Subgrade stabilization alternatives to lime and cement.

Science.gov (United States)

2010-04-15

This project involved four distinct research activities, (1) the influence of temperature on lime-stabilized soils, (2) the influence of temperature on cement-stabilized soils (3) temperature modeling of stabilized subgrade and (4) use of calcium chl...

Effect of Cement Replacement with Carbide Waste on the Strength of Stabilized Clay Subgrade

Directory of Open Access Journals (Sweden)

Muntohar A.S.

2016-03-01

Full Text Available Cement is commonly used for soil stabilization and many other ground improvement techniques. Cement is believed to be very good to improve the compressive and split-tensile strength of clay subgrades. In some application cement could be partly or fully replaced with carbide waste. This research is to study the effectiveness of the cement replacement and to find the maximum carbide waste content to be allowed for a clay subgrade. The quantities of cement replaced with the carbide waste were 30, 50, 70, 90, and 100% by its mass. The results show that replacing the cement with carbide waste decreased both the compressive and split tensile strength. Replacing cement content with carbide waste reduced its ability for stabilization. The carbide waste content should be less than 70% of the cement to provide a sufficient stabilizing effect on a clay subgrade.

Pavement system with rubber tire chips in subgrade

Energy Technology Data Exchange (ETDEWEB)

Ashtakala, B.; Hoque, A.K.M.M. [Concordia Univ., Montreal, PQ (Canada). Dept. of Civil Engineering

1995-12-31

A pavement design method was developed in which shredded rubber tire chips mixed with sand were used as a material for pavement subgrade. Rubber tire chips are highly compressible and produce both elastic and plastic deformations under the application of loads. Sand was added to fill the void between the tire chips and make the mixture a strong material. The design method considered the vertical compressive strain produced by the design life traffic load 18k (80 KN) repetitions. The equivalent thicknesses of the layers above the subgrade corresponding to this vertical compressive strain were determined using contour charts. From this equivalent thickness, the thicknesses for asphalt pavement, base, and sub-base were determined by Odemark`s method. 3 refs., 1 tab., 3 figs.

Instability improvement of the subgrade soils by lime addition at Borg El-Arab, Alexandria, Egypt

Science.gov (United States)

El Shinawi, A.

2017-06-01

Subgrade soils can affect the stability of any construction elsewhere, instability problems were found at Borg El-Arab, Alexandria, Egypt. This paper investigates geoengineering properties of lime treated subgrade soils at Borg El-Arab. Basic laboratory tests, such as water content, wet and dry density, grain size, specific gravity and Atterberg limits, were performed for twenty-five samples. Moisture-density (compaction); California Bearing Ratio (CBR) and Unconfined Compression Strength (UCS) were conducted on treated and natural soils. The measured geotechnical parameters of the treated soil shows that 6% lime is good enough to stabilize the subgrade soils. It was found that by adding lime, samples shifted to coarser side, Atterberg limits values of the treated soil samples decreased and this will improve the soil to be more stable. On the other hand, Subgrade soils improved as a result of the bonding fine particles, cemented together to form larger size and reduce the plastiCity index which increase soils strength. The environmental scanning electron microscope (ESEM) is point to the presence of innovative aggregated cement materials which reduce the porosity and increase the strength as a long-term curing. Consequently, the mixture of soil with the lime has acceptable mechanical characteristics where, it composed of a high strength base or sub-base materials and this mixture considered as subgrade soil for stabilizations and mitigation the instability problems that found at Borg Al-Arab, Egypt.

Rate coefficients for hydrogen abstraction reaction of pinonaldehyde

Indian Academy of Sciences (India)

The H abstraction reaction from the –CHO group was found to be the most dominant reaction channelamong all the possible reaction pathways and its corresponding rate coefficient at 300 K is kEckart's unsymmetrical= 3.86 ×10-10 cm3 molecule-1 s-1. Whereas the channel with immediate lower activation energy is the ...

Evaluation of Carbonation Effects on Cement-Solidified Contaminated Soil Used in Road Subgrade

Directory of Open Access Journals (Sweden)

Yundong Zhou

2018-01-01

Full Text Available Cement solidification/stabilization is widely used towards contaminated soil since it has a low price and significant improvement for the structural capacity of soil. To increase the usage of the solidified matrix, cement-solidified contaminated soil was used as road subgrade material. In this study, carbonation effect that reflected the durability on strength characteristics of cement-solidified contaminated soil and the settlement of pavement were evaluated through experimental and numerical analysis, respectively. According to results, compressive strengths of specimens with 1% Pb(II under carbonation and standard curing range from 0.44 MPa to 1.17 MPa and 0.14 MPa to 2.67 MPa, respectively. The relatively low strengths were attributed to immobilization of heavy metal, which consumed part of SiO2, Al2O3, and CaO components in the cement or kaolin and reduced the hydration and pozzolanic reaction materials. This phenomenon further decreased the strength of solidified soils. The carbonation depth of 1% Cu(II or Zn(II contaminated soils was 18 mm, which significantly increased with the increase of curing time and contamination concentration. Furthermore, the finite element calculation results showed that surface settlements decreased with the increase of modulus of subgrade and the distance away from the center. At the center, the pavement settlement was proportional to the level of traffic load.

Rate coefficient for the reaction N + NO

Science.gov (United States)

Fox, J. L.

1994-01-01

Evidence has been advanced that the rate coefficient for the reaction N + NO right arrow N2 + O has a small positive temperature dependence at the high temperatures (900 to 1500 K) that prevail in the terrestrial middle and upper thermosphere by Siskind and Rusch (1992), and at the low temperatures (100 to 200 K) of the Martian lower thermosphere by Fox (1993). Assuming that the rate coefficient recommended by the Jet Propulsion Laboratory evaluation (DeMore et al., 1992) is accurate at 300 K, we derive here the low temperature value of the activation energy for this reaction and thus the rate coefficient that best fits the Viking 1 measured NO densities. We find that the fit is acceptable for a rate coefficient of about 1.3 x 10(exp -10)(T/300)(exp 0.5)exp(-400/T) and better for a value of about 2.5 x 10(exp -10)(T/300)(exp 0.5)exp(-600/T)cu cm/s.

Pemanfaatan Limbah Pabrik Tekstil (Sludge) Sebagai Penstabil Tanah Lempung untuk Subgrade Jalan

OpenAIRE

Subarkah, Subarkah

2009-01-01

Soil subgrade has an important role in supporting road pavement construction, especially in establishment of the pavement structure. Swelling characteristic and bearing capacity of the clay soil as a subgrade should be carefully considered in the design to fit the specification. In fact, poor soil such as clay, in some cases, should be replaced by another soil from remote location, or by stabilization of this origin soils to overcome the weakness. In other hand, textile industry has a d...

Drying shrinkage problems in high PI subgrade soils.

Science.gov (United States)

2014-01-01

The main objective of this study was to investigate the longitudinal cracking in pavements due to drying : shrinkage of high PI subgrade soils. The study involved laboartory soil testing and modeling. The : shrinkage cracks usually occur within the v...

Reaction rate calculations via transmission coefficients

International Nuclear Information System (INIS)

Feit, M.D.; Alder, B.J.

1985-01-01

The transmission coefficient of a wavepacket traversing a potential barrier can be determined by steady state calculations carried out in imaginary time instead of by real time dynamical calculations. The general argument is verified for the Eckart barrier potential by a comparison of transmission coefficients calculated from real and imaginary time solutions of the Schroedinger equation. The correspondence demonstrated here allows a formulation for the reaction rate that avoids difficulties due to both rare events and explicitly time dependent calculations. 5 refs., 2 figs

A comparative study of soil-structure interaction in the case of frame structures with raft foundation

Directory of Open Access Journals (Sweden)

Móczár Balázs

2016-06-01

Full Text Available Design and modelling of raft foundations and selecting the value of coefficient of vertical subgrade reaction are still actively discussed topics in geotechnical and structural engineering. In everyday practice, soil–structure interaction is mostly taken into account by using the theory of ‘beam on elastic foundation’, in which the soil is substituted by a certain set of coefficients of subgrade reaction. In this study, finite element analysis of a building was performed using a geotechnical software (Plaxis 3D, which is capable of modelling the subsoil as a continuum, and a structural software (Axis VM, which uses the concept of ‘beam on elastic foundation’. The evaluation of the results and recommendations for everyday engineering practice are introduced in this paper.

The estimation of parameter compaction values for pavement subgrade stabilized with lime

Science.gov (United States)

Lubis, A. S.; Muis, Z. A.; Simbolon, C. A.

2018-02-01

The type of soil material, field control, maintenance and availability of funds are several factors that must be considered in compaction of the pavement subgrade. In determining the compaction parameters in laboratory desperately requires considerable materials, time and funds, and reliable laboratory operators. If the result of soil classification values can be used to estimate the compaction parameters of a subgrade material, so it would save time, energy, materials and cost on the execution of this work. This is also a clarification (cross check) of the work that has been done by technicians in the laboratory. The study aims to estimate the compaction parameter values ie. maximum dry unit weight (γdmax) and optimum water content (Wopt) of the soil subgrade that stabilized with lime. The tests that conducted in the laboratory of soil mechanics were to determine the index properties (Fines and Liquid Limit/LL) and Standard Compaction Test. Soil samples that have Plasticity Index (PI) > 10% were made with additional 3% lime for 30 samples. By using the Goswami equation, the compaction parameter values can be estimated by equation γd max # = -0,1686 Log G + 1,8434 and Wopt # = 2,9178 log G + 17,086. From the validation calculation, there was a significant positive correlation between the compaction parameter values laboratory and the compaction parameter values estimated, with a 95% confidence interval as a strong relationship.

Field Verification of Undercut Criteria and Alternatives for Subgrade Stabilization-Coastal Plain

Science.gov (United States)

2012-06-01

The North Carolina Department of Transportation (NCDOT) is progressing toward developing quantitative and systematic : criteria that address the implementation of undercutting as a subgrade stabilization measure. As part of this effort, a : laborator...

Geogrid reinforced road subgrade influence on the pavement evenness

Science.gov (United States)

Šiukščius, A.; Vorobjovas, V.; Vaitkus, A.

2018-05-01

As a result of increasing geogrid reinforcement applications in the road subgrade, there are number of projects where geogrid reinforcement is used to control road pavement evenness when there are small layers of peat or mud deeper under road construction. For this task geogrid reinforcement application is not documented but widely used in Lithuania for over a decade. This paper evaluates the long term influence of the geogrid reinforced soil influence on the road surface evenness, when the organic soils stratify in the deeper layers of the subgrade. The geological conditions of the investigated sections are reviewed. The experiment methodology and test results are described, which leads to the conclusions and insights how the pavement evenness depend on the geological conditions and its enhancement. The question is raised about the need for including this geogrid application to the normative documentation. Explanation of the problems that are encountered and the need for further research is given.

The rate coefficients of unimolecular reactions in the systems with power-law distributions

Science.gov (United States)

Yin, Cangtao; Guo, Ran; Du, Jiulin

2014-08-01

The rate coefficient formulae of unimolecular reactions are generalized to the systems with the power-law distributions based on nonextensive statistics, and the power-law rate coefficients are derived in the high and low pressure limits, respectively. The numerical analyses are made of the rate coefficients as functions of the ν-parameter, the threshold energy, the temperature and the number of degrees of freedom. We show that the new rate coefficients depend strongly on the ν-parameter different from one (thus from a Boltzmann-Gibbs distribution). Two unimolecular reactions, CH3CO→CH3+CO and CH3NC→CH3CN, are taken as application examples to calculate their power-law rate coefficients, which obtained with the ν-parameters slightly different from one can be exactly in agreement with all the experimental studies on these two reactions in the given temperature ranges.

Melanoidins extinction coefficient in the glucose/glycine Maillard reaction

NARCIS (Netherlands)

Martins, S.I.F.S.; Boekel, van M.A.J.S.

2003-01-01

Melanoidins (brown, nitrogenous polymers and co-polymers) are the final products of the Maillard reaction. The glucose/glycine melanoidins extinction coefficient was determined using C-14-labelled glucose at three different reaction conditions. The absorbance was measured at different wavelengths

Evaluation of Subgrade Soils using California Bearing Ratio (Cbr) in ...

African Journals Online (AJOL)

The two options that are fit for the upgrade are the over – excavation and stabilization options. The over - excavation method of enhancement of the performance of the subgrade materials that have been studied will require the excavation of the sub- grade soil to the depth of 0.7m and the subsequent replacement with ...

The Influence of Particle Charge on Heterogeneous Reaction Rate Coefficients

Science.gov (United States)

Aikin, A. C.; Pesnell, W. D.

2000-01-01

The effects of particle charge on heterogeneous reaction rates are presented. Many atmospheric particles, whether liquid or solid are charged. This surface charge causes a redistribution of charge within a liquid particle and as a consequence a perturbation in the gaseous uptake coefficient. The amount of perturbation is proportional to the external potential and the square of the ratio of debye length in the liquid to the particle radius. Previous modeling has shown how surface charge affects the uptake coefficient of charged aerosols. This effect is now included in the heterogeneous reaction rate of an aerosol ensemble. Extension of this analysis to ice particles will be discussed and examples presented.

PLUTONIUM FINISHING PLANT (PFP) SUB-GRADE EE/CA EVALUATION OF ALTERNATIVES: A NEW MODEL

International Nuclear Information System (INIS)

HOPKINS, A.M.

2007-01-01

An engineering evaluation/cost analysis (EE/CA) was performed at the Hanford Site's Plutonium Finishing Plant (PFP). The purpose of the EVCA was to identify the sub-grade items to be evaluated; determine the Comprehensive Environmental Response, Compensation, and Liability Act of 1980 (CERCLA) hazardous substances through process history and available data; evaluate these hazards; and as necessary, identify the available alternatives to reduce the risk associated with the contaminants. The sub-grade EWCA considered four alternatives for an interim removal action: (1) No Action; (2) Surveillance and Maintenance (S and M); (3) Stabilize and Leave in Place (Stabilization); and (4) Remove, Treat and Dispose (RTD). Each alternative was evaluated against the CERCLA criteria for effectiveness, implementability, and cost

Pembuatan Makanan Ringan Produk Ekstrusi Dari Subgrade Ubi Jalar Goreng Beku Sebagai Bahan Substitusi Serta Analisis Kelayakan Finansial

Directory of Open Access Journals (Sweden)

Betha Ika Wilistien

2017-03-01

Full Text Available The objective of this research is to determine the influential proportion of sweet potato Subgrade frozen usage as the substitution material toward the production of an extract product snack by using corn grits and rice. The parameters examined were organoleptic characteristic and proper analysis of financial. The organoleptic analysis comprises taste, crispiness, appearance, color, and aroma. The chemical analysis includes sucrose, water, and essence, as well as protein content. The result of this research shows that organoleptic testing toward the taste of an extract product snack by using Beni azzuma sweet potato subgrade indicates that the combination treatments give a positive influence toward organoleptic characteristics of the product. An extract product of snack product from Beni azzuma sweet potato Subgrade as the substitution material with 95% rice formula and 5% Beni azzuma sweet potato Subgrade is chosen as the best product for having the highest weight or quality, 0.970. Proper analysis from the snack processing is shown by NPV score, Rp. 2.,016,418,748 (bigger than zero, the IRR score is 50.00% (bigger than deposit interest, 12.56%. The investment expense needed for constructing the unit of an extract product snack processing with Beni azzuma sweet potato Subgrade as the substitution material is Rp. 330,978,230. The investment will be back after 3 years 5 months, and every year the project can give the profit of 50% from the investment expense.

