% and anger (237, 36.29%. Maximum number of patients were discriminated by friends (120, 71.01% followed by discrimination at workplace (49, 67.12%, by neighbors (32, 56.14%, and by relatives (53, 43.80%. Conclusion: Male positives were granted greater acceptance, care, and support by their spouses. More percentage of females discriminated by neighbors, relatives, and friends and at workplace which might be due to factors like customs, morals, and taboos.
Rate Coefficients of the Reaction of OH with Allene and Propyne at High Temperatures
Es-Sebbar, Et Touhami
2016-09-28
Allene (H2C═C═CH2; a-C3H4) and propyne (CH3C≡CH; p-C3H4) are important species in various chemical environments. In combustion processes, the reactions of hydroxyl radicals with a-C3H4 and p-C3H4 are critical in the overall fuel oxidation system. In this work, rate coefficients of OH radicals with allene (OH + H2C═C═CH2 → products) and propyne (OH + CH3C≡CH → products) were measured behind reflected shock waves over the temperature range of 843–1352 K and pressures near 1.5 atm. Hydroxyl radicals were generated by rapid thermal decomposition of tert-butyl hydroperoxide ((CH3)3–CO–OH), and monitored by narrow line width laser absorption of the well-characterized R1(5) electronic transition of the OH A–X (0,0) electronic system near 306.7 nm. Results show that allene reacts faster with OH radicals than propyne over the temperature range of this study. Measured rate coefficients can be expressed in Arrhenius form as follows: kallene+OH(T) = 8.51(±0.03) × 10–22T3.05 exp(2215(±3)/T), T = 843–1352 K; kpropyne+OH(T) = 1.30(±0.07) × 10–21T3.01 exp(1140(±6)/T), T = 846–1335 K.
Gonzalez-Lopezlira, Rosa A. [On sabbatical leave from the Centro de Radioastronomia y Astrofisica, UNAM, Campus Morelia, Michoacan, C.P. 58089, Mexico. (Mexico); Pflamm-Altenburg, Jan; Kroupa, Pavel, E-mail: r.gonzalez@crya.unam.mx [Argelander Institut fuer Astronomie, Universitaet Bonn, Auf dem Huegel 71, D-53121 Bonn (Germany)
2013-06-20
We analyze the relationship between maximum cluster mass and surface densities of total gas ({Sigma}{sub gas}), molecular gas ({Sigma}{sub H{sub 2}}), neutral gas ({Sigma}{sub H{sub I}}), and star formation rate ({Sigma}{sub SFR}) in the grand-design galaxy M51, using published gas data and a catalog of masses, ages, and reddenings of more than 1800 star clusters in its disk, of which 223 are above the cluster mass distribution function completeness limit. By comparing the two-dimensional distribution of cluster masses and gas surface densities, we find for clusters older than 25 Myr that M{sub 3rd}{proportional_to}{Sigma}{sub H{sub I}{sup 0.4{+-}0.2}}, whereM{sub 3rd} is the median of the five most massive clusters. There is no correlation with{Sigma}{sub gas},{Sigma}{sub H2}, or{Sigma}{sub SFR}. For clusters younger than 10 Myr, M{sub 3rd}{proportional_to}{Sigma}{sub H{sub I}{sup 0.6{+-}0.1}} and M{sub 3rd}{proportional_to}{Sigma}{sub gas}{sup 0.5{+-}0.2}; there is no correlation with either {Sigma}{sub H{sub 2}} or{Sigma}{sub SFR}. The results could hardly be more different from those found for clusters younger than 25 Myr in M33. For the flocculent galaxy M33, there is no correlation between maximum cluster mass and neutral gas, but we have determined M{sub 3rd}{proportional_to}{Sigma}{sub gas}{sup 3.8{+-}0.3}, M{sub 3rd}{proportional_to}{Sigma}{sub H{sub 2}{sup 1.2{+-}0.1}}, and M{sub 3rd}{proportional_to}{Sigma}{sub SFR}{sup 0.9{+-}0.1}. For the older sample in M51, the lack of tight correlations is probably due to the combination of strong azimuthal variations in the surface densities of gas and star formation rate, and the cluster ages. These two facts mean that neither the azimuthal average of the surface densities at a given radius nor the surface densities at the present-day location of a stellar cluster represent the true surface densities at the place and time of cluster formation. In the case of the younger sample, even if the clusters have not yet
New reaction rates for improved primordial D/H calculation and the cosmic evolution of deuterium
Coc, Alain; Uzan, Jean-Philippe; Vangioni, Elisabeth; Descouvemont, Pierre; Illiadis, Christian; Longland, Richard
2015-01-01
Primordial or big bang nucleosynthesis (BBN) is one of the three historical strong evidences for the big bang model. Standard BBN is now a parameter free theory, since the baryonic density of the Universe has been deduced with an unprecedented precision from observations of the anisotropies of the cosmic microwave background (CMB) radiation. There is a good agreement between the primordial abundances of 4He, D, 3He and 7Li deduced from observations and from primordial nucleosynthesis calculations. However, the 7Li calculated abundance is significantly higher than the one deduced from spectroscopic observations and remains an open problem. In addition, recent deuterium observations have drastically reduced the uncertainty on D/H, to reach a value of 1.6%. It needs to be matched by BBN predictions whose precision is now limited by thermonuclear reaction rate uncertainties. This is especially important as many attempts to reconcile Li observations with models lead to an increased D prediction. Here, we re-evalua...
Predicting reaction rate constants of ozone with organic compounds from radical structures
Yu, Xinliang; Yi, Bing; Wang, Xueye; Chen, Jianfang
2012-05-01
The reaction rate constants of ozone with organic compounds in the atmosphere were predicted by a quantitative structure-activity relationship (QSAR) model. Density functional theory (DFT) calculations, for the first time, were carried out on the radicals from organic compounds, at the UB3LYP level of theory with 6-31G(d) basis set. A set of quantum chemical descriptors calculated from the radicals, the energy of the highest occupied molecular orbital of beta spin states (EβHOMO), the molecular average polarizability (α), and the total energy (ET), were used to build the general QSAR model for aliphatic compounds, applying the genetic algorithm (GA) technique and support vector machine (SVM) regression. The root mean square errors (RMSE) are 0.680 for the training set (68 compounds), 0.777 for the validation set (36 compounds) and 0.709 for the test set (35 compounds). Investigated results indicate that the SVM model given here has good predictivity for aliphatic compounds.
Tessier, André; Gobeil, Charles; Laforte, Lucie
2014-07-01
Sediment cores were collected at the deepest site of twelve headwater lakes from the Province of Québec, Canada that receive contaminants only from atmospheric deposition, either directly to the lake surface or indirectly from the watershed. Several of the lakes are located within relatively short distance (In2S3(s) do not precipitate in the sediments and that adsorption of In onto sedimentary FeS(s) does not occur. However, similarities in the In and Fe porewater profiles, and the presence of In in the authigenic Fe-rich solids, reveal that part of the In becomes associated with authigenic Fe oxyhydroxides in the perennially oxic lake and is coupled to the Fe redox cycling. Comparison of the In/Corg and In/Fe molar ratios in the authigenic Fe-rich material and in surface sediments (0-0.5 cm) of this lake suggests that most non-lithogenic In was bound to humic substances. From the magnitude of the net In reaction rates, we infer that the post-depositional redistribution of this element is quantitatively not important and that the In sedimentary record represents accurately In deposition at the sampling sites. Reconstructed chronologies of the anthropogenic In deposition and comparison of In inventories among lakes point to non-ferrous metal smelters as a past significant source of atmospheric In contamination and to a significant reduction of industrial In emissions into the North American atmosphere in recent decades.
Type Ia supernovae and the ^{12}C+^{12}C reaction rate
Bravo, E; Domínguez, I; Straniero, O; Isern, J; Escartín, J A
2011-01-01
The experimental determination of the cross-section of the ^{12}C+^{12}C reaction has never been made at astrophysically relevant energies (E<2 MeV). The profusion of resonances throughout the measured energy range has led to speculation that there is an unknown resonance at E\\sim1.5 MeV possibly as strong as the one measured for the resonance at 2.14 MeV. We study the implications that such a resonance would have for the physics of SNIa, paying special attention to the phases that go from the crossing of the ignition curve to the dynamical event. We use one-dimensional hydrostatic and hydrodynamic codes to follow the evolution of accreting white dwarfs until they grow close to the Chandrasekhar mass and explode as SNIa. In our simulations, we account for a low-energy resonance by exploring the parameter space allowed by experimental data. A change in the ^{12}C+^{12}C rate similar to the one explored here would have profound consequences for the physical conditions in the SNIa explosion, namely the centra...
Shimba, Nobuhisa; Yokoyama, Kei-ichi; Suzuki, Ei-ichiro
2002-03-13
Incorporation of inter- or intramolecular covalent cross-links into food proteins with microbial transglutaminase (MTG) improves the physical and textural properties of many food proteins such as tofu, boiled fish paste, and sausage. Other transglutaminases (TGases) are expected to be used in the same way, and also to extend the scope of industrial applications to materials, drugs, and so on. The TGases have great diversity, not only in amino acid sequence and size, but also in their substrate specificities and catalytic activities, and therefore, it is quite difficult to estimate their reactivity. We have developed an NMR-based method using the enzymatic labeling technique (ELT) for simultaneous analysis of the substrate specificities and reaction rates of TGases. It is quite useful for comparing the existing TGases and for screening new TGases or TGases variants. This method has shown that MTG is superior for industrial use because of its lower substrate specificity compared with those of guinea pig liver transglutaminase (GTG) and red sea bream liver transglutaminase (FTG). We have also found that an MTG variant lacking an N-terminal aspartic acid residue has higher activity than that of the native enzyme.
Kustova, Elena V.; Kremer, Gilberto M.
2014-12-01
Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman-Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.
Chiba Shigeru
2007-09-01
Full Text Available Abstract Background Computer graphics and virtual reality techniques are useful to develop automatic and effective rehabilitation systems. However, a kind of virtual environment including unstable visual images presented to wide field screen or a head mounted display tends to induce motion sickness. The motion sickness induced in using a rehabilitation system not only inhibits effective training but also may harm patients' health. There are few studies that have objectively evaluated the effects of the repetitive exposures to these stimuli on humans. The purpose of this study is to investigate the adaptation to visually induced motion sickness by physiological data. Methods An experiment was carried out in which the same video image was presented to human subjects three times. We evaluated changes of the intensity of motion sickness they suffered from by a subjective score and the physiological index ρmax, which is defined as the maximum cross-correlation coefficient between heart rate and pulse wave transmission time and is considered to reflect the autonomic nervous activity. Results The results showed adaptation to visually-induced motion sickness by the repetitive presentation of the same image both in the subjective and the objective indices. However, there were some subjects whose intensity of sickness increased. Thus, it was possible to know the part in the video image which related to motion sickness by analyzing changes in ρmax with time. Conclusion The physiological index, ρmax, will be a good index for assessing the adaptation process to visually induced motion sickness and may be useful in checking the safety of rehabilitation systems with new image technologies.
Capture cross-section and rate of the 14C(, )15C reaction from the Coulomb dissociation of 15C
Shubhchintak; Neelam; R Chatterjee
2014-10-01
We calculate the Coulomb dissociation of 15C on a Pb target at 68 MeV/u incident beam energy within the fully quantum mechanical distorted wave Born approximation formalism of breakup reactions. The capture cross-section and the subsequent rate of the 14C(, )15C reaction are calculated from the photodisintegration of 15C, using the principle of detailed balance. Our theoretical model is free from the uncertainties associated with the multipole strength distributions of the projectile.
Roy, Dipankar; Sunoj, Raghavan B
2007-11-08
The first ab initio and DFT studies on the mechanism of the MBH reaction show that the rate-limiting step involves an intramolecular proton transfer in the zwitterionic intermediate generated by the addition of enolate to electrophile. The activation barrier for the C-C bond-formation is found to be 20.2 kcal/mol lower than the proton-transfer step for the MBH reaction between methyl vinyl ketone and benzaldehyde catalyzed by DABCO.
Rivero Santamaría, Alejandro; Dayou, Fabrice; Rubayo-Soneira, Jesus; Monnerville, Maurice
2017-02-15
The dynamics of the Si((3)P) + OH(X(2)Π) → SiO(X(1)Σ(+)) + H((2)S) reaction is investigated by means of the time-dependent wave packet (TDWP) approach using an ab initio potential energy surface recently developed by Dayou et al. ( J. Chem. Phys. 2013 , 139 , 204305 ) for the ground X(2)A' electronic state. Total reaction probabilities have been calculated for the first 15 rotational states j = 0-14 of OH(v=0,j) at a total angular momentum J = 0 up to a collision energy of 1 eV. Integral cross sections and state-selected rate constants for the temperature range 10-500 K were obtained within the J-shifting approximation. The reaction probabilities display highly oscillatory structures indicating the contribution of long-lived quasibound states supported by the deep SiOH/HSiO wells. The cross sections behave with collision energies as expected for a barrierless reaction and are slightly sensitive to the initial rotational excitation of OH. The thermal rate constants show a marked temperature dependence below 200 K with a maximum value around 15 K. The TDWP results globally agree with the results of earlier quasi-classical trajectory (QCT) calculations carried out by Rivero-Santamaria et al. ( Chem. Phys. Lett. 2014 , 610-611 , 335 - 340 ) with the same potential energy surface. In particular, the thermal rate constants display a similar temperature dependence, with TDWP values smaller than the QCT ones over the whole temperature range.
Hubbard, S. M.; Coutts, D. S.; Matthews, W.; Guest, B.; Bain, H.