Influence of Subgrade and Unbound Granular Layers Stiffness on Fatigue Life of Hot Mix Asphalts - HMA

Directory of Open Access Journals (Sweden)

Hugo A. Rondón-Quintana

2013-11-01

Full Text Available The mainly factors studied to predict fatigue life of hot mix asphalt-HMA in flexible pavements are the loading effect, type of test, compaction methods, design parameters of HMA (e.g., particle size and size distribution curve, fine content, type of bitumen and the variables associated with the environment (mainly moisture, temperature, aging. This study evaluated through a computer simulation, the influence of the granular layers and subgrade on the fatigue life of asphalt layers in flexible pavement structures. Mechanics parameters of granular layers of subgrade, base and subbase were obtained using the mathematical equations currently used for this purpose in the world. The emphasis of the study was the city of Bogotá, where the average annual temperature is 14°C and soils predominantly clay, generally experience CBR magnitudes between 1% and 4%. General conclusion: stiffness of the granular layers and subgrade significantly affect the fatigue resistance of HMA mixtures. Likewise, the use of different equations reported in reference literature in order to characterize granular layers may vary the fatigue life between 4.6 and 48.5 times, varying the thickness of the pavement layers in the design.

Occurrence of shale soils along the Calabar-Itu highway, Southeastern Nigeria and their implication for the subgrade construction.

Science.gov (United States)

Ilori, Abidemi Olujide

2016-01-01

This study concerned a stretch of 17 km of a 94-km highway alignment in Southeastern Nigeria that has a high incidence of pavement failure arising from subgrade failure. The subgrade of this section of the roadway is composed of Ekenkpon shale, New Netim marl, and Nkporo shale. Under the Unified Soil Classification System, the shales classify as OH (organic clay) and the marl classifies as MH (inorganic silt). Under the American Association of State and Transportation Officials (AASHTO) M 145 soil classification, all these soils classify as A-7-5 soil. Using the AASHTO M 145 group index, none of these soils was considered suitable as subgrade in its native form. Therefore, cement was investigated as a stabilizing agent. Testing demonstrated that 7, 3 and 12 % by weight were the optimum cement contents to reinforce the Ekenkpon shale, New Netim marl, and Nkporo shale, respectively.

On application of stone filled subgrade construction technique in road construction%填石路基施工技术在公路工程中的应用

Institute of Scientific and Technical Information of China (English)

王宁

2017-01-01

介绍了填石路基的施工技术与质量控制要点,并以某公路工程为例,从基底施工、路基清理、边坡码砌、摊铺填料、路基平整等方面,阐述了填石路基的施工技术,提高了路基的性能.%The paper introduces the construction technique and quality control points for the stone filled subgrade,take a road project as an example,expounds the construction technique of the filling stone roadbed from the subgrade construction,subgrade cleaning,slope stone stocking,pavement and filling,and subgrade smoothness,so as to improve the performance of the subgrade.

Evaluation and field verification of strength and structural improvement of chemically stabilized subgrade soil.

Science.gov (United States)

2008-07-01

Often subgrade soils exhibit properties, particularly strength and/or volume change properties that limit their performance as a support element for pavements. : Typical problems include shrink-swell, settlement, collapse, erosion or simply insuffici...

Saponification reaction system: a detailed mass transfer coefficient determination.

Science.gov (United States)

Pečar, Darja; Goršek, Andreja

2015-01-01

The saponification of an aromatic ester with an aqueous sodium hydroxide was studied within a heterogeneous reaction medium in order to determine the overall kinetics of the selected system. The extended thermo-kinetic model was developed compared to the previously used simple one. The reaction rate within a heterogeneous liquid-liquid system incorporates a chemical kinetics term as well as mass transfer between both phases. Chemical rate constant was obtained from experiments within a homogeneous medium, whilst the mass-transfer coefficient was determined separately. The measured thermal profiles were then the bases for determining the overall reaction-rate. This study presents the development of an extended kinetic model for considering mass transfer regarding the saponification of ethyl benzoate with sodium hydroxide within a heterogeneous reaction medium. The time-dependences are presented for the mass transfer coefficient and the interfacial areas at different heterogeneous stages and temperatures. The results indicated an important role of reliable kinetic model, as significant difference in k(L)a product was obtained with extended and simple approach.

Temperature-Dependent Rate Coefficients for the Reaction of CH2OO with Hydrogen Sulfide.

Science.gov (United States)

Smith, Mica C; Chao, Wen; Kumar, Manoj; Francisco, Joseph S; Takahashi, Kaito; Lin, Jim Jr-Min

2017-02-09

The reaction of the simplest Criegee intermediate CH 2 OO with hydrogen sulfide was measured with transient UV absorption spectroscopy in a temperature-controlled flow reactor, and bimolecular rate coefficients were obtained from 278 to 318 K and from 100 to 500 Torr. The average rate coefficient at 298 K and 100 Torr was (1.7 ± 0.2) × 10 -13 cm 3 s -1 . The reaction was found to be independent of pressure and exhibited a weak negative temperature dependence. Ab initio quantum chemistry calculations of the temperature-dependent reaction rate coefficient at the QCISD(T)/CBS level are in reasonable agreement with the experiment. The reaction of CH 2 OO with H 2 S is 2-3 orders of magnitude faster than the reaction with H 2 O monomer. Though rates of CH 2 OO scavenging by water vapor under atmospheric conditions are primarily controlled by the reaction with water dimer, the H 2 S loss pathway will be dominated by the reaction with monomer. The agreement between experiment and theory for the CH 2 OO + H 2 S reaction lends credence to theoretical descriptions of other Criegee intermediate reactions that cannot easily be probed experimentally.

Chemical stabilization of subgrade soil for the strategic expeditionary landing field

Science.gov (United States)

Conaway, M. H.

1983-06-01

The Strategic Expeditionary Landing Field (SELF) is a military expeditionary-type airfield with an aluminum matted surface that is designed for sustained tactical and cargo airlift operations in an amphibious objective area. Because of the operational traffic parameters such as loads of the various types of aircraft, tire pressures and volume of traffic, a base layer must be constructed over subgrade soil support conditions which may be only marginal. The base layer could be constructed with conventional soil construction techniques (compaction) and yield the required strength. It would be difficult, however, to maintain this strength for the required one-year service life under many climatic conditions due to the degrading effects of water on the support capacity of many soils. Chemical soil stabilization with lime, portland cement and asphalt stabilizing agents could be used to treat the soil. These additives, when properly mixed with certain types of soils, initiate reactions which will increase soil support strength and enhance durability (resistance to the degrading effects of water). Technically, this procedure is quite viable but logistically, it may not be feasible.

Field Measurement of Dynamic Compressive Stress Response of Pavement-Subgrade Induced by Moving Heavy-Duty Trucks

Directory of Open Access Journals (Sweden)

Lingshi An

2018-01-01

Full Text Available This paper presents the dynamic compressive stress response of pavement-subgrade induced by moving heavy-duty trucks. In order to study the distribution characteristic of dynamic pressure of pavement-subgrade in more detail, truck loadings, truck speeds, and dynamic pressure distributions at different depths were monitored under twenty-five working conditions on the section of Qiqihar-Nenjiang Highway in Heilongjiang Province, China. The effects of truck loading, truck speed, and depth on dynamic compressive stress response can be concluded as follows: (1 increasing truck loading will increase the dynamic pressure amplitude of subgrade-pavement and dominant frequencies are close to the characteristic frequencies caused by heavy-duty trucks at the speed of 70 km/h; (2 as truck speed increases, the dynamic pressure amplitudes of measuring points have an increasing tendency; the dynamic pressure spectrums are also significantly influenced by truck speed: the higher the truck speed, the wider the spectrum and the higher the dominant frequencies; (3 as depth increases, the dynamic pressure amplitudes of measuring points decrease rapidly. The influence of the front axle decreases gradually until disappearing and the compressive stress superposition phenomenon caused by rear double axles can be found with increasing depth.

Engineering properties of stabilized subgrade soils for implementation of the AASHTO 2002 pavement design guide.

Science.gov (United States)

2009-06-01

A comprehensive laboratory study was undertaken to determine engineering properties of cementitiously stabilized common subgrade soils in Oklahoma for the design of roadway pavements in accordance with the AASHTO 2002 Mechanistic-Empirical Pavement D...

Rate Coefficient Measurements of the Reaction CH3 + O2 = CH3O + O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, sub -0.47 ) x 10(exp 13) e(-15813 +/- 587 K/T)/cubic cm.mol.s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Rate Coefficient Measurements of the Reaction CH3+O2+CH3O+O

Science.gov (United States)

Hwang, S. M.; Ryu, Si-Ok; DeWitt, K. J.; Rabinowitz, M. J.

1999-01-01

Rate coefficients for the reaction CH3 + O2 = CH3O + O were measured behind reflected shock waves in a series of lean CH4-O2-Ar mixtures using hydroxyl and methyl radical diagnostics. The rate coefficients are well represented by an Arrhenius expression given as k = (1.60(sup +0.67, -0.47)) X 10(exp 13) exp(- 15813 +/- 587 K/T)cc/mol s. This expression, which is valid in the temperature range 1575-1822 K, supports the downward trend in the rate coefficients that has been reported in recent determinations. All measurements to date, including the present study, have been to some extent affected by secondary reactions. The complications due to secondary reactions, choice of thermochemical data, and shock-boundary layer interactions that affect the determination of the rate coefficients are examined.

Measurement of seasonal changes and spatial variations in pavement unbound base and subgrade properties.

Science.gov (United States)

2009-01-01

Soils often undergo cyclic wetting/drying, but there is very limited research on unsaturated : soils subjected to variations in moisture content. More specifically, field moisture variation : over time in highway unbound bases and subgrade soils is a...

Resilient modulus characteristics of soil subgrade with geopolymer additive in peat

Science.gov (United States)

Zain, Nasuhi; Hadiwardoyo, Sigit Pranowo; Rahayu, Wiwik

2017-06-01

Resilient modulus characteristics of peat soil are generally very low with high potential of deformation and low bearing capacity. The efforts to improve the peat subgrade resilient modulus characteristics is required, one among them is by adding the geopolymer additive. Geopolymer was made as an alternative to replace portland cement binder in the concrete mix in order to promote environmentally friendly, low shrinkage value, low creep value, and fire resistant material. The use of geopolymer to improve the mechanical properties of peat as a road construction subgrade, hence it becomes important to identify the effect of geopolymer addition on the resilient modulus characteristics of peat soil. This study investigated the addition of 0% - 20% geopolymer content on peat soil derived from Ogan Komering Ilir, South Sumatera Province. Resilient modulus measurement was performed by using cyclic triaxial test to determine the resilience modulus model as a function of deviator stresses and radial stresses. The test results showed that an increase in radial stresses did not necessarily lead to an increase in modulus resilient, and on the contrary, an increase in deviator stresses led to a decrease in modulus resilient. The addition of geopolymer in peat soil provided an insignificant effect on the increase of resilient modulus value.

Angular distribution coefficients for γ-ray polarization produced in polarized capture reactions

International Nuclear Information System (INIS)

Wulf, E.A.; Guillemette, J.; Weller, H.R.; Seyler, R.G.

1999-01-01

The previous publications have dealt with the angular momentum formalism of both linear and circularly polarized photons in (γ, x) reactions on both polarized and unpolarized targets, and the inverse (capture) reactions initiated by polarized beams. In the present work, utilizing the general formalism of Welton, the authors deal with the linear polarization of the γ-rays which are produced in capture reactions on unpolarized targets, including the possibility of having incident polarized spin 1/2 projectiles. These capture reactions are denoted by a(rvec x, rvec L)c, where rvec x is the incident polarized spin 1/2 projectile and rvec L represents the outgoing polarized γ-ray. They present here the formalism in a convenient form, display a sample table of coefficients, and illustrate its use by means of several examples. A FORTRAN code will be made available for generating similar coefficients for other reactions

Simplified method of ''push-pull'' test data analysis for determining in situ reaction rate coefficients

International Nuclear Information System (INIS)

Haggerty, R.; Schroth, M.H.; Istok, J.D.

1998-01-01

The single-well, ''''push-pull'''' test method is useful for obtaining information on a wide variety of aquifer physical, chemical, and microbiological characteristics. A push-pull test consists of the pulse-type injection of a prepared test solution into a single monitoring well followed by the extraction of the test solution/ground water mixture from the same well. The test solution contains a conservative tracer and one or more reactants selected to investigate a particular process. During the extraction phase, the concentrations of tracer, reactants, and possible reaction products are measured to obtain breakthrough curves for all solutes. This paper presents a simplified method of data analysis that can be used to estimate a first-order reaction rate coefficient from these breakthrough curves. Rate coefficients are obtained by fitting a regression line to a plot of normalized concentrations versus elapsed time, requiring no knowledge of aquifer porosity, dispersivity, or hydraulic conductivity. A semi-analytical solution to the advective-dispersion equation is derived and used in a sensitivity analysis to evaluate the ability of the simplified method to estimate reaction rate coefficients in simulated push-pull tests in a homogeneous, confined aquifer with a fully-penetrating injection/extraction well and varying porosity, dispersivity, test duration, and reaction rate. A numerical flow and transport code (SUTRA) is used to evaluate the ability of the simplified method to estimate reaction rate coefficients in simulated push-pull tests in a heterogeneous, unconfined aquifer with a partially penetrating well. In all cases the simplified method provides accurate estimates of reaction rate coefficients; estimation errors ranged from 0.1 to 8.9% with most errors less than 5%

Communication: Rate coefficients from quasiclassical trajectory calculations from the reverse reaction: The Mu + H2 reaction re-visited

Science.gov (United States)

Homayoon, Zahra; Jambrina, Pablo G.; Aoiz, F. Javier; Bowman, Joel M.