2015-12-01
In basins adjacent to continually active arcs, detrital zircon geochronology can be used to establish a high-resolution chronostratigraphic framework for deep-time strata. Large-nU-Pb geochronological datasets can yield a statistically significant signature from the youngest sub-population of detrital zircons, which we deduce from maximum depositional age (MDA) calculations. MDA is determined through numerous methods such as the mean age of three or more overlapping grain ages at 2σ error, favored in this analysis. Positive identification of the youngest detrital zircon population in a rock is the limiting factor on precision and resolution. The Campanian-Paleogene Nanaimo Group of B.C., Canada, was deposited in a forearc basin, outboard of the Coast Mountain Batholith. The record of a deep-water sediment-routing system is exhumed at Denman and Hornby islands; sandstone- and conglomerate- dominated strata compose a composite sedimentary unit 20 km across and 1.5 km thick, in strike section. Volcanic ashes are absent from the succession, which has been constrained biostratigraphically. Eleven detrital zircon samples are analyzed to define stratigraphic architecture and provide insight into sedimentation rates. Our dataset (n=3081) constrains the overall duration of channelization to ~18 Ma. A series of at least five distinct composite channel fills 3-6 km wide and 400-600 m thick are identified. The MDA of these units are statistically distinct and constrained to better than 3% precision. Sedimentation rates amongst the channel fills increase upward, from 60-100 m/Ma to >500 m/Ma. This is likely linked to the tendency of a slope channel system to be dominated by sediment bypass early in its evolution, and later dominated by aggradation as large-scale levees develop. Channel processes were not continuous, with the longest hiatus ~6 Ma. The large-n detrital zircon dataset provides unprecedented insight into long-term sediment routing, evidence for which is
Opeida, I. A.; Litvinov, Yu. E.; Kushch, O. V.; Kompanets, M. A.; Shendrik, A. N.; Matvienko, A. G.; Novokhatko, A. A.
2016-11-01
The kinetics of the reactions of hydrogen atom abstraction from the C-H bonds of substrates of different structures by phthalimide- N-oxyl radicals is studied. The rate constants of this reaction are measured and the kinetic isotope effects are determined. It is shown that in addition to the thermodynamic factor, Coulomb forces and donor-acceptor interactions affect the reaction between phthalimide- N-oxyl radicals and substrate molecules, altering the shape of the transition state. This favors the tunneling of hydrogen atoms and leads to a substantial reduction in the activation energy of the process.
Measurement of rate constant for gas-phase reaction of DDVP with OH radical by using LP-FTIR
无
2002-01-01
Pollution caused by organic pesticides has received increasing attention. Until now, studies on organic pesticides pollution are mainly focused on soil and water. For reactions of organic pesticides in gas-phase, there are very little research results reported. Using a long path quartz reactor to simulate the atmospheric reaction of dimethyl_dichloro_vinyl_phosphate(DDVP) with OH radicals, the rate constant for the reaction at room temperature is measured at (3.06±0.46)×10-11 cm3 s-1 with Fourier transform infrared spectrograph.The result indicates that DDVP degrades relatively fast in the atmosphere and is unlikely to cause persistent pollution.
Lee, Chang-Seop; Lee, Kang-Hyu; Jung, Min-Hee; Lee, Heung-Bum
2008-11-01
To determine the vaccination rate and its adverse reactions after influenza vaccination, we administered an anonymous questionnaire survey during the last three influenza seasons from 2005-2006 to 2007-2008. In total, the rate of Influenza vaccination was 82.3% in health-care personnel. Dividing the subjects into four groups by work category, the vaccine coverage rates were as follows: physicians 67.9%; nurses and nursing assistants 91.2%; technicians, pharmacists, therapists, and administrative personnel 80.2%; and other personnel not directly involved in patient care but having the potential of being exposed to infectious agents 89%. The most frequent adverse reaction after vaccination was soreness at the injection site in 33.4%, followed by skin redness in 18.1%, myalgia in 17.7%, fatigue in 17%, and febrile sensation in 15.2%. After vaccination, such adverse reactions began within 24 h in 70.6% of subjects. Eighty-nine percent of those adverse reactions persisted for 1-3 days, but 11% persisted more than 4 days. Serious adverse reactions were not noted; the reported adverse reactions were relatively minor and transient. Surprisingly, among those who were vaccinated, the physicians' participation was the lowest. We believe that influenza vaccination is safe and that physicians should be more concerned with influenza vaccination and its impact on the health-care community.
Variational RRKM calculation of thermal rate constant for C–H bond fission reaction of nitro methane
Afshin Taghva Manesh
2017-02-01
Full Text Available The present work provides quantitative results for the rate constants of unimolecular C–H bond fission reactions in the nitro methane at elevated temperatures up to 2000 K. In fact, there are three different hydrogen atoms in the nitro methane. The potential energy surface for each C–H bond fission reaction of nitro methane was investigated by ab initio calculations. The geometry and vibrational frequencies of the species involved in this process were optimized at the MP2 level of theory, using the cc-pvdz basis set. Since C–H bond fission channel is a barrierless reaction, we have used variational RRKM theory to predict rate coefficients. By means of calculated rate coefficients at different temperatures, the Arrhenius expression of the channel over the temperature range of 100–2000 K is k(T = 5.9E19∗exp(−56274.6/T.
Shell model based reaction rates for rp-process nuclei in the mass range A=44-63
Fisker, J L; Görres, J; Langanke, K; Martínez-Pinedo, G; Wiescher, M C
2001-01-01
We have used large-scale shell-model diagonalization calculations to determine the level spectra, proton spectroscopic factors, and electromagnetic transition probabilities for proton rich nuclei in the mass range A=44-63. Based on these results and the available experimental data, we calculated the resonances for proton capture reactions on neutron deficient nuclei in this mass range. We also calculated the direct capture processes on these nuclei in the framework of a Woods-Saxon potential model. Taking into account both resonant and direct contributions, we determined the ground-state proton capture reaction rates for these nuclei under hot hydrogen burning conditions for temperatures between 10 sup 8 and 10 sup 1 sup 0 K. The calculated compound-nucleus level properties and the reaction rates are presented here; the rates are also available in computer-readable format from the authors.
Determination of the 36Mg(n ,γ )37Mg reaction rate from Coulomb dissociation of 37Mg
Shubhchintak; Chatterjee, R.; Shyam, R.
2017-08-01
We use the Coulomb dissociation (CD) method to calculate the rate of the 36Mg(n ,γ )37Mg radiative capture reaction. The CD cross sections of the 37Mg nucleus on a 208Pb target at the beam energy of 244 MeV/nucleon, for which new experimental data have recently become available, were calculated within the framework of a finite-range distorted-wave Born approximation theory that is extended to include the projectile deformation effects. Invoking the principle of detailed balance, these cross sections are used to determine the excitation function and subsequently the rate of the 36Mg(n ,γ )37Mg reaction. We compare these rates to those of the 36Mg(α ,n )39Si reaction calculated within a Hauser-Feshbach model. We find that for T9 as large as up to 1.0 (in units of 109 K) the 36Mg(n ,γ )37Mg reaction is much faster than the 36Mg(α ,n )39Si one. The inclusion of the effects of 37Mg projectile deformation in the breakup calculations enhances the (n ,γ ) reaction rate even further. Therefore, it is highly unlikely that the (n ,γ )β -decay r -process flow will be broken at the 36Mg isotope by the α process.
Peters, Catherine A [Princeton University
2013-05-15
This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE legacy waste problems.
Levay, B.; Mogensen, O.E.
1977-03-10
o-Ps yields were determined in various liquid hydrocarbons, tetramethylsilane, and mixtures thereof as a function of C/sub 2/H/sub 5/Br and CCl/sub 4/ concentration. These molecules are known to be good electron scavengers and positronium inhibitors as well. The spur reaction model of Ps formation predicts a correlation between the inhibition coefficient and the chemical rate constant of electrons with scavenger molecules. We found that the dependence of the inhibition coefficient on the work function (V/sub 0/) of electrons in different liquids shows a very unusual behavior, similar to that recently found for the chemical rate constants of quasifree electrons with the same scavenger molecules. The inhibition coefficient as a function of V/sub 0/ had a maximum for C/sub 2/H/sub 5/Br, while it increased monotonously with decreasing V/sub 0/ for CCl/sub 4/. The inhibition coefficient for C/sub 2/H/sub 5/Br in a 1 : 1 molar tetramethylsilane-n-tetradecane mixture was found to be greater than in both of the pure components. The clear correlation found between electron scavenging rate constants and positronium inhibition constitutes the severest test to date of the spur reaction model of positronium formation. The importance of the positron annihilation method from the point of view of radiation chemistry is also emphasized.
Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie
2015-01-01
ABSTRACT Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second‐order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140‐mL gas‐phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10−12 (95% confidence interval (CI): (1.7–2.2) × 10−12) and 2.6 × 10−12 (CI: (2.3–2.9) × 10−12) cm3 molecule−1 s−1, respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10−12 (CI: (2.5–3.2) × 10−12) cm3 molecule−1 s−1 and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30–37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5–10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol. PMID:27708500
Safron, Andreas; Strandell, Michael; Kierkegaard, Amelie; Macleod, Matthew
2015-07-01
Reaction with hydroxyl radicals (OH) is the major pathway for removal of cyclic volatile methyl siloxanes (cVMS) from air. We present new measurements of second-order rate constants for reactions of the cVMS octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5), and dodecamethylcyclohexasiloxane (D6) with OH determined at temperatures between 313 and 353 K. Our measurements were made using the method of relative rates with cyclohexane as a reference substance and were conducted in a 140-mL gas-phase reaction chamber with online mass spectrometry analysis. When extrapolated to 298 K, our measured reaction rate constants of D4 and D5 with the OH radical are 1.9 × 10(-12) (95% confidence interval (CI): (1.7-2.2) × 10(-12)) and 2.6 × 10(-12) (CI: (2.3-2.9) × 10(-12)) cm(3) molecule(-1) s(-1), respectively, which are 1.9× and 1.7× faster than previous measurements. Our measured rate constant for D6 is 2.8 × 10(-12) (CI: (2.5-3.2) × 10(-12)) cm(3) molecule(-1) s(-1) and to our knowledge there are no comparable laboratory measurements in the literature. Reaction rates for D5 were 33% higher than for D4 (CI: 30-37%), whereas the rates for D6 were only 8% higher than for D5 (CI: 5-10%). The activation energies of the reactions of D4, D5, and D6 with OH were not statistically different and had a value of 4300 ± 2800 J/mol.
Charting an Alternate Pathway to Reaction Orders and Rate Laws in Introductory Chemistry Courses
Rushton, Gregory T.; Criswell, Brett A.; McAllister, Nicole D.; Polizzi, Samuel J.; Moore, Lamesha A.; Pierre, Michelle S.
2014-01-01
Reaction kinetics is an axiomatic topic in chemistry that is often addressed as early as the high school course and serves as the foundation for more sophisticated conversations in college-level organic, physical, and biological chemistry courses. Despite the fundamental nature of reaction kinetics, students can struggle with transforming their…
An Interactive Classroom Activity Demonstrating Reaction Mechanisms and Rate-Determining Steps
Jennings, Laura D.; Keller, Steven W.
2005-01-01
An interactive classroom activity that includes two-step reaction of unwrapping and eating chocolate candies is described which brings not only the reaction intermediate, but also the reactants and products into macroscopic view. The qualitative activation barriers of both steps can be adjusted independently.
Pyrite oxidation in unsaturated aquifer sediments. Reaction stoichiometry and rate of oxidation
Andersen, Martin Søgaard; Larsen, Flemming; Postma, Diederik Jan
2001-01-01
the reaction stoichiometry and partitioning of gases between the solution and the gas phase. Pyrite oxidation with concurrent calcite dissolution was found to be consistent with the experimental data while organic carbon oxidation was not. The reaction involves changes in the total volume of the gas phase...
Effect of low and high heating rates on reaction path of Ni(V)/Al multilayer
Maj, Łukasz, E-mail: l.maj@imim.pl [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Morgiel, Jerzy; Szlezynger, Maciej [Institute of Metallurgy and Materials Science, Polish Academy of Sciences, 25 Reymonta St., 30-059 Kraków (Poland); Bała, Piotr; Cios, Grzegorz [AGH University of Science and Technology, Academic Centre for Materials and Nanotechnology, 30 Kawiory St., 30-055 Kraków (Poland)
2017-06-01
The effect of heating rates of Ni(V)/Al NanoFoils{sup ®} was investigated with transmission electron microscopy (TEM). The Ni(V)/Al were subjected to heating by using differential scanning calorimetry (DSC), in-situ TEM or electric pulse. Local chemical analysis was carried out using energy dispersive X-ray spectroscopy (EDS). Phase analysis was done with X-ray diffractions (XRD) and selected area electron diffractions (SAED). The experiments showed that slow heating in DSC results in development of separate exothermic effects at ∼230 °C, ∼280 °C and ∼390 °C, corresponding to precipitation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl phases, respectively, i.e. like in vanadium free Ni/Al multilayers. Further heating to 700 °C allowed to obtain a single phase NiAl foil. The average grain size (g.s.) of NiAl phase produced in the DSC heat treated foil was comparable with the Ni(V)/Al multilayer period (∼50 nm), whereas in the case of reaction initiated with electric pulse the g.s. was in the micrometer range. Upon slow heating vanadium tends to segregate to zones parallel to the original multilayer internal interfaces, while in SHS process vanadium-rich phases precipitates at grain boundaries of the NiAl phase. - Highlights: • Peaks in DSC heating of Ni(V)/Al were explained by in-situ TEM observations. • Nucleation of Al{sub 3}Ni, Al{sub 3}Ni{sub 2} and NiAl at slow heating of Ni(V)/Al was documented. • Near surface NiAl obtained from NanoFoil show Ag precipitates at grain boundaries.
Hufnagel, Todd C.
2014-06-09
Materials subjected to extreme conditions, such as very rapid heating, behave differently than materials under more ordinary conditions. In this program we examined the effect of rapid heating on solid-state chemical reactions in metallic materials. One primary goal was to develop experimental techniques capable of observing these reactions, which can occur at heating rates in excess of one million degrees Celsius per second. One approach that we used is x-ray diffraction performed using microfocused x-ray beams and very fast x-ray detectors. A second approach is the use of a pulsed electron source for dynamic transmission electron microscopy. With these techniques we were able to observe how the heating rate affects the chemical reaction, from which we were able to discern general principles about how these reactions proceed. A second thrust of this program was to develop computational tools to help us understand and predict the reactions. From atomic-scale simulations were learned about the interdiffusion between different metals at high heating rates, and about how new crystalline phases form. A second class of computational models allow us to predict the shape of the reaction front that occurs in these materials, and to connect our understanding of interdiffusion from the atomistic simulations to measurements made in the laboratory. Both the experimental and computational techniques developed in this program are expected to be broadly applicable to a wider range of scientific problems than the intermetallic solid-state reactions studied here. For example, we have already begun using the x-ray techniques to study how materials respond to mechanical deformation at very high rates.
Determination of the reaction rate coefficient of sulphide mine tailings deposited under water.
Awoh, Akué Sylvette; Mbonimpa, Mamert; Bussière, Bruno
2013-10-15
The efficiency of a water cover to limit dissolved oxygen (DO) availability to underlying acid-generating mine tailings can be assessed by calculating the DO flux at the tailings-water interface. Fick's equations, which are generally used to calculate this flux, require knowing the effective DO diffusion coefficient (Dw) and the reaction (consumption) rate coefficient (Kr) of the tailings, or the DO concentration profile. Whereas Dw can be accurately estimated, few studies have measured the parameter Kr for submerged sulphide tailings. The objective of this study was to determine Kr for underwater sulphide tailings in a laboratory experiment. Samples of sulphide mine tailings (an approximately 6 cm layer) were placed in a cell under a water cover (approximately 2 cm) maintained at constant DO concentration. Two tailings were studied: TA1 with high sulphide content (83% pyrite) and TA2 with low sulphide content (2.8% pyrite). DO concentration was measured with a microelectrode at various depths above and below the tailings-water interface at 1 mm intervals. Results indicate that steady-state condition was rapidly attained. As expected, a diffusive boundary layer (DBL) was observed in all cases. An iterative back-calculation process using the numerical code POLLUTEv6 and taking the DBL into account provided the Kr values used to match calculated and experimental concentration profiles. Kr obtained for tailings TA1 and TA2 was about 80 d(-1) and 6.5 d(-1), respectively. For comparison purposes, Kr obtained from cell tests on tailings TA1 was lower than Kr calculated from the sulphate production rate obtained from shake-flask tests. Steady-state DO flux at the water-tailings interface was then calculated with POLLUTEv6 using tailings characteristics Dw and Kr. For the tested conditions, DO flux ranged from 608 to 758 mg O2/m(2)/d for tailings TA1 and from 177 to 221 mg O2/m(2)/d for tailings TA2. The impact of placing a protective layer of inert material over
Tur, Clarisse; Austin, Sam M
2007-01-01
We explore the dependence of pre-supernova evolution and supernova nucleosynthesis yields on the uncertainties in helium burning reaction rates. Using the revised solar abundances of Lodders (2003) for the initial stellar composition, instead of those of Anders & Grevesse (1989), changes the supernova yields and limits the constraints that those yields place on the 12C(a,g)16O reaction rate. The production factors of medium-weight elements (A = 16 to 40) were found to be in reasonable agreement with observed solar ratios within the current experimental uncertainties in the triple alpha reaction rate. Simultaneous variations by the same amount in both reaction rates or in either of them separately, however, can induce significant changes in the central 12C abundance at core carbon ignition and in the mass of the supernova remnant. It therefore remains important to have experimental determinations of the helium burning rates so that their ratio and absolute values are known with an accuracy of 10% or better...
A model SN2 reaction ‘on water’ does not show rate enhancement
Nelson, Katherine V.; Benjamin, Ilan
2011-05-01
Molecular dynamics calculations of the benchmark nucleophilic substitution reaction (SN2) Cl- + CH3Cl are carried out at the water liquid/vapor interface. The reaction free energy profile and the activation free energy are determined as a function of the reactants' location normal to the surface. The activation free energy remains almost constant relative to that in bulk water, despite the fact that the barrier is expected to significantly decrease as the reaction is carried out near the vapor phase. We show that this is due to the combined effects of a clustering of water molecules around the nucleophile and a relatively weak hydration of the transition state.
Masayuki Shirai; Osamu Sato; Norihito Hiyoshi; Aritomo Yamaguchi
2014-03-01
The effect of pressured carbon dioxide on heterogeneous hydrogenation of benzaldehyde and homogeneous dehydration of sorbitol in water solvent was studied. Initial hydrogenation rates of benzaldehyde over a charcoal-supported palladium catalyst in water at 313 K were enhanced by the addition of carbon dioxide. The initial rate increased with an increase in carbon dioxide pressure and became a maximum at 5 MPa. Dehydration of sorbitol proceeded in water phase at 500 K and initial dehydration rates were enhanced by addition of 30 MPa of carbon dioxide.
Electrochemical reaction rates in a dye-sensitised solar cell - the iodide/tri-iodide redox system
Bay, L.; West, K.; Winther-Jensen, B.
2006-01-01
The electrochemical reaction rate of the redox couple iodide/tri-iodide in acetonitrile is characterised by impedance spectroscopy. Different electrode materials relevant for the function of dye-sensitised solar cells (DSSC) are investigated. Preferably, the reaction with the iodide....../tri-iodide couple should be fast at the counter electrode, i.e. this electrode must have a high catalytic activity towards the redox couple, and the same reaction must be slow on the photo electrode. The catalytic activity is investigated for platinum, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy......), and polyaniline (PANI)-all deposited onto fluorine-doped tin oxide (FTO) glass. Both Pt and PEDOT are found to have sufficiently high catalytic activities for practical use as counter electrodes in DSSC. The reaction resistance on FTO and anatase confirmed the beneficial effect of a compact anatase layer on top...
Strong screening by lattice confinement and resultant fusion reaction rates in fcc metals
Prados-Estévez, F. M.; Subashiev, A. V.; Nee, H. H.
2017-09-01
The effects of electronic screening on the cross sections and reactivities for the nuclear reactions between light nuclei in Pd and Ni is studied. We consider the applicability of the theory of thermonuclear burning in stars to the D-D nuclear reaction in metals. The screening model based on the mean field potential of the electron cloud in the metal plasma is used. We discuss the specifics of the screening for the H (D) atoms embedded in vacancies and divacancies. High concentration of hydrogen isotopes segregated to monovacancies and divacancies in face-centered cubic (fcc) metals such as Ni and Pd with densities of ∼ 6 ×1023atom /cm3 , makes the hydrogen cluster a favorable active site for the fusion reaction. Still the observation of a nuclear reaction requires an accumulation of energy in D nuclei of at least several eV, which is far above what can be achieved in the thermal heating experiments.
[Determination of rate constants of gas-phase reactions of alpha-pinene and beta-pinene with ozone].
Liu, Z R; Hu, D
2001-10-01
alpha-pinene and beta-pinene are the most dominating species among natural terpenes. Terpenes are mainly emitted from forest trees, flowers and grass. In the lower troposphere terpenes can react fast with OH radical, ozone, NO3 radical and ground state oxygen atom. These reactions may contribute to the occurring of aerosols, peroxides (hydrogen peroxide and organic peroxide), carbon cycle (mainly CO), acid rain (organic acids, NO3- and SO4(2-), ozone and active radicals such as OH radical. Reactions with ozone occur both in the daytime and in the night. The study in this field in China began in the late 1980. The main work focus on the source emission and the experimental simulation has just started. It is most of our group's work. In this paper preliminary experimental simulation of the gas-phase reactions of alpha-pinene and beta-pinene with ozone were carried out in the quartz chamber. The rate constants of these reactions were measured using long-path Fourier transform infra-red combined with relative rate constant method. And the rate constants for the gas-phase reactions of alpha-pinene, beta-pinene with ozone were determined as 2.83 x 10(17) cm3.molecule-1.s-1 and 1.48 x 10(17) cm3.molecule-1.s-1 at 1.0 x 10(5) Pa and 296 +/- 3 K. The results are quite similar to the data from Atkinson group. No cyclohexane was added to the reaction system during the measurement to restrain the formation of OH radical. The formation of OH radical could not be quantified, so that the effect of subsidiary reactions induced by OH radical has not been calculated. In the later simulation study and model this effect should be considered.
Xu, Y.; Takahashi, K.; Goriely, S.; Arnould, M.
2013-03-01
The status of a new evaluation of astrophysical nuclear reaction rates, referred as NACRE- II, is reported. It includes 19 radiative capture and 15 transfer reactions on targets with mass numbers A < 16. This work is meant to supersede the NACRE compilation. Post-NACRE experimental data are taken into account. Extrapolations of the astrophysical S-factor to largely sub-Coulomb energies are based on the use of the potential model and of the distorted wave Born approximation (DWBA) for capture and transfer reactions, respectively. Adopted rates and their lower and upper limits are provided. Here, we illustrate with some results the general procedure followed in the construction of NACRE-II.
Effects of a new triple-$\\alpha$ reaction rate on the helium ignition of accreting white dwarfs
Saruwatari, Motoaki
2010-01-01
Effects of a new triple-alpha reaction rate on the ignition of carbon-oxygen white dwarfs accreting helium in a binary systems have been investigated. The ignition points determine the properties of a thermonuclear explosion of a Type Ia supernova. We examine the cases of different accretion rates of helium and different initial masses of the white dwarf, which was studied in detail by Nomoto. We find that for all cases from slow to intermediate accretion rates, nuclear burnings are ignited at the helium layers. As a consequence, carbon deflagration would be triggered for the lower accretion rate compared to that of $dM/dt\\simeq 4\\times10^{-8} M_{\\odot} \\rm yr^{-1}$ which has been believed to the lower limit of the accretion rate for the deflagration supernova. Furthermore, off-center helium detonation should result for intermediate and slow accretion rates and the region of carbon deflagration for slow accretion rate is disappeared.
Rate and mechanism of the reactions of OH and Cl with 2-methyl-3-buten-2-ol
Ferronato, C.; Orlando, J. J.; Tyndall, G. S.
1998-10-01
An environmental chamber/Fourier transform infrared system was used to determine the rate coefficient k1 for the gas-phase reaction of OH with 2-methyl-3-buten-2-ol (MBO, (CH3)2C(OH)CH=CH2), relative to the rate of its reaction with ethylene (k2) and propylene (k3). Experiments performed at 295±1 K, in 700 torr total pressure of air, gave k1 = (6.9±1.0) × 10-11 cm3 molecule-1 s-1. At 295±1 K, the reaction of OH with MBO yielded, on a per mole basis, (52±5)% acetone, (50±5)% glycolaldehyde, and (35±4)% formaldehyde. The production of acetone from the oxidation of MBO may be of significance globally. The kinetics and mechanism of the reaction of chlorine atoms with MBO (k15) have also been studied at 700 torr total pressure of air and 295±1 K. The rate coefficient was determined using a relative rate technique, with ethane (k16), ethylene (k17), and cyclohexane (k18) as reference compounds. The value of k15 was found to be (3.3±0.4) × 10-10 cm3 molecule-1 s-1 at 295 K. The major carbon-containing products obtained in the Cl-atom oxidation of MBO were acetone (47±5)%, chloroacetaldehyde (53±5)%, HCOCl (<11%), and formaldehyde (6 ± 2)%.
Gillespie, S. A.; Parikh, A.; Barton, C. J.; Faestermann, T.; José, J.; Hertenberger, R.; Wirth, H.-F.; de Séréville, N.; Riley, J. E.; Williams, M.
2017-08-01
Sulphur isotopic ratio measurements may help to establish the astrophysical sites in which certain presolar grains were formed. Nova model predictions of the 34S/32S ratio are, however, unreliable due to the lack of an experimental 34S(p ,γ )35Cl reaction rate. To this end, we have measured the 34S(3He,d )35Cl reaction at 20 MeV using a high resolution quadrupole-dipole-dipole-dipole magnetic spectrograph. Twenty-two levels over 6.2 MeV transfer spectroscopic factors have been measured for the first time over the energy range relevant for novae. With this new spectroscopic information a new 34S(p ,γ )35Cl reaction rate has been determined using a Monte Carlo method. Hydrodynamic nova model calculations have been performed using this new reaction rate. These models show that remaining uncertainties in the 34S(p ,γ ) rate affect nucleosynthesis predictions by less than a factor of 1.4, and predict a 34S/32S isotopic ratio of 0.014-0.017. Since recent type II supernova models predict 34S/32S=0.026 -0.053 , the 34S/32S isotopic ratio may be used, in conjunction with other isotopic signatures, to distinguish presolar grains from oxygen-neon nova and type II supernova origin. Our results address a key nuclear physics uncertainty on which recent considerations discounting the nova origin of several grains depend.
American Society for Testing and Materials. Philadelphia
2008-01-01
1.1 The purpose of this test method is to define a general procedure for determining an unknown thermal-neutron fluence rate by neutron activation techniques. It is not practicable to describe completely a technique applicable to the large number of experimental situations that require the measurement of a thermal-neutron fluence rate. Therefore, this method is presented so that the user may adapt to his particular situation the fundamental procedures of the following techniques. 1.1.1 Radiometric counting technique using pure cobalt, pure gold, pure indium, cobalt-aluminum, alloy, gold-aluminum alloy, or indium-aluminum alloy. 1.1.2 Standard comparison technique using pure gold, or gold-aluminum alloy, and 1.1.3 Secondary standard comparison techniques using pure indium, indium-aluminum alloy, pure dysprosium, or dysprosium-aluminum alloy. 1.2 The techniques presented are limited to measurements at room temperatures. However, special problems when making thermal-neutron fluence rate measurements in high-...