2012-07-01

In a previous paper [P. G. Jambrina et al., J. Chem. Phys. 135, 034310 (2011), 10.1063/1.3611400] various calculations of the rate coefficient for the Mu + H2 → MuH + H reaction were presented and compared to experiment. The widely used standard quasiclassical trajectory (QCT) method was shown to overestimate the rate coefficients by several orders of magnitude over the temperature range 200-1000 K. This was attributed to a major failure of that method to describe the correct threshold for the reaction owing to the large difference in zero-point energies (ZPE) of the reactant H2 and product MuH (˜0.32 eV). In this Communication we show that by performing standard QCT calculations for the reverse reaction and then applying detailed balance, the resulting rate coefficient is in very good agreement with the other computational results that respect the ZPE, (as well as with the experiment) but which are more demanding computationally.

Molecular extinction coefficients of lead sulfide and polymerized diaminobenzidine as final reaction products of histochemical phosphatase reactions

NARCIS (Netherlands)

van Noorden, C. J.; Jonges, G. N.

1992-01-01

Molar extinction coefficients of precipitated lead sulfide (PbS) and polymerized diaminobenzidine (polyDAB) have been determined at wavelengths of 450 nm and 480 nm, respectively, for quantitative histochemical analysis of phosphatase reactions. These values are essential for the conversion of

Microscopic calculation of friction coefficients for use in heavy-ion reaction

International Nuclear Information System (INIS)

Iwamoto, A.; Harada, K.; Yoshida, S.

1981-01-01

A microscopic calculation has been done for the friction coefficient for use in the deep-inelastic collision of heavy nuclei. We adopted the formalism of the linear response theory as a basis and used the adiabatic base of the two-center shell model. Several reaction channels with the total mass numbers of 236 and 260 systems were investigated. The friction coefficients for the radial and deforming motions including the coupling term were calculated as a function of the distance between two nuclei and deformation of the two nuclei for each channel. The general feature of the friction coefficient, its strength and form factor, was clarified in this model and comparison with the results of other models were done. It was found that our model gives a physically plausible value for the friction coefficient as a whole. (orig.)

Evaluation of AM2 2 1 Lay Pattern Over a 25 CBR Subgrade

Science.gov (United States)

2018-04-30

Geotechnical and Structures Laboratory U.S. Army Engineer Research and Development Center 3909 Halls Ferry Road Vicksburg, MS 39180-6199 Final...which no subgrade maintenance is required during expeditionary operations. Recent investigations showed that the 2-1 configuration significantly... maintenance requirements for F-15E and C-17 operations. DISCLAIMER: The contents of this report are not to be used for advertising, publication

The Atmospherically Important Reaction of Hydroxyl Radicals with Methyl Nitrate: A Theoretical Study Involving the Calculation of Reaction Mechanisms, Enthalpies, Activation Energies, and Rate Coefficients.

Science.gov (United States)

Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

2017-09-07

A theoretical study, involving the calculation of reaction enthalpies, activation energies, mechanisms, and rate coefficients, was made of the reaction of hydroxyl radicals with methyl nitrate, an important process for methyl nitrate removal in the earth's atmosphere. Four reaction channels were considered: formation of H 2 O + CH 2 ONO 2 , CH 3 OOH + NO 2 , CH 3 OH + NO 3 , and CH 3 O + HNO 3 . For all channels, geometry optimization and frequency calculations were performed at the M06-2X/6-31+G** level, while relative energies were improved at the UCCSD(T*)-F12/CBS level. The major channel is found to be the H abstraction channel, to give the products H 2 O + CH 2 ONO 2 . The reaction enthalpy (ΔH 298 K RX ) of this channel is computed as -17.90 kcal mol -1 . Although the other reaction channels are also exothermic, their reaction barriers are high (>24 kcal mol -1 ), and therefore these reactions do not contribute to the overall rate coefficient in the temperature range considered (200-400 K). Pathways via three transition states were identified for the H abstraction channel. Rate coefficients were calculated for these pathways at various levels of variational transition state theory including tunneling. The results obtained are used to distinguish between two sets of experimental rate coefficients, measured in the temperature range of 200-400 K, one of which is approximately an order of magnitude greater than the other. This comparison, as well as the temperature dependence of the computed rate coefficients, shows that the lower experimental values are favored. The implications of the results to atmospheric chemistry are discussed.

Estimating Reaction Rate Coefficients Within a Travel-Time Modeling Framework

Energy Technology Data Exchange (ETDEWEB)

Gong, R [Georgia Institute of Technology; Lu, C [Georgia Institute of Technology; Luo, Jian [Georgia Institute of Technology; Wu, Wei-min [Stanford University; Cheng, H. [Stanford University; Criddle, Craig [Stanford University; Kitanidis, Peter K. [Stanford University; Gu, Baohua [ORNL; Watson, David B [ORNL; Jardine, Philip M [ORNL; Brooks, Scott C [ORNL

2011-03-01

A generalized, efficient, and practical approach based on the travel-time modeling framework is developed to estimate in situ reaction rate coefficients for groundwater remediation in heterogeneous aquifers. The required information for this approach can be obtained by conducting tracer tests with injection of a mixture of conservative and reactive tracers and measurements of both breakthrough curves (BTCs). The conservative BTC is used to infer the travel-time distribution from the injection point to the observation point. For advection-dominant reactive transport with well-mixed reactive species and a constant travel-time distribution, the reactive BTC is obtained by integrating the solutions to advective-reactive transport over the entire travel-time distribution, and then is used in optimization to determine the in situ reaction rate coefficients. By directly working on the conservative and reactive BTCs, this approach avoids costly aquifer characterization and improves the estimation for transport in heterogeneous aquifers which may not be sufficiently described by traditional mechanistic transport models with constant transport parameters. Simplified schemes are proposed for reactive transport with zero-, first-, nth-order, and Michaelis-Menten reactions. The proposed approach is validated by a reactive transport case in a two-dimensional synthetic heterogeneous aquifer and a field-scale bioremediation experiment conducted at Oak Ridge, Tennessee. The field application indicates that ethanol degradation for U(VI)-bioremediation is better approximated by zero-order reaction kinetics than first-order reaction kinetics.

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

International Nuclear Information System (INIS)

Alves, Giselle M; Kremer, Gilberto M; Marques, Wilson Jr; Soares, Ana Jacinta

2011-01-01

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman–Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal–diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode

A kinetic model for chemical reactions without barriers: transport coefficients and eigenmodes

Science.gov (United States)

Alves, Giselle M.; Kremer, Gilberto M.; Marques, Wilson, Jr.; Jacinta Soares, Ana

2011-03-01

The kinetic model of the Boltzmann equation proposed in the work of Kremer and Soares 2009 for a binary mixture undergoing chemical reactions of symmetric type which occur without activation energy is revisited here, with the aim of investigating in detail the transport properties of the reactive mixture and the influence of the reaction process on the transport coefficients. Accordingly, the non-equilibrium solutions of the Boltzmann equations are determined through an expansion in Sonine polynomials up to the first order, using the Chapman-Enskog method, in a chemical regime for which the reaction process is close to its final equilibrium state. The non-equilibrium deviations are explicitly calculated for what concerns the thermal-diffusion ratio and coefficients of shear viscosity, diffusion and thermal conductivity. The theoretical and formal analysis developed in the present paper is complemented with some numerical simulations performed for different concentrations of reactants and products of the reaction as well as for both exothermic and endothermic chemical processes. The results reveal that chemical reactions without energy barrier can induce an appreciable influence on the transport properties of the mixture. Oppositely to the case of reactions with activation energy, the coefficients of shear viscosity and thermal conductivity become larger than those of an inert mixture when the reactions are exothermic. An application of the non-barrier model and its detailed transport picture are included in this paper, in order to investigate the dynamics of the local perturbations on the constituent number densities, and velocity and temperature of the whole mixture, induced by spontaneous internal fluctuations. It is shown that for the longitudinal disturbances there exist two hydrodynamic sound modes, one purely diffusive hydrodynamic mode and one kinetic mode.

Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

International Nuclear Information System (INIS)

Janev, R.K.; Kato, T.; Wang, J.G.

2001-05-01

The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C x H y charge exchange reactions from thermal energies up to several hundreds keV for all C x H y molecules with x=1, 2, 3 and 1 ≤ y ≤ 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

A numerical evaluation of prediction accuracy of CO2 absorber model for various reaction rate coefficients

Directory of Open Access Journals (Sweden)

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].

Cross sections and rate coefficients for charge exchange reactions of protons with hydrocarbon molecules

Energy Technology Data Exchange (ETDEWEB)

Janev, R.K.; Kato, T. [National Inst. for Fusion Science, Toki, Gifu (Japan); Wang, J.G. [Department of Physics and Astronomy, University of Georgia, Athens (United States)

2001-05-01

The available experimental and theoretical cross section data on charge exchange processes in collisions of protons with hydrocarbon molecules have been collected and critically assessed. Using well established scaling relationships for the charge exchange cross sections at low and high collision energies, as well as the known rate coefficients for these reactions in the thermal energy region, a complete cross section database is constructed for proton-C{sub x}H{sub y} charge exchange reactions from thermal energies up to several hundreds keV for all C{sub x}H{sub y} molecules with x=1, 2, 3 and 1 {<=} y {<=} 2x + 2. Rate coefficients for these charge exchange reactions have also been calculated in the temperature range from 0.1 eV to 20 keV. (author)

Rate Coefficients for the OH + (CHO)2 (Glyoxal) Reaction Between 240 and 400 K

Science.gov (United States)

Feierabend, K. J.; Talukdar, R. K.; Zhu, L.; Ravishankara, A. R.; Burkholder, J. B.

2006-12-01

Glyoxal (CHO)2, the simplest dialdehyde, is an end product formed in the atmospheric oxidation of biogenic hydrocarbons, for example, isoprene. As such, glyoxal plays a role in regional air quality and ozone production in certain locations. Glyoxal is lost in the atmosphere via UV photolysis and reaction with OH. However, the currently available rate coefficient data for the OH + glyoxal reaction is limited to a single room- temperature measurement made using the relative rate method. A determination of the rate coefficient temperature dependence is therefore needed for a more complete interpretation of the atmospheric processing of glyoxal. This study reports the rate coefficient for the OH + (CHO)2 reaction measured under pseudo- first-order conditions in OH ([(CHO)2] > 1000 [OH]0). OH radicals were produced using 248 nm pulsed laser photolysis of H2O2 or HNO3 and detected by pulsed laser induced fluorescence. The concentration of glyoxal in the reactor was determined using three independent techniques; gas flow rates as well as in situ UV and IR absorption. The total pressure in the reactor was varied from 40 to 300 Torr (He), and the rate coefficient was found to be independent of pressure over the temperature range studied. The rate coefficient exhibits a negative temperature dependence between 240 and 400 K consistent with the dependence previously observed for many other aldehydes. Our room-temperature rate coefficient is smaller than the relative rate value that is currently recommended for use in atmospheric model calculations. Our measured rate coefficients are discussed with respect to those for other aldehydes. The atmospheric implications of our work will also be discussed.

Rate Coefficient Measurements and Theoretical Analysis of the OH + ( E) CF3CH=CHCF3 Reaction.

Science.gov (United States)

Baasandorj, Munkhbayar; Marshall, Paul; Waterland, Robert L; Ravishankara, Akkihebbal R; Burkholder, James B

2018-04-25

Rate coefficients, k, for the gas-phase reaction of the OH radical with (E) CF3CH=CHCF3 ((E)-1,1,14,4,4-hexafluoro-2-butene, HFO-1336mzz(E)) were measured over a range of temperature (211-374 K) and bath gas pressure (20-300 Torr; He, N2) using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique. k1(T) was independent of pressure over this range of conditions with k1(296 K) = (1.31 ± 0.15) × 10 13 cm3 molecule 1 s 1 and k1(T) = (6.94 ± 0.80) × 10 13 exp[ (496 ± 10)/T] cm3 molecule 1 s 1, where the uncertainties are 2 and the pre-exponential term includes estimated systematic error. Rate coefficients for the OD reaction were also determined over a range of temperature (262-374 K) at 100 Torr (He). The OD rate coefficients were ~15% greater than the OH values and showed similar temperature dependent behavior with k2(T) = (7.52 ± 0.44) × 10 13 exp[ (476 ± 20)/T] and k2(296 K) = (1.53 ± 0.15) × 10 13 cm3 molecule 1 s 1. The rate coefficients for reaction 1 were also measured using a relative rate technique between 296 and 375 K with k1(296 K) measured to be (1.22 ± 0.1) × 10 13 cm3 molecule 1 s 1 in agreement with the PLP-LIF results. In addition, the 296 K rate coefficient for the O3 + (E) CF3CH=CHCF3 reaction was determined to be reaction and the significant decrease in OH reactivity compared to the (Z) CF3CH=CHCF3 stereoisomer reaction. The estimated atmospheric lifetime of (E) CF3CH=CHCF3, due to loss by reaction with OH, is estimated to be ~90 days, while the actual lifetime will depend on the location and season of its emission. Infrared absorption spectra of (E) CF3CH=CHCF3 were measured and used to estimate the 100-year time horizon global warming potentials (GWP) of 32 (atmospherically well-mixed) and 14 (lifetime-adjusted).

Calculation of rate coefficients of some proton-transfer ion-molecule reactions in weakly ionized gases

International Nuclear Information System (INIS)

Stiller, W.

1985-01-01

A classical collision theory is used to describe thermal bimolecular rate coefficeints for reaction between positive and negative ions and polar molecules in a carrier gas. Special attention is paid to ion-molecule reaction in which proton transfer occurs. These reactions play an important role in terrestrial plasma devices, in ionosphere, in planetary atmospheres and in interstellar matter. The equilibrium rate coefficients of the reactions are calculated based on a microscopic reactive cross section derived from a long distance polar molecule-ion potential. The results are compared with experimental values of afterglow measurements. (D.Gy.)

Experimental Study on the Utilization of Fine Steel Slag on Stabilizing High Plastic Subgrade Soil

Directory of Open Access Journals (Sweden)

Hussien Aldeeky

2017-01-01

Full Text Available The three major steel manufacturing factories in Jordan dump their byproduct, steel slag, randomly in open areas, which causes many environmental hazardous problems. This study intended to explore the effectiveness of using fine steel slag aggregate (FSSA in improving the geotechnical properties of high plastic subgrade soil. First soil and fine steel slag mechanical and engineering properties were evaluating. Then 0%, 5%, 10%, 15%, 20%, and 25% dry weight of soil of fine steel slag (FSSA were added and mixed into the prepared soil samples. The effectiveness of the FSSA was judged by the improvement in consistency limits, compaction, free swell, unconfined compression strength, and California bearing ratio (CBR. From the test results, it is observed that 20% FSSA additives will reduce plasticity index and free swell by 26.3% and 58.3%, respectively. Furthermore, 20% FSSA additives will increase the unconfined compressive strength, maximum dry density, and CBR value by 100%, 6.9%, and 154%. By conclusion FSSA had a positive effect on the geotechnical properties of the soil and it can be used as admixture in proving geotechnical characteristics of subgrade soil, not only solving the waste disposal problem.