Jim On SC
2016-08-01
Full Text Available Shelbi C Jim On,1 Kim Mark Knudsen,2 Torsten Skov,2 Mark Lebwohl,1 1Department of Dermatology, Mount Sinai School of Medicine, New York, NY, USA; 2LEO Pharma A/S, Biostatistics, Ballerup, Denmark Background: Ingenol mebutate gel is a topical field treatment for actinic keratosis (AK. The treatment elicits application-site reactions in most patients. This analysis evaluated the relationship between the severity of reactions and the speed of their resolution. Methods: Patients in Phase III studies were treated for AKs on the face (n=218, scalp (n=56, and trunk and extremities (n=209. All of the patients were treated with either ingenol mebutate gel 0.015% once daily for three consecutive days (face/scalp or ingenol mebutate gel 0.05% once daily for two consecutive days (trunk/extremities. Local skin reactions (LSRs were assessed on a 5-point scale from 0 to 4 in six categories, yielding composite scores in the range of 0 to 24. Results: The composite LSR score on the day after the last application of ingenol mebutate gel was an important predictor of the speed of resolution of LSRs. The rate of resolution was greatest for AKs treated on the face, followed by the scalp, and then the trunk and extremities. All patients were expected to have minimal LSR scores for the face and scalp at 2 weeks, and for the trunk and extremities at 4 weeks. Conclusion: The absolute reduction in LSR scores was proportional to the composite LSR score on the day after the last application of ingenol mebutate gel treatment. The rate of resolution for LSRs was dependent on the anatomic site treated as well as the day 4 composite score. Keywords: ingenol mebutate, local skin reaction, actinic keratosis
Allison, Thomas C
2016-03-03
Rate constants for reactions of chemical compounds with hydroxyl radical are a key quantity used in evaluating the global warming potential of a substance. Experimental determination of these rate constants is essential, but it can also be difficult and time-consuming to produce. High-level quantum chemistry predictions of the rate constant can suffer from the same issues. Therefore, it is valuable to devise estimation schemes that can give reasonable results on a variety of chemical compounds. In this article, the construction and training of an artificial neural network (ANN) for the prediction of rate constants at 298 K for reactions of hydroxyl radical with a diverse set of molecules is described. Input to the ANN consists of counts of the chemical bonds and bends present in the target molecule. The ANN is trained using 792 (•)OH reaction rate constants taken from the NIST Chemical Kinetics Database. The mean unsigned percent error (MUPE) for the training set is 12%, and the MUPE of the testing set is 51%. It is shown that the present methodology yields rate constants of reasonable accuracy for a diverse set of inputs. The results are compared to high-quality literature values and to another estimation scheme. This ANN methodology is expected to be of use in a wide range of applications for which (•)OH reaction rate constants are required. The model uses only information that can be gathered from a 2D representation of the molecule, making the present approach particularly appealing, especially for screening applications.
Engdahl, N. B.
2016-12-01
Mixing rates in porous media have been a heavily research topic in recent years covering analytic, random, and structured fields. However, there are some persistent assumptions and common features to these models that raise some questions about the generality of the results. One of these commonalities is the orientation of the flow field with respect to the heterogeneity structure, which are almost always defined to be parallel each other if there is an elongated axis of permeability correlation. Given the vastly different tortuosities for flow parallel to bedding and flow transverse to bedding, this assumption of parallel orientation may have significant effects on reaction rates when natural flows deviate from this assumed setting. This study investigates the role of orientation on mixing and reaction rates in multi-scale, 3D heterogeneous porous media with varying degrees of anisotropy in the correlation structure. Ten realizations of a small flow field, with three anisotropy levels, were simulated for flow parallel and transverse to bedding. Transport was simulated in each model with an advective-diffusive random walk and reactions were simulated using the chemical Langevin equation. The reaction system is a vertically segregated, transverse mixing problem between two mobile reactants. The results show that different transport behaviors and reaction rates are obtained by simply rotating the direction of flow relative to bedding, even when the net flux in both directions is the same. This kind of behavior was observed for three different weightings of the initial condition: 1) uniform, 2) flux-based, and 3) travel time based. The different schemes resulted in 20-50% more mass formation in the transverse direction than the longitudinal. The greatest variability in mass was observed for the flux weights and these were proportionate to the level of anisotropy. The implications of this study are that flux or travel time weights do not provide any guarantee of a fair
Rate of pozzolanic reaction of two kinds of activated coal gangue
ZHOU Shuang-xi
2009-01-01
Two kinds of activated ways are used to prepare activated coal gangue fine powder,one is calcining coal gangue at 800 ℃ (gangue A),and the other is calcining coal gangue with a certain calcite at 800 ℃ (gangue B).The experiment shows that strengths of blended cement mortar with coal gangue B are higher than that of blended cement with coal gangue A.Hydration of cements with the two kinds of activated coal gangue is investigated through a differential thermal analysis.The weight loss due to Ca(OH)2 decomposition of hydration products by differential thermal anaiysis/thermo gravimetric (DTA/TG) can be used to quantify the pozzolanic reaction.A new method based on the composition of hydration cement is proposed to determine the degree of pozzolanic reaction.The results obtained suggest that the degree of pozzolanic reaction of gangue B is faster than that of gangue A.
Determination of 8B(p,gamma)9C reaction rate from 9C breakup
Fukui, Tokuro; Minomo, Kosho; Yahiro, Masanobu
2012-01-01
The astrophysical factor of the 8B(p,gamma)9C at zero energy, S18(0), is determined from three-body model analysis of 9C breakup processes. The elastic breakup 208Pb(9C,p8B)208Pb at 65 MeV/nucleon and the one-proton removal reaction of 9C at 285 MeV/nucleon on C and Al targets are calculated with the continuum-discretized coupled-channels method (CDCC) and the eikonal reaction theory (ERT), respectively. The asymptotic normalization coefficient (ANC) of 9C in the p-8B configuration extracted from the two reactions show good consistency, in contrast to in the previous studies. As a result of the present analysis, S18(0) = 66 \\pm 10 eVb is obtained.
Gokoglu, Suleyman A.
1988-01-01
This paper investigates the role played by vapor-phase chemical reactions on CVD rates by comparing the results of two extreme theories developed to predict CVD mass transport rates in the absence of interfacial kinetic barrier: one based on chemically frozen boundary layer and the other based on local thermochemical equilibrium. Both theories consider laminar convective-diffusion boundary layers at high Reynolds numbers and include thermal (Soret) diffusion and variable property effects. As an example, Na2SO4 deposition was studied. It was found that gas phase reactions have no important role on Na2SO4 deposition rates and on the predictions of the theories. The implications of the predictions of the two theories to other CVD systems are discussed.
N. Alavizadeh
2017-01-01
Full Text Available ims: Apelin is an adipokine, which secreted from adipose tissue and has positive effects against the insulin resistance. The aim of this study was to investigate the effect of 8-week aerobic exercise on levels of apelin and insulin resistance index in sedentary men. Materials & Methods: In this semi-experimental study with controlled group pre/post-test design in 2015, 27 healthy sedentary men living in Mashhad City, Iran, were selected by convenience sampling method. They were divided into two groups; experimental group (n=14 and control group (n=13. In the trained group, the volunteers participated in 8 weeks aerobic exercise, 3 days/week (equivalent to 75-85% of maximum oxygen consumption for 60 minutes per session. The research variables were assessed before and after the intervention in both groups. The collected data were analyzed using SPSS 20 software using paired and independent sample T tests. Findings: 8-week aerobic exercise significantly decreased the weight, BMI and apelin, insulin and insulin resistance index levels and increased the maximum oxygen consumption in experimental group sedentary men (p<0.05. Moreover, there were significant differences in levels of FBS, insulin, apelin, insulin resistance index and maximum oxygen consumption between experimental and control groups (p<0.05. Conclusion: 8-week aerobic exercise reduces apelin levels and insulin resistance index in sedentary men.
W. B. Bush
1997-01-01
are the activation, adiabatic-flame (and/or burned-gas, and unburned-gas temperatures, respectively]; and (2 the exponent, a, which characterizes the pre-exponential thermal dependence of the reaction-rate term, unity. The examination indicates that, as in the order-unity heat-addition case, this deflagration has a four-region structure: the upstream diffusion-convection and downstream diffusion-reaction regions, and the far-upstream (or cold-boundary and the far-downstream (or hot-boundary regions.
The Effect of Nuclear Reaction Rates & Convective Mixing on the Evolution of a 6M$_{\\odot}$ Star
Halabi, Ghina M
2014-01-01
We present the evolution of a 6M$_{\\odot}$ star, of solar-like initial metallicity, and investigate the effects of key nuclear reaction rates, as well as the treatment of the convective mixing on its evolution along the Cepheid instability strip. In particular, we study the effect of recent estimates of the $^{14}$N(p,{\\gamma})$^{15}$O reaction on the formation and extension of the blue loop during core helium burning. We also investigate the effects induced on this blue loop by the adoption of non-standard convective mixing prescriptions, as well as the implications of modifying the Mixing Length Theory.
Glassley, W.E.; Meike, A.
2000-03-13
The history geological terrains experience can be traced as a series of temperature and pressure changes. Each change drives the system toward a new state of thermodynamic equilibrium. The resultant overprinted rock fabrics, textures and chemical heterogeneities can be difficult to interpret. However, if carefully chosen, features from the scale of kilometers to nanometers can be used to reconstruct the history of mountain systems. Uplift of the Sri Lankan Central Highlands was rapid enough to preserve well-developed symplectite textures, some of which represent arrested solid-state diffusion-controlled reactions of garnet + O{sub 2} to form orthopyroxene + plagioclase + magnetite, as the rocks were exhumed from over 30 km in the earth's crust. Our objective has been to determine the reaction mechanisms responsible for symplectite development, and to establish the time interval over which these reactions occurred, to constrain the rate of mountain uplift. Considering that the most rapid mechanism is solid state grain-boundary diffusion of oxygen, the reaction time can be constrained by bounding the rate of oxygen supply to the reaction site. The solid state grain boundary diffusion rate of oxygen has been inferred to be ca. 10{sup -14}m{sup 2}-sec (Farver and Yund, 1991), but is sensitive to inferred grain boundary width. The range of rates thus determined allows the distinction between rapid uplift similar to that of the Himalayan Mountains, and the slow and progressive erosion of a less dramatic terrain. Further constraints on diffusion control and energetic relationships are determined from crystallographic relationships between the reactant and product phases, and submicron scale microstructure.
Sekine, Akiko
2016-08-01
Our recent results on the photochromic reactions in dual mode cobaloxime crystals containing azobenzene derivatives are briefly reviewed. This work represents the first step toward the design of functional materials which can be controlled by two independent external stimuli, one by visible light and the other by UV radiation.
Electrochemical reaction rates in a dye sentisised solar cell - the iodide/tri-iodide redox system
Bay, Lasse; West, Keld; Winter-Jensen, Bjørn
2006-01-01
-iodide couple should be fast at the counter electrode, i.e. this electrode must have a high catalytic activity towards the redox couple, and the same reaction must be slow on the photo electrode. The catalytic activity is investigated for platinum, poly(3,4-ethylenedioxythiophene) (PEDOT), polypyrrole (PPy...
On the relationship between structure and reaction rate in olefin ring-closing metathesis.
Ashworth, Ian W; Carboni, Davide; Hillier, Ian H; Nelson, David J; Percy, Jonathan M; Rinaudo, Giuseppe; Vincent, Mark A
2010-10-14
In the RCM reactions of a series of simple α,ω-dienes, the relative order of reactivity has been unambiguously determined showing that cyclohexene forms faster than cyclopentene or cycloheptene. 1,5-Hexadiene inhibits the RCM of 1,7-octadiene; 1,5-hexadiene cannot progress to the RCM product (cyclobutene) but forms an unexpectedly stable cyclic η(2)-complex.
Defense Nuclear Agency Reaction Rate Handbook. Second Edition. Revision Number 6
1972-03-01
257 (1972). 17-55. Gilmore, F. R., J. Quant. Spectry. Radiative Transfer S_t 369(1965). 17-56. Herzberg , G., Electronic Spectra of...1F»O •BBS • \\ CHAPTER 19 19. NEUTRAL REACTIONS Frederick Kaufman, University of Pittsburgh (Latest Revision 14 May 1975) o 19.1
Shu, Shi; Morrison, Glenn C
2011-05-15
Ozone can react homogeneously with unsaturated organic compounds in buildings to generate undesirable products. However, these reactions can also occur on indoor surfaces, especially for low-volatility organics. Conversion rates of ozone with α-terpineol, a representative low-volatility compound, were quantified on surfaces that mimic indoor substrates. Rates were measured for α-terpineol adsorbed to beads of glass, polyvinylchloride (PVC), and dry latex paint, in a plug flow reactor. A newly defined second-order surface reaction rate coefficient, k(2), was derived from the flow reactor model. The value of k(2) ranged from 0.68 × 10(-14) cm(4)s(-1)molecule(-1) for α-terpineol adsorbed to PVC to 3.17 × 10(-14) cm(4)s(-1)molecule(-1) for glass, but was insensitive to relative humidity. Further, k(2) is only weakly influenced by the adsorbed mass but instead appears to be more strongly related to the interfacial activity α-terpineol. The minimum reaction probability ranged from 3.79 × 10(-6) for glass at 20% RH to 6.75 × 10(-5) for PVC at 50% RH. The combination of high equilibrium surface coverage and high reactivity for α-terpineol suggests that surface conversion rates are fast enough to compete with or even overwhelm other removal mechanisms in buildings such as gas-phase conversion and air exchange.
Saylam, A; Ribaucour, M; Pitz, W J; Minetti, R
2006-11-29
A new technique of reduction of detailed mechanisms for autoignition, which is based on two analysis methods is described. An analysis of reaction rates is coupled to an analysis of reaction sensitivity for the detection of redundant reactions. Thresholds associated with the two analyses have a great influence on the size and efficiency of the reduced mechanism. Rules of selection of the thresholds are defined. The reduction technique has been successfully applied to detailed autoignition mechanisms of two reference hydrocarbons: n-heptane and iso-octane. The efficiency of the technique and the ability of the reduced mechanisms to reproduce well the results generated by the full mechanism are discussed. A speedup of calculations by a factor of 5.9 for n-heptane mechanism and by a factor of 16.7 for iso-octane mechanism is obtained without losing accuracy of the prediction of autoignition delay times and concentrations of intermediate species.