AN APPROACH TO CHARACTERIZING and EVALUATING ALTERNATIVES FOR THE DECOMMISSIONING OF SUB-GRADE STRUCTURES AT THE PLUTONIUM FINISHING PLANT

International Nuclear Information System (INIS)

HOPKINS, A.M.; KLOS, D.B.

2007-01-01

In 2002, the Richland Operations Office (RL) of the US Department of Energy (DOE), the US Environmental Protection Agency (EPA), and the Washington State Department of Ecology (Ecology) developed milestones for transitioning the Plutonium Finishing Plant (PFP) facility to a clean slab-on-grade configuration. These milestones required developing an engineering evaluation/cost analysis (EF/CA) for the facility's sub-grade structures and installations as part of a series of evaluations intended to provide for the transition of the facility to a clean slab-on-grade configuration. In addition to supporting decisions for interim actions, the analyses of sub-grade structures and installations performed through this EE/CA will contribute to the remedial investigation feasibility study(ies) and subsequently to the final records of decision for the relevant operable units responsible for site closure in the 200 West Area of the Hanford Site

Effect of moisture content and dry unit weight on the resilient modulus of subgrade soils predicted by cone penetration test.

Science.gov (United States)

2002-06-01

The objective of this study was to investigate the effect of moisture content and dry unit weight on the resilient characteristics of subgrade soil predicted by the cone penetration test. An experimental program was conducted in which cone penetratio...

Rate coefficients for the reaction of OH radicals with cis-3-hexene: an experimental and theoretical study.

Science.gov (United States)

Barbosa, Thaís da Silva; Peirone, Silvina; Barrera, Javier A; Abrate, Juan P A; Lane, Silvia I; Arbilla, Graciela; Bauerfeldt, Glauco Favilla

2015-04-14

The kinetics of the cis-3-hexene + OH reaction were investigated by an experimental relative rate method and at the density functional theory level. The experimental set-up consisted of a 200 L Teflon bag, operated at atmospheric pressure and 298 K. OH radicals were produced by the photolysis of H2O2 at 254 nm. Relative rate coefficients were determined by comparing the decays of the cis-3-hexene and reference compounds (cyclohexene, 2-buten-1-ol and allyl ether). The mean second-order rate coefficient value found was (6.27 ± 0.66) × 10(-11) cm(3) molecule(-1) s(-1), the uncertainty being estimated by propagation of errors. Theoretical calculations for the addition reaction of OH to cis-3-hexene have also been performed, at the BHandHLYP/aug-cc-pVDZ level, in order to investigate the reaction mechanism, to clarify the experimental observations and to model the reaction kinetics. Different conformations of the reactants, pre-barrier complexes and saddle points were considered in our calculations. The individual rate coefficients, calculated for each conformer of the reactant, at 298 K, using a microcanonical variational transition state method, are 4.19 × 10(-11) and 1.23 × 10(-10) cm(3) molecule(-1) s(-1). The global rate coefficient was estimated from the Boltzmann distribution of the conformers to be 8.10 × 10(-11) cm(3) molecule(-1) s(-1), which is in agreement with the experimental value. Rate coefficients calculated over the temperature range from 200-500 K are also given. Our results suggest that the complex mechanism, explicitly considering different conformations for the stationary points, must be taken into account for a proper description of the reaction kinetics.

Evaluation of the base/subgrade soil under repeated loading : phase II, in-box and ALF cyclic plate load tests.

Science.gov (United States)

2012-03-01

This research study aims at evaluating the performance of base and subgrade soil in flexible pavements under repeated loading test conditions. For this purpose, an indoor cyclic plate load testing equipment was developed and used to conduct a series ...

Molar extinction coefficients and other properties of an improved reaction center preparation from Rhodopseudomonas viridis

Energy Technology Data Exchange (ETDEWEB)

Clayton, R.K.; Clayton, B.J.

1978-01-01

Reaction centers have been purified from chromatophores of Rhodopseudomonas viridis by treatment with lauryl dimethyl amine oxide followed by hydroxyapatite chromatography and precipitation with ammonium sulfate. The absorption spectrum at low temperature shows bands at 531 and 543 nm, assigned to two molecules of bacteriopheophytin b. The 600 nm band of bacteriochlorophyll b is resolved at low temperature into components at 601 and 606.5 nm. At room temperature the light-induced difference spectrum shows a negative band centered at 615 nm, where the absorption spectrum shows only a week shoulder adjacent to the 600 nm band. The fluorescence spectrum shows a band at 1000 nm and no fluorescence corresponding to the 830 nm absorption band. Two molecules of cytochrome 558 and three of cytochrome 552 accompany each reaction center. The differential extinction coefficient (reduced minus oxidized) of cytochrome 558 nm was estimated as 20 +- 2 mM/sup -1/.cm/sup -1/ through a coupled reaction with equine cytochrome c. The extinction coefficient of reaction centers at 960 nm was determined to be 123 +- 25 mM/sup -1/.cm/sup -1/ by measuring the light-induced bleaching of P-960 and the coupled oxidation of cytochrome 558. The corresponding extinction coefficient at 830 nm is 300 +- 65 mM/sup -1/.cm/sup -1/. The absorbance ratio ..cap alpha../sub 280nm/..cap alpha../sub 830nm/ in our preparations was 2.1, and there was 190 kg protein per mol of reaction centers. Sodium dodecyl sulfate-polyacrylamide gel electrophoresis showed three major components of apparent molecular weights 31,000, 37,000, and 41,000.

Characterization of cementitiously stabilized subgrades for mechanistic-empirical pavement design

Science.gov (United States)

Solanki, Pranshoo

Pavements are vulnerable to subgrade layer performance because it acts as a foundation. Due to increase in the truck traffic, pavement engineers are challenged to build more strong and long-lasting pavements. To increase the load-bearing capacity of pavements, subgrade layer is often stabilized with cementitious additives. Thus, an overall characterization of stabilized subgrade layer is important for enhanced short- and long-term pavement performance. In this study, the effect of type and amount of additive on the short-term performance in terms of material properties recommended by the new Mechanistic-Empirical Pavement Design Guide (MEPDG) is examined. A total of four soils commonly encountered as subgrades in Oklahoma are utilized. Results show that the changes in the Mr, ME and UCS values stabilized specimens depend on the soil type and properties of additives. The long-term performance (or durability) of stabilized soil specimens is investigated by conducting freeze-thaw (F-T) cycling, vacuum saturation and tube suction tests on 7-day cured P-, K- and C-soil specimens stabilized with 6% lime, 10% CFA and 10% CKD. This study is motivated by the fact that during the service life of pavement stabilized layers are subjected to F-T cycles and moisture variations. It is found that that UCS value of all the stabilized specimens decreased with increase in the number of F-T cycles. A strong correlation was observed between UCS values retained after vacuum saturation and F-T cycles indicating that vacuum saturation could be used as a time-efficient and inexpensive method for evaluating durability of stabilized soils. In this study, short- and long-term observations from stabilization of sulfate bearing soil with locally available low (CFA), moderate (CKD) and high (lime) calcium-based stabilizers are determined to evaluate and compare the effect of additive type on the phenomenon of sulfate-induced heave. The impact of different factors on the development of the

Computer investigations on the asymptotic behavior of the rate coefficient for the annihilation reaction A + A → product and the trapping reaction in three dimensions.

Science.gov (United States)

Litniewski, Marek; Gorecki, Jerzy

2011-06-28

We have performed intensive computer simulations of the irreversible annihilation reaction: A + A → C + C and of the trapping reaction: A + B → C + B for a variety of three-dimensional fluids composed of identical spherical particles. We have found a significant difference in the asymptotic behavior of the rate coefficients for these reactions. Both the rate coefficients converge to the same value with time t going to infinity but the convergence rate is different: the O(t(-1/2)) term for the annihilation reaction is higher than the corresponding term for the trapping reaction. The simulation results suggest that ratio of the terms is a universal quantity with the value equal to 2 or slightly above. A model for the annihilation reaction based on the superposition approximation predicts the difference in the O(t(-1/2)) terms, but overestimates the value for the annihilation reaction by about 30%. We have also performed simulations for the dimerization process: A + A → E, where E stands for a dimer. The dimerization decreases the reaction rate due to the decrease in the diffusion constant for A. The effect is successfully predicted by a simple model.

Gas-phase rate coefficients of the reaction of ozone with four sesquiterpenes at 295 ± 2 K.

Science.gov (United States)

Richters, Stefanie; Herrmann, Hartmut; Berndt, Torsten

2015-05-07

The rate coefficients of the reaction of ozone with the four atmospherically relevant sesquiterpenes β-caryophyllene, α-humulene, α-cedrene and isolongifolene were investigated at 295 ± 2 K and atmospheric pressure by at least two independent experimental investigations for each reaction. Relative rate experiments were carried out in a flow tube using two different experimental approaches with GC-MS detection (RR 1) and PTR-MS analysis (RR 2) as the analytical techniques. Absolute rate coefficients were determined in a stopped-flow experiment following the ozone depletion by means of UV spectroscopy. The average rate coefficients from the combined investigations representing the mean values of the different experimental methods are (unit: cm(3) molecule(-1) s(-1)): k(O3+β-caryophyllene) = (1.1 ± 0.3) × 10(-14) (methods: RR 1, RR 2, absolute), k(O3+α-humulene) = (1.2 ± 0.3) × 10(-14) (RR 1, RR 2), k(O3+α-cedrene) = (1.7 ± 0.5) × 10(-16) (RR 2, absolute) and k(O3+isolongifolene) = (1.1 ± 0.5) × 10(-17) (RR 2, absolute). The high ozonolysis rate coefficients for β-caryophyllene and α-humulene agree well with the results by Shu and Atkinson (Int. J. Chem. Kinet., 1994, 26) and lead to short atmospheric lifetimes of about two minutes with respect to the ozone reaction. The relatively small rate coefficients for α-cedrene and isolongifolene differ from the available literature values by a factor of about 2.5-6. Possible reasons for the deviations are discussed. Finally, calibrated sesquiterpene FT-IR spectra were recorded for the first time.

Experimental Study on the Utilization of Fine Steel Slag on Stabilizing High Plastic Subgrade Soil

OpenAIRE

Hussien Aldeeky; Omar Al Hattamleh

2017-01-01

The three major steel manufacturing factories in Jordan dump their byproduct, steel slag, randomly in open areas, which causes many environmental hazardous problems. This study intended to explore the effectiveness of using fine steel slag aggregate (FSSA) in improving the geotechnical properties of high plastic subgrade soil. First soil and fine steel slag mechanical and engineering properties were evaluating. Then 0%, 5%, 10%, 15%, 20%, and 25% dry weight of soil of fine steel slag (FSSA) w...

Rate coefficients for the reactions of ions with polar molecules at interstellar temperatures

International Nuclear Information System (INIS)

Adams, N.G.; Smith, D.; Clary, D.C.

1985-01-01

A theory has been developed recently which predicts that the rate coefficients, k, for the reactions of ions with polar molecules at low temperatures will be much greater than the canonical value of 10 -9 cm 3 s -1 . The new theory indicates that k is greatest for low-lying rotational sates and increases rapidly with decreasing temperature. We refer to recent laboratory measurements which validate the theory, present calculated values of k for the reactions of H + 3 ions with several polar molecules, and discuss their significance to interstellar chemistry. For the reactions of ions with molecules having large dipole moments, we recommend that k values as large as 10 -7 cm 3 s -1 should be used in ion-chemical models of low-temperature interstellar clouds

Atmospheric reactions of methylcyclohexanes with Cl atoms and OH radicals: determination of rate coefficients and degradation products.

Science.gov (United States)

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

Rate coefficients of exchange reactions accounting for vibrational excitation of reagents and products

Science.gov (United States)

Kustova, E. V.; Savelev, A. S.; Kunova, O. V.

2018-05-01

Theoretical models for the vibrational state-resolved Zeldovich reaction are assessed by comparison with the results of quasi-classical trajectory (QCT) calculations. An error in the model of Aliat is corrected; the model is generalized taking into account NO vibrational states. The proposed model is fairly simple and can be easily implemented to the software for non-equilibrium flow modeling. It provides a good agreement with the QCT rate coefficients in the whole range of temperatures and reagent/product vibrational states. The developed models are tested in simulations of vibrational and chemical relaxation of air mixture behind a shock wave. The importance of accounting for excitated NO vibrational states and accurate prediction of Zeldovich reactions rates is shown.

Nickel group cluster anion reactions with carbon monoxide: Rate coefficients and chemisorption efficiency

Science.gov (United States)

Hintz, Paul A.; Ervin, Kent M.

1994-04-01

Reactions of Ni-n(n=3-10), Pd-n(n=3-8), and Pt-n(n=3-7) with CO are studied in a flow tube reactor. Bimolecular rate coefficients are measured for the association reaction of CO adsorbing on the cluster surface. The rate coefficients range from about 10% of the collision rate for the trimer anions to near the collision rate for clusters larger than four atoms. The maximum number of CO molecules that bind to each cluster is determined. Whereas the saturation limits for nickel are typical for an 18 electron transition metal, the limits for platinum are lower, reflecting the electron deficient structures observed in condensed phase chemistry. The CO saturated palladium clusters represent the first examples of saturated binary palladium carbonyl compounds. Comparisons are made to similar studies on metal cation and neutral clusters and also to surface scattering studies of nickel group metals.

Evaluation of techniques for the improvement of subgrade soils in flood and rainfall inundation affected areas

International Nuclear Information System (INIS)

Khan, A.H.

2016-01-01

Highways are amongst the most costly resources contributing directly to the growth of any Country's economy. Subgrade soils as component of highways deteriorate normally from numerous factors resulting into flushing or excessive settlements of embankment involving huge maintenance costs. In this research, an attempt has been made to evaluate suitable technique for stabilization of commonly available subgrade soils of Pakistan based on cost effectiveness and ease in construction. The soils identified as A-3(0) by American Association of State Highway and Transportation Officials (AASHTO) criteria has been stabilized with conventional additives i.e. cement and bitumen in this research. The optimum content of each additive for stabilization based on their relative effectiveness was used. Trials were also made to economize the cost of stabilization from both conventional additives by controlled replacing of them with waste polythene and polyester fibers. The construction methodology for stabilization using waste fibers was also proposed. Cement was observed to be the most effective stabilizer with respect to strength and durability for A-3(0) soils. Bitumen was found effective but uneconomical for A-3(0) soils. Waste polythene and polyester wastes (organic materials) have potential to economize the cost of stabilization with cement and bitumen for A-3(0) soils. However, long term degradation of these organic materials in soil stabilized mixtures needs further exploration. (author)

Gas-Phase Reaction Pathways and Rate Coefficients for the Dichlorosilane-Hydrogen and Trichlorosilane-Hydrogen Systems

Science.gov (United States)

Dateo, Christopher E.; Walch, Stephen P.