Ballesteros, Bernabé; Ceacero-Vega, Antonio A; Jiménez, Elena; Albaladejo, José
2015-04-01
As the result of biogenic and anthropogenic activities, large quantities of chemical compounds are emitted into the troposphere. Alkanes, in general, and cycloalkanes are an important chemical class of hydrocarbons found in diesel, jet and gasoline, vehicle exhaust emissions, and ambient air in urban areas. In general, the primary atmospheric fate of organic compounds in the gas phase is the reaction with hydroxyl radicals (OH). The oxidation by Cl atoms has gained importance in the study of atmospheric reactions because they may exert some influence in the boundary layer, particularly in marine and coastal environments, and in the Arctic troposphere. The aim of this paper is to study of the atmospheric reactivity of methylcylohexanes with Cl atoms and OH radicals under atmospheric conditions (in air at room temperature and pressure). Relative kinetic techniques have been used to determine the rate coefficients for the reaction of Cl atoms and OH radicals with methylcyclohexane, cis-1,4-dimethylcyclohexane, trans-1,4-dimethylcyclohexane, and 1,3,5-trimethylcyclohexane at 298 ± 2 K and 720 ± 5 Torr of air by Fourier transform infrared) spectroscopy and gas chromatography-mass spectrometry (GC-MS) in two atmospheric simulation chambers. The products formed in the reaction under atmospheric conditions were investigated using a 200-L Teflon bag and employing the technique of solid-phase microextraction coupled to a GC-MS. The rate coefficients obtained for the reaction of Cl atoms with the studied compounds are the following ones (in units of 10(-10) cm(3) molecule(-1) s(-1)): (3.11 ± 0.16), (2.89 ± 0.16), (2.89 ± 0.26), and (2.61 ± 0.42), respectively. For the reactions with OH radicals the determined rate coefficients are (in units of 10(-11) cm(3) molecule(-1) s(-1)): (1.18 ± 0.12), (1.49 ± 0.16), (1.41 ± 0.15), and (1.77 ± 0.23), respectively. The reported error is twice the standard deviation. A detailed
Blok, Chris; Jackson, Brian E.; Guo, Xianfeng; Visser, De Pieter H.B.; Marcelis, Leo F.M.
2017-01-01
Growing on rooting media other than soils in situ -i.e., substrate-based growing- allows for higher yields than soil-based growing as transport rates of water, nutrients, and oxygen in substrate surpass those in soil. Possibly water-based growing allows for even higher yields as transport rates of
Lu, Chih-Wei; Chou, Shen-Long; Lee, Yuan-Pern; Xu, Shucheng; Xu, Z F; Lin, M C
2005-06-22
Rate coefficients of the reaction O((3)P) + CH(3)OH in the temperature range of 835-1777 K were determined using a diaphragmless shock tube. O atoms were generated by photolysis of SO(2) with a KrF excimer laser at 248 nm or an ArF excimer laser at 193 nm; their concentrations were monitored via atomic resonance absorption excited by emission from a microwave-discharged mixture of O(2) and He. The rate coefficients determined for the temperature range can be represented by the Arrhenius equation, k(T) = (2.29 +/- 0.18) x 10(-10) exp[-(4210 +/- 100)T] cm(3) molecule(-1) s(-1); unless otherwise noted, all the listed errors represent one standard deviation in fitting. Combination of these and previous data at lower temperature shows a non-Arrhenius behavior described as the three-parameter equation, k(T) = (2.74 +/- 0.07) x 10(-18)T(2.25 +/- 0.13) exp[-(1500 +/- 90)T] cm(3)molecule(-1) s(-1). Theoretical calculations at the Becke-3-Lee-Yang-Parr (B3LYP)6-311 + G(3df,2p) level locate three transition states. Based on the energies computed with coupled clusters singles, doubles (triples) [CCSD(T)]/6-311 + G(3df,2p)B3LYP6-311 + G(3df,2p), the rate coefficients predicted with canonical variational transition state theory with small curvature tunneling corrections agree satisfactorily with the experimental observations. The branching ratios of two accessible reaction channels forming OH + CH(2)OH (1a) and OH + CH(3)O (1b) are predicted to vary strongly with temperature. At 300 K, reaction (1a) dominates, whereas reaction (1b) becomes more important than reaction (1a) above 1700 K.
The triple alpha reaction rate and the 2$^+$ resonances in $^{12}$C
de Diego, R; Fedorov, D V; ~Jensen, A S
2010-01-01
The triple alpha rate is obtained from the three-body bound and continuum states computed in a large box. The results from this genuine full three-body calculation are compared with standard reference rates obtained by two sequential two-body processes. The fairly good agreement relies on two different assumptions about the lowest $2^+$ resonance energy. With the same $2^+$ energy the rates from the full three-body calculation are smaller than those of the standard reference. We discuss the rate dependence on the experimentally unknown $2^+$ energy. Substantial deviations from previous results appear for temperatures above $3$~GK.
Measurement and analysis of the 238U(n, 2n) reaction rate in depleted uranium/polyethylene shells
YAN Xiao-Song; LIU Rong; LU Xin-Xin; JIANG Li; WEN Zhong-Wei; HAN Zi-Jie
2012-01-01
In order to check the conceptual design of the subcritical blanket in a fnsion-fission hybrid reactor,a depleted uranium/polyethylene simulation device with alternate shells has been established.The measurement of the 238U(n,2n) reaction rate was carried out using an activation technique,by measuring the 208 keV γ rays emitted from 237 U.The self-absorption of depleted uranium foils with different thicknesses was experimentally corrected.The distribution of the 238U(n,2n) reaction rate at 90° to the incident D+ beam was obtained,with uncertainty between 5.3％ and 6.0％.The experiment was analyzed using MCNP5 code with the ENDF/BVI library,and the calculated results are all about 5％ higher than the measured results.
Jianling, Li; Higgins, Andrew J
2014-01-01
The propagation of detonation waves in reactive media bounded by an inert, compressible layer is examined via computational simulations in two different geometries, axisymmetric cylinders and two dimensional, planar slabs. For simplicity, an ideal gas equation of state is used with a pressure-dependent reaction rate that results in a stable detonation wave structure. The detonation is initiated as an ideal Chapman-Jouguet (CJ) detonation with a one-dimensional structure, and then allowed to propagate into a finite diameter or thickness layer of explosive surrounded by an inert layer. The yielding confinement of the inert layer results in the detonation wave decaying to a sub-CJ steady state velocity or failing entirely. Simulations are performed with different values of the reaction rate pressure exponent (n = 2 and 3) and different impedance confinement (greater than, less than, and equal to the confinement of the explosive). The velocity decrement and critical dimension (critical diameter or thickness) are ...
Xu, Y.; Takahashi, K.; Goriely, S.; Arnould, M.
2011-10-01
We report on the status of a new evaluation of the rates in astrophysical conditions of 19 capture and 15 transfer reactions on stable targets with mass numbers A<16, referred as NACRE-II. This work is meant to supersede the NACRE compilation. Post-NACRE experimental data are taken into account. Extrapolations of the astrophysical S-factor to largely sub-Coulomb energies are based on the use of the potential model and of the distorted wave Born approximation for capture and transfer reactions, respectively. Adopted rates and their lower and upper limits are provided. Here, we illustrate the general procedure followed in the NACRE-II construction with two examples.
Banks, Harold D
2008-04-04
In a previous study we reported that fluorine substitution at the carbon positions of aziridine results in profound enhancements of the rate of reaction with ammonia, a typical nucleophile, in the gas phase. In this study the investigation is extended to include chloro- and bromoaziridines. Because syntheses are largely performed in the condensed phase, the present computational investigation [(MP2(Full)/6-311++G(d,p)//MP2(Full)/6-31+G(d) level] was conducted with three typical solvents that cover a wide range of polarity: THF, CH3CN, and H2O. Nucleophiles can react with haloaziridines 1 by displacing a substituted amide ion by means of an SN2 mechanism (pathway a), producing 1,2-diaminohaloethanes (from the initially formed dipolar species 2). Alternatively, a rearrangement mechanism involving rate-determining departure of a halide ion (pathway b) to form an imidoyl halide, 3, is possible. Transition-state theory was used to compute relative reaction rates of these mechanistic possibilities and to assess the role of the halogen substituents and the reaction solvent. Gas-phase results provided the basis of mechanistic insights that were more apparent in the absence of intermolecular interactions. Fluoroaziridines were found to react at accelerated rates relative to aziridine exclusively by means of the a Menshutkin-type mechanism (SN2) in each solvent tested, while the reactions of the chloro- and bromoaziridines could be directed toward 2 in the highly nonpolar solvent, cyclohexane, or toward 3 in the more polar solvents. An assessment is made of the feasibility of using this chemistry of the haloazirdines in the synthetic laboratory.
Nagai, Keisuke; Iida, Kazuki; Shimizu, Kimiaki; Kinugasa, Ryo; Izumi, Motoki; Kato, Dai-Ichiro; Takeo, Masahiro; Mochiji, Kozo; Negoro, Seiji
2014-10-01
Nylon hydrolase degrades various aliphatic nylons, including nylon-6 and nylon-66. We synthesized a nylon-66 copolymer (M w = 22,900, M n = 7,400), in which a part of an adipoyl unit (32 % molar ratio) of nylon-66 was replaced with a succinyl unit by interfacial polymerization. To quantify the reaction rate of the enzymatic hydrolysis of nylons at the surface of solid polymers, we prepared a thin layer of nylons on the bottom surface of each well in a polystyrene-based micro-assay plate. The thickness of the nylon layer was monitored by imaging analysis of the photographic data. More than 99 % of the copolymer with thicknesses of 260 nm (approximately 600 layers of polymer strands) were converted to water-soluble oligomers by nylon hydrolase (3 mg enzyme ml(-1)) at 30 °C within 60 h. These results were further confirmed by TLC analysis of the reaction products and by assay of liberated amino groups in the soluble fractions. The degradation rate of the thin-layered nylon-6 was similarly analyzed. We demonstrate that this assay enables a quantitative evaluation of the reaction rate of hydrolysis at the interface between the solid and aqueous phases and a quantitative comparison of the degradability for various polyamides.
The H2 + CO ↔ H2CO Reaction: Rate Constants and Relevance to Hot and Dense Astrophysical Media
Vichietti, R. M.; Spada, R. F. K.; da Silva, A. B. F.; Machado, F. B. C.; Haiduke, R. L. A.
2016-07-01
A theoretical thermochemical and kinetic investigation of the thermal H2 + CO ↔ H2CO reaction was performed for a temperature range from 200 to 4000 K. Geometries and vibrational frequencies of reactants, product, and transition state (TS) were obtained at CCSD/cc-pVxZ (x = T and Q) levels and scaling factors were employed to consider anharmonicity effects on vibrational frequencies, zero-point energies, and thermal corrections provided by these methodologies. Enthalpies Gibbs energies, and rate constants for this reaction were determined by including a complete basis set extrapolation correction for the electronic properties calculated at CCSD(T)/cc-pVyZ (y = Q and 5) levels. Our study indicates that enthalpy changes for this reaction are highly dependent on temperature. Moreover, forward and reverse (high-pressure limit) rate constants were obtained from variational TS theory with quantum tunneling corrections. Thus, modified Arrhenius’ equations were fitted by means of the best forward and reverse rate constant values, which provide very reliable estimates for these quantities within the temperature range between 700 and 4000 K. To our knowledge, this is the first kinetic study done for the forward H2 + CO \\to H2CO process in a wide temperature range. Finally, these results can be used to explain the formaldehyde abundance in hot and dense interstellar media, possibly providing data about the physical conditions associated with H2CO masers close to massive star-forming regions.
Sander, Pia; Mouritsen, L; Andersen, J Thorup
2002-01-01
OBJECTIVE: The aim of this study was to evaluate the value of routine measurements of urinary flow rate and residual urine volume as a part of a "minimal care" assessment programme for women with urinary incontinence in detecting clinical significant bladder emptying problems. MATERIAL AND METHOD...... female urinary incontinence. Thus, primary health care providers can assess women based on simple guidelines without expensive equipment for assessment of urine flow rate and residual urine....
Nguyen, Thanh Lam; Stanton, John F.
2017-10-01
Hydrogen abstraction from NH3 by OH to produce H2O and NH2—an important reaction in combustion of NH3 fuel—was studied with a theoretical approach that combines high level quantum chemistry and advanced chemical kinetics methods. Thermal rate constants calculated from first principles agree well (within 5%-20%) with available experimental data over a temperature range that extends from 200 to 2500 K. Quantum mechanical tunneling effects were found to be important; they lead to a decided curvature and non-Arrhenius behavior for the rate constant.
Schiefelbein, Sarah; Fröhlich, Alexander; John, Gernot T; Beutler, Falco; Wittmann, Christoph; Becker, Judith
2013-08-01
Dissolved oxygen plays an essential role in aerobic cultivation especially due to its low solubility. Under unfavorable conditions of mixing and vessel geometry it can become limiting. This, however, is difficult to predict and thus the right choice for an optimal experimental set-up is challenging. To overcome this, we developed a method which allows a robust prediction of the dissolved oxygen concentration during aerobic growth. This integrates newly established mathematical correlations for the determination of the volumetric gas-liquid mass transfer coefficient (kLa) in disposable shake-flasks from the filling volume, the vessel size and the agitation speed. Tested for the industrial production organism Corynebacterium glutamicum, this enabled a reliable design of culture conditions and allowed to predict the maximum possible cell concentration without oxygen limitation.
Harada M
2000-08-01
Full Text Available We developed a sensitive polymerase chain reaction (PCR method for the detection of Plasmodium falciparum DNA from mosquitoes collected in the field. Plasmodium falciparum was detected from 15.2% of 1-parous mosquitoes, Anopheles farauti, in the Solomon Islands through use of the PCR method. A novel mathematical model was developed to estimate the sporozoite rate based on the malaria-positive rate of 1-parous mosquitoes. Using this model, the sporozoite rate of Anopheles farauti in the Solomon Islands was calculated to be 0.09%. This method enables estimation of the sporozoite rate based on a relatively small number (100-200 of mosquitoes compared with the number needed for the ELISA method.
Strasser, Barbara; Schwarz, Joachim; Haber, Paul; Schobersberger, Wolfgang
2011-12-01
Aim of this study was to evaluate reliable guide values for heart rate (HF) and blood pressure (RR) with reference to defined sub maximum exertion considering age, gender and body mass. One hundred and eighteen healthy but non-trained subjects (38 women, 80 men) were included in the study. For interpretation, finally facts of 28 women and 59 men were used. We found gender differences for HF and RR. Further, we noted significant correlations between HF and age as well as between RR and body mass at all exercise levels. We established formulas for gender-specific calculation of reliable guide values for HF and RR on sub maximum exercise levels.
Ogawa, T.; Morev, M. N.; Iimoto, T.; Kosako, T.
2012-01-01
Reaction rate distributions were measured inside a 60-cm thick concrete pile placed at the lateral position of a thick (stopping length) iron target that was bombarded with heavy ions, 400 MeV/u C and 800 MeV/u Si. Foils of aluminum and gold, as well as gold, tungsten and manganese covered with cadmium were inserted at various locations in the concrete pile to serve as activation detectors. Features of reaction rate distribution, such as the shape of the reaction rate profile, contribution of the neutrons from intra-nuclear cascade and that from evaporation to the activation reactions are determined by the analysis of measured reaction rates. The measured reaction rates were compared with those calculated with radiation transport simulation codes, FLUKA and PHITS, to verify their capability to predict induced activity. The simulated reaction rates agree with the experimental results within a factor of three in general. However, systematic discrepancies between simulated reaction rates and measured reaction rates attributed to the neutron source terms are observed.
Solubility and Reaction Rates of Aluminum Solid Phases Under Geothermal Conditions
Benezeth, P.; Palmer, D.A.; Wesolowski, D.J.; Anovitz, L.M.
2000-05-28
Experimental studies involving equilibrium solubility and dissolution/precipitation rates were initiated on aluminum hydroxide phases prevalent under geothermal reservoir conditions. A large capacity, hydrogen-electrode concentration cell (HECC) was constructed specifically for this purpose.
Pegis, Michael L.; McKeown, Bradley A.; Kumar, Neeraj; Lang, Kai; Wasylenko, Derek J.; Zhang, X. Peter; Raugei, Simone; Mayer, James M.
2016-10-28
Improvement of electrocatalysts for the oxygen reduction reaction (ORR) is critical for the advancement of fuel cell technologies. Herein, we report a series of eleven soluble iron porphyrin ORR electrocatalysts that possess turnover frequencies (TOFs) from 3 s^{-1} to an unprecedented 2.2 x 10^{6} s^{-1}. These TOFs correlate with the ORR overpotential, which can be changed by modulating the ancillary ligand, by varying the reaction conditions or by changing the catalyst’s protonation state. This is the first such correlation for homogeneous ORR electrocatalysis, and it demonstrates that the remarkably fast TOFs are a consequence of the high overpotential. Computational studies indicate that the correlation is analogous to the volcano plot analysis developed for heterogeneous ORR materials. This unique parallel between homo- and heterogeneous ORR electrocatalysts allows a fundamental understanding of intrinsic barriers associated with the ORR, which can aid the design of new catalytic systems that operate at low overpotential. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy (DOE), Office of Science, Office of Basic Energy Sciences. Additional data is given in the Electronic Supporting Information.
Recommended Thermal Rate Coefficients for the C + H3 + Reaction and Some Astrochemical Implications
Vissapragada, S.; Buzard, C. F.; Miller, K. A.; O'Connor, A. P.; de Ruette, N.; Urbain, X.; Savin, D. W.
2016-11-01
We incorporate our experimentally derived thermal rate coefficients for C + {{{H}}}3+ forming CH+ and CH2 + into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and instead we use a more versatile fitting formula. At a temperature of 10 K and a density of 104 cm-3, we find no significant differences in the predicted chemical abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. In addition, we find that the relatively small error on our thermal rate coefficients, ˜15%, significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.
Vissapragada, S; Miller, K A; O'Connor, A P; de Ruette, N; Urbain, X; Savin, D W
2016-01-01
We have incorporated our experimentally derived thermal rate coefficients for C + H$_3^+$ forming CH$^+$ and CH$_2^+$ into a commonly used astrochemical model. We find that the Arrhenius-Kooij equation typically used in chemical models does not accurately fit our data and use instead a more versatile fitting formula. At a temperature of 10 K and a density of 10$^4$ cm$^{-3}$, we find no significant differences in the predicted chemical abundances, but at higher temperatures of 50, 100, and 300 K we find up to factor of 2 changes. Additionally, we find that the relatively small error on our thermal rate coefficients, $\\sim15\\%$, significantly reduces the uncertainties on the predicted abundances compared to those obtained using the currently implemented Langevin rate coefficient with its estimated factor of 2 uncertainty.
Pressure dependence of the absolute rate constant for the reaction Cl + C2H2 from 210-361 K
Brunning, J.; Stief, L. J.
1985-01-01
In recent years, considerable attention has been given to the role of chlorine compounds in the catalytic destruction of stratospheric ozone. However, while some reactions have been studied extensively, the kinetic data for the reaction of Cl with C2H2 is sparse with only three known determinations of the rate constant k3. The reactions involved are Cl + C2H2 yields reversibly ClC2H2(asterisk) (3a) and ClC2H2(asterisk) + M yields ClC2H2 + M (3b). In the present study, flash photolysis coupled with chlorine atomic resonance fluorescence have been employed to determine the pressure and temperature dependence of k3 with the third body M = Ar. Room temperature values are also reported for M = N2. The pressure dependence observed in the experiments confirms the expectation that the reaction involves addition of Cl to the unsaturated C2H2 molecule followed by collisional stabilization of the resulting adduct radical.
Timothy Q. Cook; Thomas K. Hahn
1986-01-01
Considerable attention has been devoted to the reaction of interest rates, foreign exchange rates, and stock prices to unanticipated money growth revealed by the weekly M1 money stock announcement. Numerous articles have attempted to explain why nominal interest rates rise following the announcement of an M1 figure higher than expected and fall when an M1 figure is lower than expected. The major controversy in this literature is whether the observed reaction of interest rates reflects changes...
Ross, F; Ross, A B
1977-01-01
Rates of reactions of OH and HO/sub 2/ with organic and inorganic molecules, ions and transients in aqueous solution have been tabulated, as well as the rates for the corresponding radical ions in aqueous solution (O/sup -/ and O/sub 2//sup -/). Most of the rates have been obtained by radiation chemistry methods, both pulsed and steady-state; data from photochemistry and thermal methods are also included. Rates for over one thousand reactions are listed.
Shizgal, Bernie D.
2016-08-01
Nonclassical quadratures based on a new set of half-range polynomials, Tn(x) , orthogonal with respect to w(x) =e - x - b /√{ x } for x ∈ [ 0 , ∞) are employed in the efficient calculation of the nuclear fusion reaction rate coefficients from cross section data. The parameter b = B /√{kB T } in the weight function is temperature dependent and B is the Gamow factor. The polynomials Tn(x) satisfy a three term recurrence relation defined by two sets of recurrence coefficients, αn and βn. These recurrence coefficients define in turn the tridiagonal Jacobi matrix whose eigenvalues are the quadrature points and the weights are calculated from the first components of the eigenfunctions. For nonresonant nuclear reactions for which the astrophysical function can be expressed as a lower order polynomial in the relative energy, the convergence of the thermal average of the reactive cross section with this nonclassical quadrature is extremely rapid requiring in many cases 2-4 quadrature points. The results are compared with other libraries of nuclear reaction rate coefficient data reported in the literature.
Bush W. B.
1997-01-01
Full Text Available The structure of the quasi-isothermal deflagration is examined by means of an asymptotic analysis of the physical-plane boundary-value problem, with Lewis–Semenov number unity, in the limit of the activation-temperature ratio, β = T a / T b , greater than order unity, for the generalized reaction-rate-model case of: (1 the heat-addition-temperature ratio, α = ( T b − T u / T u , of order β − 1 / 2 , less than order unity [where T a , T b , and T u are the activation, adiabatic-flame (and/or burned-gas, and unburned-gas temperatures, respectively]; and (2 the exponent, a , which characterizes the pre-exponential thermal dependence of the reaction-rate term, unity. The examination indicates that, as in the order-unity heat-addition case, this deflagration has a four-region structure: the upstream diffusion-convection and downstream diffusion-reaction regions, and the far-upstream (or cold-boundary and the far-downstream (or hot-boundary regions.
Revision of the 15N(p,{\\gamma})16O reaction rate and oxygen abundance in H-burning zones
Caciolli, A; Capogrosso, V; Bemmerer, D; Broggini, C; Corvisiero, P; Costantini, H; Elekes, Z; Formicola, A; Fulop, Zs; Gervino, G; Guglielmetti, A; Gustavino, C; Gyurky, Gy; Imbriani, G; Junker, M; Lemut, A; Marta, M; Menegazzo, R; Palmerini, S; Prati, P; Roca, V; Rolfs, C; Alvarez, C Rossi; Somorjai, E; Straniero, O; Strieder, F; Terrasi, F; Trautvetter, H P; Vomiero, A
2011-01-01
The NO cycle takes place in the deepest layer of a H-burning core or shell, when the temperature exceeds T {\\simeq} 30 {\\cdot} 106 K. The O depletion observed in some globular cluster giant stars, always associated with a Na enhancement, may be due to either a deep mixing during the RGB (red giant branch) phase of the star or to the pollution of the primordial gas by an early population of massive AGB (asymptotic giant branch) stars, whose chemical composition was modified by the hot bottom burning. In both cases, the NO cycle is responsible for the O depletion. The activation of this cycle depends on the rate of the 15N(p,{\\gamma})16O reaction. A precise evaluation of this reaction rate at temperatures as low as experienced in H-burning zones in stellar interiors is mandatory to understand the observed O abundances. We present a new measurement of the 15N(p,{\\gamma})16O reaction performed at LUNA covering for the first time the center of mass energy range 70-370 keV, which corresponds to stellar temperatures...
Maximum Likelihood Associative Memories
Gripon, Vincent; Rabbat, Michael
2013-01-01
Associative memories are structures that store data in such a way that it can later be retrieved given only a part of its content -- a sort-of error/erasure-resilience property. They are used in applications ranging from caches and memory management in CPUs to database engines. In this work we study associative memories built on the maximum likelihood principle. We derive minimum residual error rates when the data stored comes from a uniform binary source. Second, we determine the minimum amo...
USE OF ROUGH SETS AND SPECTRAL DATA FOR BUILDING PREDICTIVE MODELS OF REACTION RATE CONSTANTS
A model for predicting the log of the rate constants for alkaline hydrolysis of organic esters has been developed with the use of gas-phase min-infrared library spectra and a rule-building software system based on the mathematical theory of rough sets. A diverse set of 41 esters ...
Molins, Sergi [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Trebotich, David [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division; Steefel, Carl I. [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Earth Sciences Division; Shen, Chaopeng [Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Computational Research Division
2012-03-30
The scale-dependence of geochemical reaction rates hinders their use in continuum scale models intended for the interpretation and prediction of chemical fate and transport in subsurface environments such as those considered for geologic sequestration of CO_{2}. Processes that take place at the pore scale, especially those involving mass transport limitations to reactive surfaces, may contribute to the discrepancy commonly observed between laboratory-determined and continuum-scale or field rates. In this study we investigate the dependence of mineral dissolution rates on the pore structure of the porous media by means of pore scale modeling of flow and multicomponent reactive transport. The pore scale model is composed of high-performance simulation tools and algorithms for incompressible flow and conservative transport combined with a general-purpose multicomponent geochemical reaction code. The model performs direct numerical simulation of reactive transport based on an operator-splitting approach to coupling transport and reactions. The approach is validated with a Poiseuille flow single-pore experiment and verified with an equivalent 1-D continuum-scale model of a capillary tube packed with calcite spheres. Using the case of calcite dissolution as an example, the high-resolution model is used to demonstrate that nonuniformity in the flow field at the pore scale has the effect of decreasing the overall reactivity of the system, even when systems with identical reactive surface area are considered. In conclusion, the effect becomes more pronounced as the heterogeneity of the reactive grain packing increases, particularly where the flow slows sufficiently such that the solution approaches equilibrium locally and the average rate becomes transport-limited.
Blazevich, Anthony J; Horne, Sara; Cannavan, Dale
2008-01-01
knee extension training was performed 3 x week(-1) for 10 weeks. Maximal isometric strength (+11.2%) and RFD (measured from 0-30/50/100/200 ms, respectively; +10.5%-20.5%) increased after 10 weeks (P training mode. Peak EMG amplitude and rate of EMG rise......This study examined the effects of slow-speed resistance training involving concentric (CON, n = 10) versus eccentric (ECC, n = 11) single-joint muscle contractions on contractile rate of force development (RFD) and neuromuscular activity (EMG), and its maintenance through detraining. Isokinetic...... were not significantly altered with training or detraining. Subjects with below-median normalized RFD (RFD/MVC) at 0 weeks significantly increased RFD after 5- and 10-weeks training, which was associated with increased neuromuscular activity. Subjects who maintained their higher RFD after detraining...
Dependence of reaction rate of pyrite oxidation on temperature, pH and oxidant concentration
LU; Long; WANG; Rucheng; XUE; Jiyue; CHEN; Fanrong; CHEN; J
2005-01-01
The kinetic sstudy of pyrite oxidation was performed in a series of experiments by a mixed flow reactor. The release rates of Fe(II) are in the order of 3.22×10-9-5.51×10-7 mol·m-2·s-1 at temperature (T ) 25 to 44℃, initial pH (pH )1.4 to 2.7, and initial Fe(III) concentration ([Fe(III)]I) 10-5 to 5×10-3 mol·kg-1. The release rate of Fe(II) increased with increasing T or/and pH or/and [Fe(III)]I in the above range. The rate law and activation energy of pyrite oxidation were derived by statistical analyses of Rfe(II) vs. [Fe(III)]I, Rfe(II) vs. pH and Rfe(II) vs. T, and are given as (1) Rate law: Rfe(II)=104.65e-64.54×103/8.31T[Fe(III)]i0.6./[H+]0.45 ; (2) activation energy: 64.54 ( 8.07 kJ·mol-1. The expression can be applied to more cases (e.g., quantifying the pollutant released from sulfide-rich mining waste and assessing reliable performance of underground repository sites where pyrite acts as an engineered barrier material). Using the rate law derived from this study, the magnitude of the pollutants transferred to secondary phases, soil and water from oxidized pyrite during Jiguanshan mine waste weathering was preliminarily estimated. The estimated magnitude is very high, suggesting that the pile has possibly posed significant impact on the water quality in this region.