2002-01-01

As part of NASA Ames Research Center's Integrated Process Team on Device/Process Modeling and Nanotechnology our goal is to create/contribute to a gas-phase chemical database for use in modeling microelectronics devices. In particular, we use ab initio methods to determine chemical reaction pathways and to evaluate reaction rate coefficients. Our initial studies concern reactions involved in the dichlorosilane-hydrogen (SiCl2H2--H2) and trichlorosilane-hydrogen (SiCl2H-H2) systems. Reactant, saddle point (transition state), and product geometries and their vibrational harmonic frequencies are determined using the complete-active-space self-consistent-field (CASSCF) electronic structure method with the correlation consistent polarized valence double-zeta basis set (cc-pVDZ). Reaction pathways are constructed by following the imaginary frequency mode of the saddle point to both the reactant and product. Accurate energetics are determined using the singles and doubles coupled-cluster method that includes a perturbational estimate of the effects of connected triple excitations (CCSD(T)) extrapolated to the complete basis set limit. Using the data from the electronic structure calculations, reaction rate coefficients are obtained using conventional and variational transition state and RRKM theories.

A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

Science.gov (United States)

Shaw, Jacob T.; Lidster, Richard T.; Cryer, Danny R.; Ramirez, Noelia; Whiting, Fiona C.; Boustead, Graham A.; Whalley, Lisa K.; Ingham, Trevor; Rickard, Andrew R.; Dunmore, Rachel E.; Heard, Dwayne E.; Lewis, Ally C.; Carpenter, Lucy J.; Hamilton, Jacqui F.; Dillon, Terry J.

2018-03-01

Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs) observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k = 5.7 (±0.3) × 10-11 cm3 molecule-1 s-1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10) K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T = 323 (±10) K.

A self-consistent, multivariate method for the determination of gas-phase rate coefficients, applied to reactions of atmospheric VOCs and the hydroxyl radical

Directory of Open Access Journals (Sweden)

J. T. Shaw

2018-03-01

Full Text Available Gas-phase rate coefficients are fundamental to understanding atmospheric chemistry, yet experimental data are not available for the oxidation reactions of many of the thousands of volatile organic compounds (VOCs observed in the troposphere. Here, a new experimental method is reported for the simultaneous study of reactions between multiple different VOCs and OH, the most important daytime atmospheric radical oxidant. This technique is based upon established relative rate concepts but has the advantage of a much higher throughput of target VOCs. By evaluating multiple VOCs in each experiment, and through measurement of the depletion in each VOC after reaction with OH, the OH + VOC reaction rate coefficients can be derived. Results from experiments conducted under controlled laboratory conditions were in good agreement with the available literature for the reaction of 19 VOCs, prepared in synthetic gas mixtures, with OH. This approach was used to determine a rate coefficient for the reaction of OH with 2,3-dimethylpent-1-ene for the first time; k =  5.7 (±0.3  ×  10−11 cm3 molecule−1 s−1. In addition, a further seven VOCs had only two, or fewer, individual OH rate coefficient measurements available in the literature. The results from this work were in good agreement with those measurements. A similar dataset, at an elevated temperature of 323 (±10 K, was used to determine new OH rate coefficients for 12 aromatic, 5 alkane, 5 alkene and 3 monoterpene VOC + OH reactions. In OH relative reactivity experiments that used ambient air at the University of York, a large number of different VOCs were observed, of which 23 were positively identified. Due to difficulties with detection limits and fully resolving peaks, only 19 OH rate coefficients were derived from these ambient air samples, including 10 reactions for which data were previously unavailable at the elevated reaction temperature of T =  323 (±10 K.

Pavement mechanic response of sulfate saline soil subgrade section based on fluid–structure interaction model

Directory of Open Access Journals (Sweden)

Xueying Zhao

2017-11-01

Full Text Available It is a consensus that salt heaving and frost heaving are urgent and typical distress in the sulfate saline soil area. To further investigate the microscopic performance of pavement structure in this special area, Jinan-Dongying Freeway in Shandong Province is selected as a case study engineering and the mechanic responses under salt heaving, frost heaving and traffic loads were analyzed through the finite element (FE Program (ANSYS. In this paper, the process of salt heaving and frost heaving was divided into 3 stages and FE models were established based on fluid–structure interaction (FSI model. It is shown that under both effects of salt heaving and frost heaving, the tensile stress of asphalt surface course could be up to 96.75% of its tensile strength, which means its tensile strength was seriously inadequate; however, traffic loads could help to dramatically counteract effects of salt heaving and frost heaving, which could decrease 40–80% of the tensile stress in asphalt surface course. It is also shown that in Jinan-Dongying Freeway effects of salt heaving had slightly larger effects on pavement compared with that of frost heaving, probably because salt heaving occurred from the top to the bottom of subgrade. However, as a whole, in sulfate saline soil area, compared with general area, crack resistance of asphalt courses and foundation treatment should always be strengthened. Keywords: Sulfate saline soil subgrade, Asphalt pavement, Pavement mechanic, FEM, FSI, Cracks and bulging

Atmospheric chemistry of (Z)-CF3CH═CHCF3: OH radical reaction rate coefficient and global warming potential.

Science.gov (United States)

Baasandorj, Munkhbayar; Ravishankara, A R; Burkholder, James B

2011-09-29

Rate coefficients, k, for the gas-phase reaction of the OH radical with (Z)-CF(3)CH═CHCF(3) (cis-1,1,1,4,4,4-hexafluoro-2-butene) were measured under pseudo-first-order conditions in OH using pulsed laser photolysis (PLP) to produce OH and laser-induced fluorescence (LIF) to detect it. Rate coefficients were measured over a range of temperatures (212-374 K) and bath gas pressures (20-200 Torr; He, N(2)) and found to be independent of pressure over this range of conditions. The rate coefficient has a non-Arrhenius behavior that is well-described by the expression k(1)(T) = (5.73 ± 0.60) × 10(-19) × T(2) × exp[(678 ± 10)/T] cm(3) molecule(-1) s(-1) where k(1)(296 K) was measured to be (4.91 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1) and the uncertainties are at the 2σ level and include estimated systematic errors. Rate coefficients for the analogous OD radical reaction were determined over a range of temperatures (262-374 K) at 100 Torr (He) to be k(2)(T) = (4.81 ± 0.20) × 10(-19) × T(2) × exp[(776 ± 15)/T], with k(2)(296 K) = (5.73 ± 0.50) × 10(-13) cm(3) molecule(-1) s(-1). OH radical rate coefficients were also measured at 296, 345, and 375 K using a relative rate technique and found to be in good agreement with the PLP-LIF results. A room-temperature rate coefficient for the O(3) + (Z)-CF(3)CH═CHCF(3) reaction was measured using an absolute method with O(3) in excess to be reaction was estimated to be ~20 days. Infrared absorption spectra of (Z)-CF(3)CH═CHCF(3) measured in this work were used to determine a (Z)-CF(3)CH═CHCF(3) global warming potential (GWP) of ~9 for the 100 year time horizon. A comparison of the OH reactivity of (Z)-CF(3)CH═CHCF(3) with other unsaturated fluorinated compounds is presented.

Diffusion-controlled reaction. V. Effect of concentration-dependent diffusion coefficient on reaction rate in graft polymerization

International Nuclear Information System (INIS)

Imre, K.; Odian, G.

1979-01-01

The effect of diffusion on radiation-initiated graft polymerization has been studied with emphasis on the single- and two-penetrant cases. When the physical properties of the penetrants are similar, the two-penetrant problems can be reduced to the single-penetrant problem by redefining the characteristic parameters of the system. The diffusion-free graft polymerization rate is assumed to be proportional to the upsilon power of the monomer concentration respectively, and, in which the proportionality constant a = k/sub p/R/sub i//sup w//k/sub t//sup z/, where k/sub p/ and k/sub t/ are the propagation and termination rate constants, respectively, and R/sub i/ is the initiation rate. The values of upsilon, w, and z depend on the particular reaction system. The results of earlier work were generalized by allowing a non-Fickian diffusion rate which predicts an essentially exponential dependence on the monomer concentration of the diffusion coefficient, D = D 0 [exp(deltaC/M)], where M is the saturation concentration. A reaction system is characterized by the three dimensionless parameters, upsilon, delta, and A = (L/2)[aM/sup (upsilon--1)//D 0 ]/sup 1/2/, where L is the polymer film thickness. Graft polymerization tends to become diffusion controlled as A increases. Larger values of delta and ν cause a reaction system to behave closer to the diffusion-free regime. Transition from diffusion-free to diffusion-controlled reaction involves changes in the dependence of the reaction rate on film thickness, initiation rate, and monomer concentration. Although the diffusion-free rate is w order in initiation rate, upsilon order in monomer, and independent of film thickness, the diffusion-controlled rate is w/2 order in initiator rate and inverse first-order in film thickness. Dependence of the diffusion-controlled rate on monomer is dependent in a complex manner on the diffusional characteristics of the reaction system. 11 figures, 4 tables

On determination of enthalpies of complex formation reactions by means of temperature coefficient of complexing degree

International Nuclear Information System (INIS)

Povar, I.G.

1995-01-01

Equations describing the relation between temperature coefficient of ∂lnα/∂T complexing degree and the sum of changes in the enthalpy of complex formation of the composition M m L n δH mn multiplied by the weight coefficients k mm , are presented. A method to determine changes in the enthalpy of certain ΔH mm reactions from ∂lnα/∂T derivatives has been suggested. The best approximating equation from lnα/(T) dependence has been found. Errors of thus determined δH mm values are estimated and the results of calculation experiment for the system In 3+ -F - are provided. 10 refs., 2 figs., 3 tabs

Effects of large rate coefficients for ion-polar neutral reactions on chemical models of dense interstellar clouds

International Nuclear Information System (INIS)

Herbst, E.; Leung, C.M.; Rensselaer Polytechnic Institute, Troy, NY)

1986-01-01

Pseudo-time-dependent models of the gas phase chemistry of dense interstellar clouds have been run with large rate coefficients for reactions between ions and polar neutral species, as advocated by Adams, Smith, and Clary. The higher rate coefficients normally lead to a reduction in both the peak and steady state abundances of polar neutrals, which can be as large as an order of magnitude but is more often smaller. Other differences between the results of these models and previous results are also discussed. 38 references

Investigation on Insar Time Series Deformation Model Considering Rheological Parameters for Soft Clay Subgrade Monitoring

Science.gov (United States)

Xing, X.; Yuan, Z.; Chen, L. F.; Yu, X. Y.; Xiao, L.

2018-04-01

The stability control is one of the major technical difficulties in the field of highway subgrade construction engineering. Building deformation model is a crucial step for InSAR time series deformation monitoring. Most of the InSAR deformation models for deformation monitoring are pure empirical mathematical models, without considering the physical mechanism of the monitored object. In this study, we take rheology into consideration, inducing rheological parameters into traditional InSAR deformation models. To assess the feasibility and accuracy for our new model, both simulation and real deformation data over Lungui highway (a typical highway built on soft clay subgrade in Guangdong province, China) are investigated with TerraSAR-X satellite imagery. In order to solve the unknows of the non-linear rheological model, three algorithms: Gauss-Newton (GN), Levenberg-Marquarat (LM), and Genetic Algorithm (GA), are utilized and compared to estimate the unknown parameters. Considering both the calculation efficiency and accuracy, GA is chosen as the final choice for the new model in our case study. Preliminary real data experiment is conducted with use of 17 TerraSAR-X Stripmap images (with a 3-m resolution). With the new deformation model and GA aforementioned, the unknown rheological parameters over all the high coherence points are obtained and the LOS deformation (the low-pass component) sequences are generated.

Laboratory Evaluation of the Effects of 3-Chloride Compounds on the Geotechnical Properties of an Expansive Subgrade Soil

Science.gov (United States)

Radhakrishnan, G.; Anjan Kumar, M.; Raju, G. V. R. Prasada

2017-12-01

Expansive soils are known to be problematic due to their nature and behavior. These soils show volume changes due to changes in moisture content, which cause distortions to structures constructed on them. Relentless efforts are being made all over the world to find solution to the problems of expansive soils. In the case of flexible pavements, unless the subgrade is appropriately treated during the construction stage, the maintenance cost will increase substantially due to deterioration. There are many methods of stabilising expansive subgrade soils. Chemical stabilisation is one such technique employed in improving the engineering properties of the expansive soil. Investigations on chemical stabilization of expansive soils revealed that conventionally used lime could be replaced by the chloride compound chemicals because of their ready dissolvability in water, ease of mixing with soil and supply of sufficient cations for ready cation exchange. The main objective of this work is to study the effectiveness of three chloride compound chemicals, ammonium chloride (NH4Cl), magnesium chloride (MgCl2) and aluminum chloride (AlCl3) on the geotechnical properties of an expansive soil. The chemicals content up to 2% were added to the soil and its effect on the index limits, swell pressure, compaction characteristics as well as California bearing ratio are studied. It was observed that aluminum chloride chemical content has a significantly higher influence than the other two chemicals and it could be recognized as an effective chemical stabilizer.

A theoretical study of the mechanism of the atmospherically relevant reaction of chlorine atoms with methyl nitrate, and calculation of the reaction rate coefficients at temperatures relevant to the troposphere.

Science.gov (United States)

Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

2015-03-21

The reaction between atomic chlorine (Cl) and methyl nitrate (CH3ONO2) is significant in the atmosphere, as Cl is a key oxidant, especially in the marine boundary layer, and alkyl nitrates are important nitrogen-containing organic compounds, which are temporary reservoirs of the reactive nitrogen oxides NO, NO2 and NO3 (NOx). Four reaction channels HCl + CH2ONO2, CH3OCl + NO2, CH3Cl + NO3 and CH3O + ClNO2 were considered. The major channel is found to be the H abstraction channel, to give the products HCl + CH2ONO2. For all channels, geometry optimization and frequency calculations were carried out at the M06-2X/6-31+G** level, while relative electronic energies were improved to the UCCSD(T*)-F12/CBS level. The reaction barrier (ΔE(‡)0K) and reaction enthalpy (ΔH(RX)298K) of the H abstraction channel were computed to be 0.61 and -2.30 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS//M06-2X/6-31+G** level. Reaction barriers (ΔE(‡)0K) for the other channels are more positive and these pathways do not contribute to the overall reaction rate coefficient in the temperature range considered (200-400 K). Rate coefficients were calculated for the H-abstraction channel at various levels of variational transition state theory (VTST) including tunnelling. Recommended ICVT/SCT rate coefficients in the temperature range 200-400 K are presented for the first time for this reaction. The values obtained in the 200-300 K region are particularly important as they will be valuable for atmospheric modelling calculations involving reactions with methyl nitrate. The implications of the results to atmospheric chemistry are discussed. Also, the enthalpies of formation, ΔHf,298K, of CH3ONO2 and CH2ONO2 were computed to be -29.7 and 19.3 kcal mol(-1), respectively, at the UCCSD(T*)-F12/CBS level.

Ground reaction force analysed with correlation coefficient matrix in group of stroke patients.

Science.gov (United States)

Szczerbik, Ewa; Krawczyk, Maciej; Syczewska, Małgorzata

2014-01-01

Stroke is the third cause of death in contemporary society and causes many disorders. Clinical scales, ground reaction force (GRF) and objective gait analysis are used for assessment of patient's rehabilitation progress during treatment. The goal of this paper is to assess whether signal correlation coefficient matrix applied to GRF can be used for evaluation of the status of post-stroke patients. A group of patients underwent clinical assessment and instrumented gait analysis simultaneously three times. The difference between components of patient's GRF (vertical, fore/aft, med/lat) and normal ones (reference GRF of healthy subjects) was calculated as correlation coefficient. Patients were divided into two groups ("worse" and "better") based on the clinical functional scale tests done at the beginning of rehabilitation process. The results obtained by these two groups were compared using statistical analysis. An increase of median value of correlation coefficient is observed in all components of GRF, but only in non-paretic leg. Analysis of GRF signal can be helpful in assessment of post-stroke patients during rehabilitation. Improvement in stroke patients was observed in non-paretic leg of the "worse" group. GRF analysis should not be the only tool for objective validation of patient's improvement, but could be used as additional source of information.

Influence of Excessive Moisture in the Subgrade on the Durability and Load-Bearing Capacity of Road Pavements

Science.gov (United States)

Mieczkowski, P.; Budziński, B.

2018-05-01

When well performed, pavement renewal or alteration shall ensure the desired properties of the road during the assumed period of operation. Presence of water in the subgrade can be one of the main factors affecting the structural capacity of pavement and can result in cracking of the bituminous layers, even after a very short period of trafficking. Reconstruction of one of regional roads in Poland has been chosen to serve as an example of inappropriate approach to the problem of the presence of water in the road structure. The project included construction of new layers of pavement and increasing the design life of the whole pavement structure to 4.06 million ESAL of 100 kN (as per the Standard Catalogue of Typical Flexible and Semi-rigid Road Pavement Structures, issue of 1997). After a relatively short period of trafficking (3-5 years) localised alligator cracking appeared on the surface along with structural deformations. The pavement condition assessment including FWD tests was carried out to reveal excessive deflections (over 500 μm) which classify the road for renewal. The analysis of data showed that the main cause of distress was softening of the subgrade caused by an ingress of precipitation water under the pavement layers through the roadway and shoulder edges. The deficiencies of the performed reconstruction occurred both in the roadway (including small step-outs in the cement-treated layer) and partly in the shoulders where the existing soil was in places replaced with impervious material, with the existing (cohesive) material left in place on a major part of the overall length.

Rate coefficients of the CF3CHFCF3 + H → CF3CFCF3 + H2 reaction at different temperatures calculated by transition state theory with ab initio and DFT reaction paths.

Science.gov (United States)

Ng, Maggie; Mok, Daniel K W; Lee, Edmond P F; Dyke, John M

2013-03-15

The minimum energy path (MEP) of the reaction, CF(3)CHFCF(3) + H → transition state (TS) → CF(3)CFCF(3) + H(2), has been computed at different ab initio levels and with density functional theory (DFT) using different functionals. The computed B3LYP/6-31++G**, BH&HLYP/cc-pVDZ, BMK/6-31++G**, M05/6-31+G**, M05-2X/6-31+G**, UMP2/6-31++G**, PUMP2/6-31++G**//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVDZ//UMP2/6-31++G**, RCCSD(T)/aug-cc-pVTZ(spd,sp)//UMP2//6-31++G**, RCCSD(T)/CBS//M05/6-31+G**, and RCCSD(T)/CBS//UMP2/6-31++G** MEPs, and associated gradients and Hessians, were used in reaction rate coefficient calculations based on the transition state theory (TST). Reaction rate coefficients were computed between 300 and 1500 K at various levels of TST, which include conventional TST, canonical variational TST (CVT) and improved CVT (ICVT), and with different tunneling corrections, namely, Wigner, zero-curvature, and small-curvature (SCT). The computed rate coefficients obtained at different ab initio, DFT and TST levels are compared with experimental values available in the 1000-1200 K temperature range. Based on the rate coefficients computed at the ICVT/SCT level, the highest TST level used in this study, the BH&HLYP functional performs best among all the functionals used, while the RCCSD(T)/CBS//MP2/6-31++G** level is the best among all the ab initio levels used. Comparing computed reaction rate coefficients obtained at different levels of theory shows that, the computed barrier height has the strongest effect on the computed reaction rate coefficients as expected. Variational effects on the computed rate coefficients are found to be negligibly small. Although tunneling effects are relatively small at high temperatures (~1500 K), SCT corrections are significant at low temperatures (~300 K), and both barrier heights and the magnitudes of the imaginary frequencies affect SCT corrections. Copyright © 2012 Wiley Periodicals, Inc.

Effect of drains on the seepage of contaminants from subgrade tailings disposal areas

International Nuclear Information System (INIS)

Witten, A.J.; Pin, F.G.; Sharp, R.D.

1984-01-01

A numerical simulation study is performed to investigate the influence of ponded water and a bottom drain on the pathways for contaminant migration from a subgrade uranium mill tailings disposal pit. A numerical model is applied to a generic disposal pit constructed with a bottom clay liner and steep unlined sidewalls. The migration of a two-contaminant system is modeled assuming that neither contaminant decays and only one contaminant is retarded. Two dominant pathways are identified; one associated with lateral sidewall leakage and the other associated with transport through the bottom clay liner. It is found that the drain serves to reduce migration through the sidewall which, in turn, prevents the retarded contaminant from reaching the aquifer. The ponded water provides increased head which causes an accelerated vertical movement of moisture through the clay liner. 2 references, 8 figures

Guideline for Adopting the Local Reaction Assumption for Porous Absorbers in Terms of Random Incidence Absorption Coefficients

DEFF Research Database (Denmark)

Jeong, Cheol-Ho

2011-01-01

resistivity and the absorber thickness on the difference between the two surface reaction models are examined and discussed. For a porous absorber backed by a rigid surface, the assumption of local reaction always underestimates the random incidence absorption coefficient and the local reaction models give...... incidence acoustical characteristics of typical building elements made of porous materials assuming extended and local reaction. For each surface reaction, five well-established wave propagation models, the Delany-Bazley, Miki, Beranek, Allard-Champoux, and Biot model, are employed. Effects of the flow...... errors of less than 10% if the thickness exceeds 120 mm for a flow resistivity of 5000 Nm-4s. As the flow resistivity doubles, a decrease in the required thickness by 25 mm is observed to achieve the same amount of error. For an absorber backed by an air gap, the thickness ratio between the material...

The effect of drains on the seepage of contaminants from subgrade tailings disposal areas

International Nuclear Information System (INIS)

Witten, A.J.; Pin, F.G.; Sharp, R.D.

1984-01-01

A numerical simulation study is performed to investigate the influence of ponded water and a bottom drain on the pathways for contaminant migration from a subgrade uranium mill tailings disposal pit. A numerical model is applied to a generic disposal pit constructed with a bottom clay liner and steep unlined sidewalls. The migration of a two-contaminant system is modeled assuming that neither contaminant decays and only one contaminant is retarded. Two dominant pathways are indentified; one associated with lateral sidewall leakage and the other associated with transport through the bottom clay liner. It is found that the drain serves to reduce migration through the sidewall which, in turn, prevents the retarded contaminant from reaching the aquifer. The ponded water provides increased head which causes an accelarated vertical movement of moisture through the clay liner

Precisiones para el empleo del método del módulo de balasto en edificación

OpenAIRE

Freiré Tellado, M. J.

1999-01-01

It has only been recently that computers were available to analyze the combined of structure and foundation, introducing more accuracy in structural analysis. Obviously, this technique involves the soil modeling as necessary. The model of the coefficient of subgrade reaction has been often used for this task. At last, the accuracy of the model depends on the agreement between predictions and soil behavior. The appropriate use of Winkler theory and the suitable determination of k are esse...

Interacción del suelo, cimiento y estructura: el caso de las zapatas (1ª parte)

OpenAIRE

Freire Tellado, Manuel J.

2001-01-01

This paper proposes the improvement of the structural analysis models introducing both soil and foundation, in the model. Next the soil modelling is analyzed, using the model of the coefficient of subgrade reaction for this task. Its application to the matrix analysis is explained, too. At last, in the second part, the proposed model is aplicated to a number of plane frames belonging to various structural types with isolated foundations. The results derived from the variation of certain param...

Rate coefficients from quantum and quasi-classical cumulative reaction probabilities for the S(1D) + H2 reaction

Science.gov (United States)

Jambrina, P. G.; Lara, Manuel; Menéndez, M.; Launay, J.-M.; Aoiz, F. J.

2012-10-01

Cumulative reaction probabilities (CRPs) at various total angular momenta have been calculated for the barrierless reaction S(1D) + H2 → SH + H at total energies up to 1.2 eV using three different theoretical approaches: time-independent quantum mechanics (QM), quasiclassical trajectories (QCT), and statistical quasiclassical trajectories (SQCT). The calculations have been carried out on the widely used potential energy surface (PES) by Ho et al. [J. Chem. Phys. 116, 4124 (2002), 10.1063/1.1431280] as well as on the recent PES developed by Song et al. [J. Phys. Chem. A 113, 9213 (2009), 10.1021/jp903790h]. The results show that the differences between these two PES are relatively minor and mostly related to the different topologies of the well. In addition, the agreement between the three theoretical methodologies is good, even for the highest total angular momenta and energies. In particular, the good accordance between the CRPs obtained with dynamical methods (QM and QCT) and the statistical model (SQCT) indicates that the reaction can be considered statistical in the whole range of energies in contrast with the findings for other prototypical barrierless reactions. In addition, total CRPs and rate coefficients in the range of 20-1000 K have been calculated using the QCT and SQCT methods and have been found somewhat smaller than the experimental total removal rates of S(1D).

Determination of the thermal rate coefficient, products, and branching ratios for the reaction of O/+/ /D-2/ with N2

Science.gov (United States)

Torr, D. G.; Torr, M. R.

1980-01-01

Atmosphere Explorer-C satellite measurements are used to determine rate coefficients (RCs) for the following reactions: O(+)(D-2) + N2 yields N2(+) + O (reaction 1), O(+)(D-2) + N2 yields O(+)(S-4) + N2 (reaction 2), and O(+)(D-2) + N2 yields NO(+) + N (reaction 3). Results show the RC for reaction 1 to be 1 (plus 1 or minus 0.5) x 10 to the -10th cu cm per sec, for reaction 2 to be 3 (plus 1 or minus 2) x 10 to the -11th cu cm per sec, and 3 to be less than 5.5 x 10 to the -11th cu cm per sec. It is also found that the reaction of O(+)(D-2) with N2 does not constitute a detectable source of NO(+) ions in the thermosphere.

Determination of the Rate Coefficients of the SO2 plus O plus M yields SO3 plus M Reaction

Science.gov (United States)

Hwang, S. M.; Cooke, J. A.; De Witt, K. J.; Rabinowitz, M. J.

2010-01-01

Rate coefficients of the title reaction R(sub 31) (SO2 +O+M yields SO3 +M) and R(sub 56) (SO2 + HO2 yields SO3 +OH), important in the conversion of S(IV) to S(VI),were obtained at T =970-1150 K and rho (sub ave) = 16.2 micro mol/cubic cm behind reflected shock waves by a perturbation method. Shock-heated H2/ O2/Ar mixtures were perturbed by adding small amounts of SO2 (1%, 2%, and 3%) and the OH temporal profiles were then measured using laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the characteristic reaction times acquired from the individual experimental absorption profiles via simultaneous optimization of k(sub 31) and k(sub 56) values in the reaction modeling (for satisfactory matches to the observed characteristic times, it was necessary to take into account R(sub 56)). In the experimental conditions of this study, R(sub 31) is in the low-pressure limit. The rate coefficient expressions fitted using the combined data of this study and the previous experimental results are k(sub 31,0)/[Ar] = 2.9 10(exp 35) T(exp ?6.0) exp(?4780 K/T ) + 6.1 10(exp 24) T(exp ?3.0) exp(?1980 K/T ) cm(sup 6) mol(exp ?2)/ s at T = 300-2500 K; k(sub 56) = 1.36 10(exp 11) exp(?3420 K/T ) cm(exp 3)/mol/s at T = 970-1150 K. Computer simulations of typical aircraft engine environments, using the reaction mechanism with the above k(sub 31,0) and k(sub 56) expressions, gave the maximum S(IV) to S(VI) conversion yield of ca. 3.5% and 2.5% for the constant density and constant pressure flow condition, respectively. Moreover, maximum conversions occur at rather higher temperatures (?1200 K) than that where the maximum k(sub 31,0) value is located (approximately 800 K). This is because the conversion yield is dependent upon not only the k(sup 31,0) and k(sup 56) values (production flux) but also the availability of H, O, and HO2 in the system (consumption flux).

Direct Determination of the Rate Coefficient for the Reaction of OH Radicals with Monoethanol Amine (MEA) from 296 to 510 K.

Science.gov (United States)

Onel, L; Blitz, M A; Seakins, P W

2012-04-05

Monoethanol amine (H2NCH2CH2OH, MEA) has been proposed for large-scale use in carbon capture and storage. We present the first absolute, temperature-dependent determination of the rate coefficient for the reaction of OH with MEA using laser flash photolysis for OH generation, monitoring OH removal by laser-induced fluorescence. The room-temperature rate coefficient is determined to be (7.61 ± 0.76) × 10(-11) cm(3) molecule(-1) s(-1), and the rate coefficient decreases by about 40% by 510 K. The temperature dependence of the rate coefficient is given by k1= (7.73 ± 0.24) × 10(-11)(T/295)(-(0.79±0.11)) cm(3) molecule(-1) s(-1). The high rate coefficient shows that gas-phase processing in the atmosphere will be competitive with uptake onto aerosols.