Thornley, John H M; Parsons, Anthony J
2014-02-07
Treating resource allocation within plants, and between plants and associated organisms, is essential for plant, crop and ecosystem modelling. However, it is still an unresolved issue. It is also important to consider quantitatively when it is efficient and to what extent a plant can invest profitably in a mycorrhizal association. A teleonomic model is used to address these issues. A six state-variable model giving exponential growth is constructed. This represents carbon (C), nitrogen (N) and phosphorus (P) substrates with structure in shoot, root and mycorrhiza. The shoot is responsible for uptake of substrate C, the root for substrates N and P, and the mycorrhiza also for substrates N and P. A teleonomic goal, maximizing proportional growth rate, is solved analytically for the allocation fractions. Expressions allocating new dry matter to shoot, root and mycorrhiza are derived which maximize growth rate. These demonstrate several key intuitive phenomena concerning resource sharing between plant components and associated mycorrhizae. For instance, if root uptake rate for phosphorus is equal to that achievable by mycorrhiza and without detriment to root uptake rate for nitrogen, then this gives a faster growing mycorrhizal-free plant. However, if root phosphorus uptake is below that achievable by mycorrhiza, then a mycorrhizal association may be a preferred strategy. The approach offers a methodology for introducing resource sharing between species into ecosystem models. Applying teleonomy may provide a valuable short-term means of modelling allocation, avoiding the circularity of empirical models, and circumventing the complexities and uncertainties inherent in mechanistic approaches. However it is subjective and brings certain irreducible difficulties with it.
Craven, Galen T; Hernandez, Rigoberto
2015-01-01
When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product -for example, an energy barrier- becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically-expensive simulation of the long-time dynamics of a large ensemble of trajectories.
Funk, Markus B; Heiden, Margarethe; Volkers, Peter; Lohmann, Annette; Keller-Stanislawski, Brigitte
2015-07-01
To assess the impact of safety measures, we compared reporting rates of transfusion-related reactions before and after the implementation of six measures in 1999, 2004, 2006, 2008 and 2009. Reporting rates of transfusion-transmitted bacterial infection (TTBI), viral infection (TTVI) and immune-mediated transfusion-related acute lung injury (TRALI) were calculated on the basis of confirmed annual reports and distributed blood components. The introduction of HCV NAT testing caused a significant reduction of HCV reporting rate from 1:0.6 to 1:83.16 million administered blood components (p blood components, p = 0.422). On the basis of haemovigilance data, a significant benefit could be demonstrated for four of six implemented safety measures.
Ariyasingha, Nuwandi M.; Broderick, Bernadette M.; Thompson, James O. F.; Suits, Arthur
2016-06-01
Chirped-Pulse Fourier-transform microwave spectroscopy in uniform supersonic flows (CPUF) has been applied to study the reaction of Cl atoms with propyne. The approach utilizes broad-band microwave spectroscopy to extract structural information with MHz resolution and near universal detection, in conjunction with a Laval flow system, which offers thermalized conditions at low temperatures and high number densities. Our previous studies have exploited this approach to obtain multichannel product branching fractions in a number of polyatomic systems, with isomer and often vibrational level specificity. This report highlights an additional capability of the CPUF technique: here, the state-specific reactant depletion is directly monitored on a microsecond timescale. In doing so, a clear dependence on the rotational quantum number K in the rate of the reaction between Cl atoms and propyne is revealed. Future prospects for the technique will be discussed.
On progress and rate of the peritectic reaction Fo + SiO2 → En in natural andesitic arc magmas
Zellmer, Georg F.; Sakamoto, Naoya; Matsuda, Nozomi; Iizuka, Yoshiyuki; Moebis, Anja; Yurimoto, Hisayoshi
2016-07-01
Using a high resolution ion microprobe with SCAPS imaging, the peritectic reaction of forsterite + silica to enstatite was studied down to submicron level in a natural andesitic tephra from the Central Plateau of North Island, New Zealand. The fayalitic component of natural olivines is stable in high-silica melts, and therefore the reaction is in fact a two-step progress: 1. Dissolution of Mg-rich olivine, rate-limited by Fe-Mg interdiffusion at the crystal rim, results in enrichment of Fe in the crystal rim and of Mg in the c. 1 μm wide melt boundary layer around the crystal. 2. Magnesian pyroxenes preferentially but not exclusively nucleate in the melt boundary layer and grow; as soon as these microlites touch the rim of the dissolving olivine, they shield the crystals from the silica-rich melt, thereby preventing further olivine dissolution. At this point, Fe-Mg interdiffusion begins to destroy the Fe-enrichment of the olivine rim. The reaction is completed when the dissolving olivine crystal is completely mantled by magnesian pyroxene microlites. Thick pyroxene mantles are likely the result of pyroxene overgrowth rather than due to peritectic transformation. The morphology of the olivine rim preserves information about the reaction history of the grain. Modeling of Fe-Mg interdiffusion in the olivine rim following its shielding from the melt by pyroxene overgrowth may yield the rates of olivine dissolution and the rates of pyroxene growth if temperature is known. For the tephra we have studied, microlite thermometry yields a temperature of 1137 (±41) °C, indicating an olivine dissolution rate of 3-6 × 10-11 ms-1 and an initially volumetric pyroxene growth rate of 2.2-5.6 × 10-21 m3 s-1. This points to timescales between olivine crystal uptake into the SiO2-rich melt and explosive eruption at the surface of a few hours to at most a day.
Jesudason, Christopher G
2011-01-01
The primary emphasis of this work on kinetics is to illustrate the a posteriori approach to applications, where focus on data leads to novel outcomes, rather than the a priori tendencies of applied analysis which imposes constructs on the nature of the observable. The secondary intention is the development of appropriate methods consonant with experimental definitions. By focusing on gradients, it is possible to determine both the average and instantaneous rate constants that can monitor changes in the rate constant with concentration changes as suggested by this theory. Here, methods are developed and discussed utilizing nonlinear analysis which does not require exact knowledge of initial concentrations. These methods are compared with those derived from standard methodology. These gradient methods are shown to be consistent with the ones from standard methods and could readily serve as alternatives for studies where there are limits or unknowns in the initial conditions, such as in the burgeoning fields of ...
Reconciling transition path time and rate measurements in reactions with large entropic barriers
Makarov, Dmitrii E.
2017-02-01
Recent experiments and simulation studies showed that protein/DNA folding barriers inferred from folding rates or from potentials of mean force are often much higher than the barriers estimated from the distributions of transition path times. Here a toy model is used to explain a possible origin of this effect: It is shown that when the transition in question involves an entropic barrier, the one-dimensional Langevin model commonly used to interpret experimental data, while adequately predicting the transition rate, fails to describe the properties of the subset of the trajectories that form the transition path ensemble; the latter may still be describable in terms of a one-dimensional model, but with a different potential, just as observed experimentally.
Sakato, Miho; Zhou, Yayan; Hingorani, Manju M
2012-02-17
The multi-subunit replication factor C (RFC) complex loads circular proliferating cell nuclear antigen (PCNA) clamps onto DNA where they serve as mobile tethers for polymerases and coordinate the functions of many other DNA metabolic proteins. The clamp loading reaction is complex, involving multiple components (RFC, PCNA, DNA, and ATP) and events (minimally: PCNA opening/closing, DNA binding/release, and ATP binding/hydrolysis) that yield a topologically linked clamp·DNA product in less than a second. Here, we report pre-steady-state measurements of several steps in the reaction catalyzed by Saccharomyces cerevisiae RFC and present a comprehensive kinetic model based on global analysis of the data. Highlights of the reaction mechanism are that ATP binding to RFC initiates slow activation of the clamp loader, enabling it to open PCNA (at ~2 s(-1)) and bind primer-template DNA (ptDNA). Rapid binding of ptDNA leads to formation of the RFC·ATP·PCNA(open)·ptDNA complex, which catalyzes a burst of ATP hydrolysis. Another slow step in the reaction follows ATP hydrolysis and is associated with PCNA closure around ptDNA (8 s(-1)). Dissociation of PCNA·ptDNA from RFC leads to catalytic turnover. We propose that these early and late rate-determining events are intramolecular conformational changes in RFC and PCNA that control clamp opening and closure, and that ATP binding and hydrolysis switch RFC between conformations with high and low affinities, respectively, for open PCNA and ptDNA, and thus bookend the clamp loading reaction.
The Experimental Study of Nuclear Astrophysics Reaction Rate of 93Zr(n,γ)94Zr
Gan, L.; Li, Z. H.; Su, J.; Yan, S. Q.; Guo, B.; Du, X. C.; Wu, Z. D.; Zeng, S.; Jin, S. J.; Wang, Y. B.; Bai, X. X.; Zhang, W. J.; Sun, H. B.; Li, E. T.
The slow neutron capture (s-) process plays a very important role in the nucleosynthesis, which produces about half of the elements heavier than iron. 94Zr is mainly from 93Zr(n,γ)94Zr in the s-process, and the direct component of the 93Zr(n,γ)94Zr capture reaction can be derived from the neutron spectroscopic factor of 94Zr. As the existing neutron spectroscopic factors of 94Zr vary from each other up to 60%, a new work should be adopted to measure it exactly. In the present work, the angular distributions of 94Zr(13C,13C)94Zr, 94Zr(12C,12C)94Zr and 94Zr(12C,13C)93Zr were obtained using the highprecision Q3D magnetic spectrograph. In addition, distorted-wave Born approximation (DWBA) calculations of the transfer differential cross sections were performed. The calculated result displays a good agreement with the experiment data, and a value of 2.60±0.20 for the neutron spectroscopic factor of 94Zr was extracted, and the direct capture cross section versus neutron energy of 93Zr(n,γ)94Zr for the ground state of 94Zr was obtained too.
Systematic effects on cross-section data derived from reaction rates at a cold neutron beam
Žerovnik, Gašper, E-mail: gasper.zerovnik@ijs.si [Jožef Stefan Institute, Jamova cesta 39, SI-1000 Ljubljana (Slovenia); European Commission, Joint Research Centre, Retieseweg 111, B-2440 Geel (Belgium); Becker, Björn [European Commission, Joint Research Centre, Retieseweg 111, B-2440 Geel (Belgium); Belgya, Tamás, E-mail: belgya.tamas@energia.mta.hu [Institute for Energy Security and Environmental Safety, Centre for Energy Research, Hungarian Academy of Sciences, 29-33 Konkoly-Thege Miklós Street, H-1121 Budapest (Hungary); Genreith, Christoph, E-mail: christoph.genreith@frm2.tum.de [Heinz Maier-Leibnitz Zentrum (MLZ), Technische Universität München, Lichtenbergstr. 1, D-85748 Garching (Germany); Harada, Hideo, E-mail: harada.hideo@jaea.go.jp [Japan Atomic Energy Agency, Tokai-mura, 319-1195 Ibaraki (Japan); Kopecky, Stefan, E-mail: stefan.kopecky@ec.europa.eu [European Commission, Joint Research Centre, Retieseweg 111, B-2440 Geel (Belgium); Radulović, Vladimir, E-mail: vladimir.radulovic@ijs.si [Jožef Stefan Institute, Jamova cesta 39, SI-1000 Ljubljana (Slovenia); CEA, DEN, DER, Instrumentation, Sensors and Dosimetry Laboratory, Cadarache, F-13108 St-Paul-Lez-Durance (France); Sano, Tadafumi, E-mail: t-sano@rri.kyoto-u.ac.jp [Research Reactor Institute, Kyoto University, Kumatori-cho, 590-0494 Osaka (Japan); Schillebeeckx, Peter, E-mail: peter.schillebeeckx@ec.europa.eu [European Commission, Joint Research Centre, Retieseweg 111, B-2440 Geel (Belgium); and others
2015-11-01
The methodology to derive cross-section data from measurements in a cold neutron beam was studied. Mostly, capture cross-sections at thermal energy are derived relative to a standard cross-section, e.g. the cross-section of the {sup 1}H(n,γ), {sup 14}N(n,γ), or {sup 197}Au(n,γ) reaction, and proportionality between the standard and the measured cross-section, evaluated at different energies in the sub-thermal region, is often assumed. Due to this assumption the derived capture cross-section at thermal energy can be biased by more than 10%. Evidently the bias depends on how much the energy dependence of the cross-section deviates from a direct proportionality with the inverse of the neutron speed. The effect is reduced in case the cross-section is not derived at thermal energy but at an energy close to the average energy of the cold neutron beam. Nevertheless, it is demonstrated that the bias can only be avoided in case the energy dependence of the cross-section is known and proper correction factors are applied. In some cases the results are also biased when the attenuation of the neutron beam within the sample is neglected in the analysis. Some of the cross-section data reported in the literature suffer from such bias effects. Hence, the results have to be corrected using the correction factors presented in this paper.
Neutron spectrum adjustment using reaction rate data acquired with a liquid dosimetry system
Smith, D.L. [Argonne National Lab., IL (United States); Ikeda, Y.; Uno, Y.; Maekawa, F. [JAERI, Tokai (Japan)
1997-08-01
A dosimetry technique based on neutron activation of circulating water with dissolved salts is discussed. The neutron source was the FNS accelerator at JAERI, Tokai, Japan. Yttrium chloride hexahydrate (YCl{sub 3{center_dot}}6H{sub 2}O) was the salt (264.9 grams dissolved in 16.094 liters of water). Gamma-ray yields were measured with an intrinsic Ge detector. The following reactions were examined: (1) {sup 16}O(n,p){sup 16}N (E{sub thresh} = 10.245 MeV, t{sub 1/2} = 7.13 sec, E{sub {gamma}} = 6.129 MeV); (2) {sup 37}Cl(n,p){sup 37}S (E{sub thresh} = 4.194 MeV, t{sub 1/2} = 5.05 min, E{sub {gamma}} = 3.104 MeV); (3) {sup 89}Y(n,n{prime}){sup 89m}Y (E{sub thresh} = 0.919 MeV, t{sub 1/2} = 16.06 sec, E{sub {gamma}} = 0.909 MeV). This paper describes use of the generalized least-squares (GLS) method to adjust the neutron spectrum.