Determination of transport and reaction swarm coefficients from the analysis of complex transient pulses from the pulsed Townsend experiment

International Nuclear Information System (INIS)

Bekstein, A; De Urquijo, J; Rodríguez-Luna, J C; Juárez, A M; Ducasse, O

2012-01-01

We present in this paper the interpretation and analysis of transient pulses from a pulsed Townsend experiment by solving the continuity equations of the charged carriers (electrons and ions) involved in the avalanche. The set of second order partial differential equations is solved by SIMAV, a simulator designed specifically for the pulsed Townsend avalanche. Complex situations involving processes such as electron detachment, ion-molecule reactions, Penning ionization and secondary electron emission from ion impact at the cathode, virtually impossible to solve analytically, are discussed here to illustrate the capability of the simulator to help explain the various reaction processes involved in the avalanche, and also to derive some of the transport and reaction coefficients.

Reaction-rate coefficients, high-energy ions slowing-down, and power balance in a tokamak fusion reactor plasma

International Nuclear Information System (INIS)

Tone, Tatsuzo

1978-07-01

Described are the reactivity coefficient of D-T fusion reaction, slowing-down processes of deuterons injected with high energy and 3.52 MeV alpha particles generated in D-T reaction, and the power balance in a Tokamak reactor plasma. Most of the results were obtained in the first preliminary design of JAERI Experimental Fusion Reactor (JXFR) driven with stationary neutral beam injection. A manual of numerical computation program ''BALTOK'' developed for the calculations is given in the appendix. (auth.)

Numerical analysis and comparison of three types of herringbone frame structure for highway subgrade slopes protection

Science.gov (United States)

Nie, Yihua; Tang, Saiqian; Xu, Yang; Mao, Kunli

2018-04-01

In order to obtain mechanical response distribution of herringbone frame structure for highway subgrade slopes protection and select the best structure type, 3D numerical models of three types herringbone frame structure were established and analyzed in finite element software ANSYS. Indoor physical model of soil slope protected by herringbone frame structure was built and mechanical response of the frame structure was measured by loading tests. Numerical results indicate slope foot is the stress most disadvantageous location. Comparative analysis shows that structure composed of mortar rubble base layer and precast concrete blocks paving layer is the best one for resisting deformation and structure with cement mortar base layer and precast concrete blocks paving layer is the best one for being of low stress.

Resilient modulus for unbound granular materials and subgrade soils in Egypt

Directory of Open Access Journals (Sweden)

Mousa Rabah

2017-01-01

Full Text Available Mechanistic Empirical (ME pavement design methods started to gain attention especially the last couple of years in Egypt and the Middle East. One of the challenges facing the spread of these methods in Egypt is lack of advanced properties of local soil and asphalt, which are needed as input data in ME design. Resilient modulus (Mr for example is an important engineering property that expresses the elastic behavior of soil/unbound granular materials (UGMs under cyclic traffic loading for ME design. In order to overcome the scarcity of the resilient modulus data for soil/UGMs in Egypt, a comprehensive laboratory testing program was conducted to measure resilient modulus of typical UGMs and subgrade soils typically used in pavement construction in Egypt. The factors that affect the resilient modulus of soil/UGMs were reviewed, studied and discussed. Finally, the prediction accuracy of the most well-known Mr Prediction models for the locally investigated materials was investigated.

A paradox: The thermal rate coefficient for the H+DCl → HCl+D exchange reaction

International Nuclear Information System (INIS)

Thompson, D.L.; Suzukawa, H.H. Jr.; Raff, L.M.

1975-01-01

Previously reported photolysis experiments indicate that the frequency factors associated with the hydrogen-exchange reactions H+DCl → HCl+D and D+HCl → DCl+H are on the order of 10 10 cm 3 /molcenter-dotsec. A series of unadjusted, quasiclassical trajectory calculations were been carried out to compute the thermal rate coefficients and activation parameters for a series of 13 thermal processes of the type A+BC → AB+C, where A=H, D, or Cl and BC=H 2 , D 2 , HCl, DCl, or Cl 2 . In addition, hot-atom yield ratios have been computed from the IRP equation for the reactions D*+DCl → D 2 +Cl, D*+Cl 2 → DCl + Cl as a function of the initial D* laboratory energy. The computations yield (1) hot-atom DCl/D 2 yield ratios within a factor of 2 of the experimental values; (2) thermal activation energies in satisfactory agreement with experiment for all processes investigated; and (3) frequency factors in reasonable accord with experiment for all the reactions except the hydrogen exchange reactions

Stabilization treatment of soft subgrade soil by sewage sludge ash and cement.

Science.gov (United States)

Chen, Li; Lin, Deng-Fong

2009-02-15

In this study, incinerated sewage sludge ash (ISSA) is mixed with cement in a fixed ratio of 4:1 for use as a stabilizer to improve the strength of soft, cohesive, subgrade soil. Five different ratios (in wt%: 0%, 2%, 4%, 8%, and 16%) of ISSA/cement admixture are mixed with cohesive soil to make soil samples. In order to understand the influences of admixtures on the soil properties, tests of the pH value, Atterberg limits, compaction, California bearing ratio (CBR), unconfined compressive strength, and triaxial compression were performed on those samples. The study shows that the unconfined compressive strength of specimens with the ISSA/cement addition was improved to approximately 3-7 times better than that of the untreated soil; furthermore, the swelling behavior was also effectively reduced as much as 10-60% for those samples. In some samples, the ISSA/cement additive improved the CBR values by up to 30 times that of untreated soil. This suggests that ISSA/cement has many potential applications in the field of geotechnical engineering.

Upper limits to the reaction rate coefficients of C(n)(-) and C(n)H(-) (n = 2, 4, 6) with molecular hydrogen.

Science.gov (United States)

Endres, Eric S; Lakhmanskaya, Olga; Hauser, Daniel; Huber, Stefan E; Best, Thorsten; Kumar, Sunil S; Probst, Michael; Wester, Roland

2014-08-21

In the interstellar medium (ISM) ion–molecule reactions play a key role in forming complex molecules. Since 2006, after the radioastronomical discovery of the first of by now six interstellar anions, interest has grown in understanding the formation and destruction pathways of negative ions in the ISM. Experiments have focused on reactions and photodetachment of the identified negatively charged ions. Hints were found that the reactions of CnH(–) with H2 may proceed with a low (rate [Eichelberger, B.; et al. Astrophys. J. 2007, 667, 1283]. Because of the high abundance of molecular hydrogen in the ISM, a precise knowledge of the reaction rate is needed for a better understanding of the low-temperature chemistry in the ISM. A suitable tool to analyze rare reactions is the 22-pole radiofrequency ion trap. Here, we report on reaction rates for Cn(–) and CnH(–) (n = 2, 4, 6) with buffer gas temperatures of H2 at 12 and 300 K. Our experiments show the absence of these reactions with an upper limit to the rate coefficients between 4 × 10(–16) and 5 × 10(–15) cm(3) s(–1), except for the case of C2(–), which does react with a finite rate with H2 at low temperatures. For the cases of C2H(–) and C4H(–), the experimental results were confirmed with quantum chemical calculations. In addition, the possible influence of a residual reactivity on the abundance of C4H(–) and C6H(–) in the ISM were estimated on the basis of a gas-phase chemical model based on the KIDA database. We found that the simulated ion abundances are already unaffected if reaction rate coefficients with H2 were below 10(–14) cm(3) s(–1).

Expansive soil stabilization with coir waste and lime for flexible pavement subgrade

Science.gov (United States)

Narendra Goud, G.; Hyma, A.; Shiva Chandra, V.; Sandhya Rani, R.

2018-03-01

Expansive soil properties can be improved by various methods to make it suitable for construction of flexible pavement. The coir pith is the by-product (bio-waste) generated from coir industry during extraction of coir fiber from coconut husk. Openly disposed coir pith can make the surrounding areas unhygienic. This bio-waste can be one of the potential materials to stabilize the expansive soils. In the present study coir pith and lime are used as stabilizers. Different combinations of coir pith contents (1%, 2% and 3%) and lime contents (2%, 3% and 4%)are used to study the behavior of expansive soil. Unconfined compressive strength (UCS) of unstabilized and stabilized soils was determined. Optimum content of coir pith and lime are determined based on UCS of the soil. California bearing ratio of soil determined at optimum contents of coir pith and lime. Flexible pavement layer compositions for two levels of traffic using stabilized soil subgrade.

Design and performance of subgrade biogeochemical reactors.

Science.gov (United States)

Gamlin, Jeff; Downey, Doug; Shearer, Brad; Favara, Paul

2017-12-15

Subgrade biogeochemical reactors (SBGRs), also commonly referred to as in situ bioreactors, are a unique technology for treatment of contaminant source areas and groundwater plume hot spots. SBGRs have most commonly been configured for enhanced reductive dechlorination (ERD) applications for chlorinated solvent treatment. However, they have also been designed for other contaminant classes using alternative treatment media. The SBGR technology typically consists of removal of contaminated soil via excavation or large-diameter augers, and backfill of the soil void with gravel and treatment amendments tailored to the target contaminant(s). In most cases SBGRs include installation of infiltration piping and a low-flow pumping system (typically solar-powered) to recirculate contaminated groundwater through the SBGR for treatment. SBGRs have been constructed in multiple configurations, including designs capable of meeting limited access restrictions at heavily industrialized sites, and at sites with restrictions on surface disturbance due to sensitive species or habitat issues. Typical performance results for ERD applications include 85 to 90 percent total molar reduction of chlorinated volatile organic compounds (CVOCs) near the SBGR and rapid clean-up of adjacent dissolved contaminant source areas. Based on a review of the literature and CH2M's field-scale results from over a dozen SBGRs with a least one year of performance data, important site-specific design considerations include: 1) hydraulic residence time should be long enough for sufficient treatment but not too long to create depressed pH and stagnant conditions (e.g., typically between 10 and 60 days), 2) reactor material should balance appropriate organic mulch as optimal bacterial growth media along with other organic additives that provide bioavailable organic carbon, 3) a variety of native bacteria are important to the treatment process, and 4) biologically mediated generation of iron sulfides along with

Accurate Determination of Tunneling-Affected Rate Coefficients: Theory Assessing Experiment.

Science.gov (United States)

Zuo, Junxiang; Xie, Changjian; Guo, Hua; Xie, Daiqian

2017-07-20

The thermal rate coefficients of a prototypical bimolecular reaction are determined on an accurate ab initio potential energy surface (PES) using ring polymer molecular dynamics (RPMD). It is shown that quantum effects such as tunneling and zero-point energy (ZPE) are of critical importance for the HCl + OH reaction at low temperatures, while the heavier deuterium substitution renders tunneling less facile in the DCl + OH reaction. The calculated RPMD rate coefficients are in excellent agreement with experimental data for the HCl + OH reaction in the entire temperature range of 200-1000 K, confirming the accuracy of the PES. On the other hand, the RPMD rate coefficients for the DCl + OH reaction agree with some, but not all, experimental values. The self-consistency of the theoretical results thus allows a quality assessment of the experimental data.

Low temperature rate coefficients of the H + CH(+) → C(+) + H2 reaction: New potential energy surface and time-independent quantum scattering.

Science.gov (United States)

Werfelli, Ghofran; Halvick, Philippe; Honvault, Pascal; Kerkeni, Boutheïna; Stoecklin, Thierry

2015-09-21

The observed abundances of the methylidyne cation, CH(+), in diffuse molecular clouds can be two orders of magnitude higher than the prediction of the standard gas-phase models which, in turn, predict rather well the abundances of neutral CH. It is therefore necessary to investigate all the possible formation and destruction processes of CH(+) in the interstellar medium with the most abundant species H, H2, and e(-). In this work, we address the destruction process of CH(+) by hydrogen abstraction. We report a new calculation of the low temperature rate coefficients for the abstraction reaction, using accurate time-independent quantum scattering and a new high-level ab initio global potential energy surface including a realistic model of the long-range interaction between the reactants H and CH(+). The calculated thermal rate coefficient is in good agreement with the experimental data in the range 50 K-800 K. However, at lower temperatures, the experimental rate coefficient takes exceedingly small values which are not reproduced by the calculated rate coefficient. Instead, the latter rate coefficient is close to the one given by the Langevin capture model, as expected for a reaction involving an ion and a neutral species. Several recent theoretical works have reported a seemingly good agreement with the experiment below 50 K, but an analysis of these works show that they are based on potential energy surfaces with incorrect long-range behavior. The experimental results were explained by a loss of reactivity of the lowest rotational states of the reactant; however, the quantum scattering calculations show the opposite, namely, a reactivity enhancement with rotational excitation.

A numerical study of one-dimensional replicating patterns in reaction-diffusion systems with non-linear diffusion coefficients

International Nuclear Information System (INIS)

Ferreri, J. C.; Carmen, A. del

1998-01-01

A numerical study of the dynamics of pattern evolution in reaction-diffusion systems is performed, although limited to one spatial dimension. The diffusion coefficients are nonlinear, based on powers of the scalar variables. The system keeps the dynamics of previous studies in the literature, but the presence of nonlinear diffusion generates a field of strong nonlinear interactions due to the presence of receding travelling waves. This field is limited by the plane of symmetry of the space domain and the last born outgoing travelling wave. These effects are discussed. (author). 10 refs., 7 figs

Rate Coefficients of the Reaction of OH with Allene and Propyne at High Temperatures

KAUST Repository

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.

On the use temperature parameterized rate coefficients in the estimation of non-equilibrium reaction rates

Science.gov (United States)

Shizgal, Bernie D.; Chikhaoui, Aziz

2006-06-01

The present paper considers a detailed analysis of the nonequilibrium effects for a model reactive system with the Chapman-Eskog (CE) solution of the Boltzmann equation as well as an explicit time dependent solution. The elastic cross sections employed are a hard sphere cross section and the Maxwell molecule cross section. Reactive cross sections which model reactions with and without activation energy are used. A detailed comparison is carried out with these solutions of the Boltzmann equation and the approximation introduced by Cukrowski and coworkers [J. Chem. Phys. 97 (1992) 9086; Chem. Phys. 89 (1992) 159; Physica A 188 (1992) 344; Chem. Phys. Lett. A 297 (1998) 402; Physica A 275 (2000) 134; Chem. Phys. Lett. 341 (2001) 585; Acta Phys. Polonica B 334 (2003) 3607.] based on the temperature of the reactive particles. We show that the Cukrowski approximation has limited applicability for the large class of reactive systems studied in this paper. The explicit time dependent solutions of the Boltzmann equation demonstrate that the CE approach is valid only for very slow reactions for which the corrections to the equilibrium rate coefficient are very small.