L. Ocola
2008-01-01
Full Text Available Post-disaster reconstruction management of urban areas requires timely information on the ground response microzonation to strong levels of ground shaking to minimize the rebuilt-environment vulnerability to future earthquakes. In this paper, a procedure is proposed to quantitatively estimate the severity of ground response in terms of peak ground acceleration, that is computed from macroseismic rating data, soil properties (acoustic impedance and predominant frequency of shear waves at a site. The basic mathematical relationships are derived from properties of wave propagation in a homogeneous and isotropic media. We define a Macroseismic Intensity Scale I_{MS} as the logarithm of the quantity of seismic energy that flows through a unit area normal to the direction of wave propagation in unit time. The derived constants that relate the I_{MS} scale and peak acceleration agree well with coefficients derived from a linear regression between MSK macroseismic rating and peak ground acceleration for historical earthquakes recorded at a strong motion station, at IGP's former headquarters, since 1954. The procedure was applied to 3-October-1974 Lima macroseismic intensity data at places where there was geotechnical data and predominant ground frequency information. The observed and computed peak acceleration values, at nearby sites, agree well.
Craven, Galen T; Bartsch, Thomas; Hernandez, Rigoberto
2014-07-28
When a chemical reaction is driven by an external field, the transition state that the system must pass through as it changes from reactant to product--for example, an energy barrier--becomes time-dependent. We show that for periodic forcing the rate of barrier crossing can be determined through stability analysis of the non-autonomous transition state. Specifically, strong agreement is observed between the difference in the Floquet exponents describing stability of the transition state trajectory, which defines a recrossing-free dividing surface [G. T. Craven, T. Bartsch, and R. Hernandez, "Persistence of transition state structure in chemical reactions driven by fields oscillating in time," Phys. Rev. E 89, 040801(R) (2014)], and the rates calculated by simulation of ensembles of trajectories. This result opens the possibility to extract rates directly from the intrinsic stability of the transition state, even when it is time-dependent, without requiring a numerically expensive simulation of the long-time dynamics of a large ensemble of trajectories.
Mohamed, Samah
2016-03-21
Accurate chemical kinetic combustion models of lightly branched alkanes (e.g., 2-methylalkanes) are important to investigate the combustion behavior of real fuels. Improving the fidelity of existing kinetic models is a necessity, as new experiments and advanced theories show inaccuracies in certain portions of the models. This study focuses on updating thermodynamic data and the kinetic reaction mechanism for a gasoline surrogate component, 2-methylhexane, based on recently published thermodynamic group values and rate rules derived from quantum calculations and experiments. Alternative pathways for the isomerization of peroxy-alkylhydroperoxide (OOQOOH) radicals are also investigated. The effects of these updates are compared against new high-pressure shock tube and rapid compression machine ignition delay measurements. It is shown that rate constant modifications are required to improve agreement between kinetic modeling simulations and experimental data. We further demonstrate the ability to optimize the kinetic model using both manual and automated techniques for rate parameter tunings to improve agreement with the measured ignition delay time data. Finally, additional low temperature chain branching reaction pathways are shown to improve the model’s performance. The present approach to model development provides better performance across extended operating conditions while also strengthening the fundamental basis of the model.
Badra, Jihad
2015-02-01
Reaction rate constants for nine site-specific hydrogen atom (H) abstraction by hydroxyl radicals (OH) have been determined using experimental measurements of the rate constants of Alkane+OH→Products reactions. Seven secondary (S 20, S 21, S 22, S 30, S 31, S 32, and S 33) and two tertiary (T 100 and T 101) site-specific rate constants, where the subscripts refer to the number of carbon atoms (C) connected to the next-nearest-neighbor (N-N-N) C atom, were obtained for a wide temperature range (250-1450K). This was done by measuring the reaction rate constants for H abstraction by OH from a series of carefully selected large branched alkanes. The rate constant of OH with four different alkanes, namely 2,2-dimethyl-pentane, 2,4-dimethyl-pentane, 2,2,4-trimethyl-pentane (iso-octane), and 2,2,4,4-tetramethyl-pentane were measured at high temperatures (822-1367K) using a shock tube and OH absorption diagnostic. Hydroxyl radicals were detected using the narrow-line-width ring-dye laser absorption of the R1(5) transition of OH spectrum near 306.69nm.Previous low-temperature rate constant measurements are added to the current data to generate three-parameter rate expressions that successfully represent the available direct measurements over a wide temperature range (250-1450. K). Similarly, literature values of the low-temperature rate constants for the reaction of OH with seven normal and branched alkanes are combined with the recently measured high-temperature rate constants from our group [1]. Subsequent to that, site-specific rate constants for abstractions from various types of secondary and tertiary H atoms by OH radicals are derived and have the following modified Arrhenius expressions:. S20=8.49×10-17T1.52exp(73.4K/T)cm3molecule-1s-1(250-1450K) S21=1.07×10-15T1.07exp(208.3K/T)cm3molecule-1s-1(296-1440K) S22=2.88×10-13T0.41exp(-291.5K/T)cm3molecule-1s-1(272-1311K) S30=3.35×10-18T1.97exp(323.1K/T)cm3molecule-1s-1(250-1366K) S31=1.60×10-18T2.0exp(500.0K/T)cm3
Measurements of Fission and Radioactive Capture Reaction Rates Inside the Fuel of the Ipen/MB-01
Mura, Luís Felipe L.; Bitelli, Ulysses d'Utra; Fanaro, Leda C. C. B.
2011-05-01
This work presents the measures of the nuclear reaction rates along the radial direction of the fuel pellet by irradiation and posterior gamma spectrometry of a thin slice of fuel pellet of UO2 at 4.3% enrichment. From its irradiation, the rate of radioactive capture and fission had been measured as a function of the radius of the pellet disk using a Ortec GMX HPGe detector. Lead collimators had been used for this purpose. Simulating the fuel pellet in the pin fuel of the IPEN/MB-01 reactor, a thin UO2 disk is used, being inserted in the interior of a dismountable fuel rod. This fuel rod is then placed in the central position of the IPEN/MB-01 reactor core and irradiated during 1 h under a neutron flux of 5 ×108 n/cm2 s. In gamma spectrometry, 10 collimators with different diameters have been used; consequently, the nuclear reactions of radioactive capture that occurs in atoms of 238U and the fission that occurs on both 235U and 238U are measured in function of 10 different regions (diameter of collimator) of the UO2 fuel pellet disk. Nuclear fission produces different fission products such as 143Ce with a yield fission of 5.9% which decay is monitored in this work. Corrections in geometric efficiency due to introduction of collimators on HPGe detection system were estimated using photon transport of MCNP-4C code. Some calculated values of nuclear reaction rate of radioactive capture and fission along the radial direction of the fuel pellet obtained by Monte Carlo methodology, using the MCNP-4C code, are presented and compared to the experimental data showing very good agreement.
Metabolic Rate and Ground Reaction Force During Motorized and Non-Motorized Treadmill Exercise
Everett, Meghan E.; Loehr, James A.; DeWitt, John K.; Laughlin, Mitzi; Lee, Stuart M. C.
2010-01-01
PURPOSE: To measure vertical ground reaction force (vGRF) and oxygen consumption (VO2) at several velocities during exercise using a ground-based version of the ISS treadmill in the M and NM modes. METHODS: Subjects (n = 20) walked or ran at 0.89, 1.34, 1.79, 2.24, 2.68, and 3.12 m/s while VO2 and vGRF data were collected. VO2 was measured using open-circuit spirometry (TrueOne 2400, Parvo-Medics). Data were averaged over the last 2 min of each 5-min stage. vGRF was measured in separate 15-s bouts at 125 Hz using custom-fitted pressure-sensing insoles (F-Scan Sport Sensors, Tekscan, Inc). A repeated-measures ANOVA was used to test for differences in VO2 and vGRF between M and NM and across speeds. Significance was set at P < 0.05. RESULTS: Most subjects were unable to exercise for 5 min at treadmill speeds above 1.79 m/s in the NM mode; however, vGRF data were obtained for all subjects at each speed in both modes. VO2 was approx.40% higher during NM than M exercise across treadmill speeds. vGRF increased with treadmill speed but was not different between modes. CONCLUSION: Higher VO2 with no change in vGRF suggests that the additional metabolic cost associated with NM treadmill exercise is accounted for in the horizontal forces required to move the treadmill belt. Although this may limit the exercise duration at faster speeds, high-intensity NM exercise activates the hamstrings and plantarflexors, which are not specifically targeted or well protected by other in-flight countermeasures.
Liu, Junjun; Zhao, Xinyun; Yang, Wenchao; Zhan, Chang-Guo
2011-05-05
First-principles quantum mechanical/molecular mechanical free energy calculations have been performed to examine the catalytic mechanism for cocaine esterase (CocE)-catalyzed hydrolysis of (+)-cocaine in comparison with CocE-catalyzed hydrolysis of (-)-cocaine. It has been shown that the acylation of (+)-cocaine consists of nucleophilic attack of the hydroxyl group of Ser117 on the carbonyl carbon of (+)-cocaine benzoyl ester and the dissociation of (+)-cocaine benzoyl ester. The first reaction step of deacylation of (+)-cocaine, which is identical to that of (-)-cocaine, is rate-determining, indicating that CocE-catalyzed hydrolyses of (+)- and (-)-cocaine have a common rate-determining step. The computational results predict that the catalytic rate constant of CocE against (+)-cocaine should be the same as that of CocE against (-)-cocaine, in contrast with the remarkable difference between human butyrylcholinesterase-catalyzed hydrolyses of (+)- and (-)-cocaine. The prediction has been confirmed by experimental kinetic analysis on CocE-catalyzed hydrolysis of (+)-cocaine in comparison with CocE-catalyzed hydrolysis of (-)-cocaine. The determined common rate-determining step indicates that rational design of a high-activity mutant of CocE should be focused on the first reaction step of the deacylation. Furthermore, the obtained mechanistic insights into the detailed differences in the acylation between the (+)- and (-)-cocaine hydrolyses provide indirect clues for rational design of amino acid mutations that could more favorably stabilize the rate-determining transition state in the deacylation and, thus, improve the catalytic activity of CocE. This study provides a valuable mechanistic base for rational design of an improved esterase for therapeutic treatment of cocaine abuse.
Lindquist, W. Brent; Jones, Keith W.; Um, Wooyong; Rockhold, mark; Peters, Catherine A.; Celia, Michael A.
2013-02-15
This project addressed the scaling of geochemical reactions to core and field scales, and the interrelationship between reaction rates and flow in porous media. We targeted reactive transport problems relevant to the Hanford site - specifically the reaction of highly caustic, radioactive waste solutions with subsurface sediments, and the immobilization of 90Sr and 129I through mineral incorporation and passive flow blockage, respectively. We addressed the correlation of results for pore-scale fluid-soil interaction with field-scale fluid flow, with the specific goals of (i) predicting attenuation of radionuclide concentration; (ii) estimating changes in flow rates through changes of soil permeabilities; and (iii) estimating effective reaction rates. In supplemental work, we also simulated reactive transport systems relevant to geologic carbon sequestration. As a whole, this research generated a better understanding of reactive transport in porous media, and resulted in more accurate methods for reaction rate upscaling and improved prediction of permeability evolution. These scientific advancements will ultimately lead to better tools for management and remediation of DOE’s legacy waste problems. We established three key issues of reactive flow upscaling, and organized this project in three corresponding thrust areas. 1) Reactive flow experiments. The combination of mineral dissolution and precipitation alters pore network structure and the subsequent flow velocities, thereby creating a complex interaction between reaction and transport. To examine this phenomenon, we conducted controlled laboratory experimentation using reactive flow-through columns. Results and Key Findings: Four reactive column experiments (S1, S3, S4, S5) have been completed in which simulated tank waste leachage (STWL) was reacted with pure quartz sand, with and without Aluminum. The STWL is a caustic solution that dissolves quartz. Because Al is a necessary element in the formation of
Pucci, M; Martin, U
2017-04-01
Poor adherence with pharmacotherapy is well recognised as one of the main barriers to achieving satisfactory blood pressure control, although accurately measuring patient adherence has historically been very challenging. Urine analysis by high-performance liquid chromatography-tandem mass spectrometry has recently become routinely available as a method of screening for non-adherence. In addition to measuring rates of adherence in hypertensive patients, this study aimed to investigate the reasons for non-adherence given by patients and how patients react when they are informed of their results. This was a retrospective observational study looking at results from the routine use of this assay in a specialist hypertension clinic in Birmingham, UK, in patients with uncontrolled hypertension and those under consideration for renal denervation. Out of the 131 patients analysed, only 67 (51%) were taking all their medications as prescribed. Forty-three patients (33%) were taking some of their medications, whilst 21 patients (16%) were completely non-adherent. The most common reasons cited for non-adherence were adverse effects of medication and forgetfulness. Adherence rates for thiazide/thiazide-like diuretics and spironolactone were lower than for other classes of antihypertensive drug. Despite the objective nature and high sensitivity of the test, 36% of non-adherent patients disputed the results. A minority of patients did not attend follow-up. Further research investigating the implications of a 'non-adherence' result on the patient-clinician relationship is required.
The Progression of Sequential Reactions
Jack McGeachy
2010-01-01
Full Text Available Sequential reactions consist of linked reactions in which the product of the first reaction becomes the substrate of a second reaction. Sequential reactions occur in industrially important processes, such as the chlorination of methane. A generalized series of three sequential reactions was analyzed in order to determine the times at which each chemical species reaches its maximum. To determine the concentration of each species as a function of time, the differential rate laws for each species were solved. The solution of each gave the concentration curve of the chemical species. The concentration curves of species A1 and A2 possessed discreet maxima, which were determined through slope-analysis. The concentration curve of the final product, A3, did not possess a discreet maximum, but rather approached a finite limit.