Rate Coefficients for Reactions of Ethynyl Radical (C2H) With HCN and CH3CN: Implications for the Formation of Comples Nitriles on Titan

Science.gov (United States)

Hoobler, Ray J.; Leone, Stephen R.

1997-01-01

Rate coefficients for the reactions of C2H + HCN yields products and C2H + CH3CN yields products have been measured over the temperature range 262-360 K. These experiments represent an ongoing effort to accurately measure reaction rate coefficients of the ethynyl radical, C2H, relevant to planetary atmospheres such as those of Jupiter and Saturn and its satellite Titan. Laser photolysis of C2H2 is used to produce C2H, and transient infrared laser absorption is employed to measure the decay of C2H to obtain the subsequent reaction rates in a transverse flow cell. Rate constants for the reaction C2H + HCN yields products are found to increase significantly with increasing temperature and are measured to be (3.9-6.2) x 10(exp 13) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 297-360 K. The rate constants for the reaction C2H + CH3CN yields products are also found to increase substantially with increasing temperature and are measured to be (1.0-2.1) x 10(exp -12) cm(exp 3) molecules(exp -1) s(exp -1) over the temperature range of 262-360 K. For the reaction C2H + HCN yields products, ab initio calculations of transition state structures are used to infer that the major products form via an addition/elimination pathway. The measured rate constants for the reaction of C2H + HCN yields products are significantly smaller than values currently employed in photochemical models of Titan, which will affect the HC3N distribution.

Thermal rate coefficients in collinear versus bent transition state reactions: the N+N{sub 2} case study

Energy Technology Data Exchange (ETDEWEB)

Lagana, Antonio; Faginas Lago, Noelia; Rampino, Sergio [Dipartimento di Chimica, Universita di Perugia, 06123 Perugia (Italy); Huarte-Larranaga, FermIn [Computer Simulation and Modeling Lab (CoSMoLab), Parc CientIfic de Barcelona, 08028 Barcelona (Spain); GarcIa, Ernesto [Departamento de Quimica Fisica, Universidad del PaIs Vasco, 01006 Vitoria (Spain)], E-mail: lagana05@gmail.com, E-mail: fhuarte@pcb.ub.es, E-mail: e.garcia@ehu.es

2008-10-15

Zero total angular momentum exact quantum calculations of the probabilities of the N+N{sub 2} reaction have been performed on the L3 potential energy surface having a bent transition state. This has allowed us to work out J-shifting estimates of the thermal rate coefficient based on the calculation of either detailed (state-to-state) or cumulative (multiconfiguration) probabilities. The results obtained are used to compare the numerical outcomes and the concurrent computational machineries of both quantum and semiclassical approaches as well as to exploit the potentialities of the J-shifting model. The implications of moving the barrier to reaction from the previously proposed collinear geometry of the LEPS to the bent one of L3 are also investigated by comparing the related detailed reactive probabilities.

Thermal Rate Coefficients and Kinetic Isotope Effects for the Reaction OH + CH4 → H2O + CH3 on an ab Initio-Based Potential Energy Surface.

Science.gov (United States)

Li, Jun; Guo, Hua

2018-03-15

Thermal rate coefficients for the title reaction and its various isotopologues are computed using a tunneling-corrected transition-state theory on a global potential energy surface recently developed by fitting a large number of high-level ab initio points. The calculated rate coefficients are found to agree well with the measured ones in a wide temperature range, validating the accuracy of the potential energy surface. Strong non-Arrhenius effects are found at low temperatures. In addition, the calculations reproduced the primary and secondary kinetic isotope effects. These results confirm the strong influence of tunneling to this heavy-light-heavy hydrogen abstraction reaction.

Atmospheric chemistry of CF3CF═CH2 and (Z)-CF3CF═CHF: Cl and NO3 rate coefficients, Cl reaction product yields, and thermochemical calculations.

Science.gov (United States)

Papadimitriou, Vassileios C; Lazarou, Yannis G; Talukdar, Ranajit K; Burkholder, James B

2011-01-20

Rate coefficients, k, for the gas-phase reactions of Cl atoms and NO(3) radicals with 2,3,3,3-tetrafluoropropene, CF(3)CF═CH(2) (HFO-1234yf), and 1,2,3,3,3-pentafluoropropene, (Z)-CF(3)CF═CHF (HFO-1225ye), are reported. Cl-atom rate coefficients were measured in the fall-off region as a function of temperature (220-380 K) and pressure (50-630 Torr; N(2), O(2), and synthetic air) using a relative rate method. The measured rate coefficients are well represented by the fall-off parameters k(0)(T) = 6.5 × 10(-28) (T/300)(-6.9) cm(6) molecule(-2) s(-1) and k(∞)(T) = 7.7 × 10(-11) (T/300)(-0.65) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and k(0)(T) = 3 × 10(-27) (T/300)(-6.5) cm(6) molecule(-2) s(-1) and k(∞)(T) = 4.15 × 10(-11) (T/300)(-0.5) cm(3) molecule(-1) s(-1) for (Z)-CF(3)C═CHF with F(c) = 0.6. Reaction product yields were measured in the presence of O(2) to be (98 ± 7)% for CF(3)C(O)F and (61 ± 4)% for HC(O)Cl in the CF(3)CF═CH(2) reaction and (108 ± 8)% for CF(3)C(O)F and (112 ± 8)% for HC(O)F in the (Z)-CF(3)CF═CHF reaction, where the quoted uncertainties are 2σ (95% confidence level) and include estimated systematic errors. NO(3) reaction rate coefficients were determined using absolute and relative rate methods. Absolute measurements yielded upper limits for both reactions between 233 and 353 K, while the relative rate measurements yielded k(3)(295 K) = (2.6 ± 0.25) × 10(-17) cm(3) molecule(-1) s(-1) and k(4)(295 K) = (4.2 ± 0.5) × 10(-18) cm(3) molecule(-1) s(-1) for CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF, respectively. The Cl-atom reaction with CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF leads to decreases in their atmospheric lifetimes and global warming potentials and formation of a chlorine-containing product, HC(O)Cl, for CF(3)CF═CH(2). The NO(3) reaction has been shown to have a negligible impact on the atmospheric lifetimes of CF(3)CF═CH(2) and (Z)-CF(3)CF═CHF. The energetics for the reaction of Cl, NO(3), and OH with CF

Determination of S17(0) from transfer reactions

International Nuclear Information System (INIS)

Tribble, R.E.; Azhari, A.; Clark, H.L.; Gagliardi, C.A.; Lui, Y.; Mukhamedzhanov, A.M.; Sattarov, A.; Trache, L.; Burjan, V.; Cejpek, J.; Kroha, V.; Piskor, S.; Vincour, J.

1998-01-01

The S-factor for the direct capture reaction 7 Be(p,γ) 8 B can be found at astrophysical energies from the asymptotic normalization coefficients which provide the normalization of the tails of the overlap functions for 8 B→ 7 Be+p. Peripheral transfer reactions offer a technique to determine these asymptotic normalization coefficients. As a test of the technique, the 16 O( 3 He,d) 17 F reaction has been used to determine asymptotic normalization coefficients for transitions to the ground and first excited states of 17 F. The S-factors for 16 O(p,γ) 17 F calculated from these 17 F→ 16 O+p asymptotic normalization coefficients are found to be in very good agreement with recent measurements. Following the same technique, the 10 B( 7 Be, 8 B) 9 Be reaction has been used to measure the asymptotic normalization coefficient for 7 Be(p,γ) 8 B. This result provides an indirect determination of S 17 (0). copyright 1998 American Institute of Physics

Asymptotic normalization coefficients and astrophysical factors

International Nuclear Information System (INIS)

Mukhamedzhanov, A.M.; Azhari, A.; Clark, H.L.; Gagliardi, C.A.; Lui, Y.-W.; Sattarov, A.; Trache, L.; Tribble, R.E.; Burjan, V.; Kroha, V.; Carstoiu, F.

2000-01-01

The S factor for the direct capture reaction 7 Be(p,γ) 8 B can be found at astrophysical energies from the asymptotic normalization coefficients (ANC's) which provide the normalization of the tails of the overlap functions for 8 B → 7 Be + p. Peripheral transfer reactions offer a technique to determine these ANC's. Using this technique, the 10 B( 7 Be, 8 B) 9 Be and 14 N( 7 Be, 8 B) 13 C reactions have been used to measure the asymptotic normalization coefficient for 7 Be(p, γ) 8 B. These results provide an indirect determination of S 17 (0). Analysis of the existing 9 Be(p, γ) 10 B experimental data within the framework of the R-matrix method demonstrates that experimentally measured ANC's can provide a reasonable determination of direct radiative capture rates. (author)

New astrophysical S factor for the 15N(p,γ)16O reaction via the asymptotic normalization coefficient (ANC) method

International Nuclear Information System (INIS)

Mukhamedzhanov, A. M.; Gagliardi, C. A.; Goldberg, V. Z.; Plunkett, A.; Trache, L.; Tribble, R. E.; Bem, P.; Burjan, V.; Hons, Z.; Kroha, V.; Mrazek, J.; Novak, J.; Piskor, S.; Simeckova, E.; Vesely, F.; Vincour, J.; La Cognata, M.; Pizzone, R. G.; Romano, S.; Spitaleri, C.

2008-01-01

The 15 N(p,γ) 16 O reaction provides a path from the CN cycle to the CNO bi-cycle and CNO tri-cycle. The measured astrophysical factor for this reaction is dominated by resonant capture through two strong J π =1 - resonances at E R =312 and 962 keV and direct capture to the ground state. Asymptotic normalization coefficients (ANCs) for the ground and seven excited states in 16 O were extracted from the comparison of experimental differential cross sections for the 15 N( 3 He,d) 16 O reaction with distorted-wave Born approximation calculations. Using these ANCs and proton and α resonance widths determined from an R-matrix fit to the data from the 15 N(p,α) 12 C reaction, we carried out an R-matrix calculation to obtain the astrophysical factor for the 15 N(p,γ) 16 O reaction. The results indicate that the direct capture contribution was previously overestimated. We find the astrophysical factor to be S(0)=36.0±6.0 keV b, which is about a factor of 2 lower than the presently accepted value. We conclude that for every 2200±300 cycles of the main CN cycle one CN catalyst is lost due to this reaction

Proton-transfer reactions in ionized gases

International Nuclear Information System (INIS)

Stiller, W.; Schmidt, R.; Schuster, R.

1985-01-01

Ion-molecule reactions play an important role in various radiolytic processes, e.g. gas-pulse radiolysis, environmental research. For a discussion of mechanisms rate coefficients have to be assessed. Here gas-phase rate coefficients of ion-(polar) molecule reactions are calculated using the ideas of interaction potentials, reactive cross-sections and distribution functions of the translational energies of both the reactants (ions I, molecules M). The starting point of our approach, directed especially to gas-phase proton-transfer reactions, is the idea that the rate coefficient k can be calculated as an ion-molecule capture-rate coefficient multiplied by a 'steric factor' representing the probability for proton transfer. Mutual capture of the reaction partners within a possible reaction zone is caused by the physical interaction between an ion and a polar molecule. A model is discussed. Results are presented. (author)

Gas-phase rate coefficients for the OH + n-, i-, s-, and t-butanol reactions measured between 220 and 380 K: non-Arrhenius behavior and site-specific reactivity.

Science.gov (United States)

McGillen, Max R; Baasandorj, Munkhbayar; Burkholder, James B

2013-06-06

Butanol (C4H9OH) is a potential biofuel alternative in fossil fuel gasoline and diesel formulations. The usage of butanol would necessarily lead to direct emissions into the atmosphere; thus, an understanding of its atmospheric processing and environmental impact is desired. Reaction with the OH radical is expected to be the predominant atmospheric removal process for the four aliphatic isomers of butanol. In this work, rate coefficients, k, for the gas-phase reaction of the n-, i-, s-, and t-butanol isomers with the OH radical were measured under pseudo-first-order conditions in OH using pulsed laser photolysis to produce OH radicals and laser induced fluorescence to monitor its temporal profile. Rate coefficients were measured over the temperature range 221-381 K at total pressures between 50 and 200 Torr (He). The reactions exhibited non-Arrhenius behavior over this temperature range and no dependence on total pressure with k(296 K) values of (9.68 ± 0.75), (9.72 ± 0.72), (8.88 ± 0.69), and (1.04 ± 0.08) (in units of 10(-12) cm(3) molecule(-1) s(-1)) for n-, i-, s-, and t-butanol, respectively. The quoted uncertainties are at the 2σ level and include estimated systematic errors. The observed non-Arrhenius behavior is interpreted here to result from a competition between the available H-atom abstraction reactive sites, which have different activation energies and pre-exponential factors. The present results are compared with results from previous kinetic studies, structure-activity relationships (SARs), and theoretical calculations and the discrepancies are discussed. Results from this work were combined with available high temperature (1200-1800 K) rate coefficient data and room temperature reaction end-product yields, where available, to derive a self-consistent site-specific set of reaction rate coefficients of the form AT(n) exp(-E/RT) for use in atmospheric and combustion chemistry modeling.

ELECTRICAL RESISTIVITY AND SEEBECK COEFFICIENT IN Ca(LaMnO COMPOUNDS PREPARED BY SOLID STATE REACTION METHOD

Directory of Open Access Journals (Sweden)

Jorge I. Villa

2017-01-01

Full Text Available By using the solid state reaction method samples of  Ca1-xLaxMnO3 (0 ≤ x ≥ 0.15 were prepared. Their transport properties were studied by electrical resistivity rho(T and Seebeck coefficient S(T measurements as a function of temperature and lanthanum content, in the temperature range between 100 and 290K. The structural and morphological properties were studied by X-ray diffraction analysis (XRD and scanning electron microscopy (SEM, respectively. The Seebeck coefficient is negative throughout the studied temperature range indicating a conduction given by negative charge carriers, its magnitude decreases with the lanthanum content from |-261| mV/K to |-120| mV/K. The electrical resistivity shows a semiconducting behavior, it was interpreted in terms of small polaron hopping model. Thermoelectric properties of the obtained compounds were studied by the thermoelectric power factor PF, which reaches maximum values around 2mW/K2cm, these values become this kind of ceramics promising thermoelectric compound, to be used in technological applications.

Global Controllability of Chemical Reactions

OpenAIRE

Drexler, Dániel András; Tóth, János

2015-01-01

Controllability of chemical reactions is an important problem in chemical engineering science. In control theory, analysis of the controllability of linear systems is well-founded, however the dynamics of chemical reactions is usually nonlinear. Global controllability properties of chemical reactions are analyzed here based on the Lie-algebra of the vector fields associated to elementary reactions. A chemical reaction is controllable almost everywhere if all the reaction rate coefficients can...

Diffusion coefficients of tracers in glassy polymer systems prepared by gamma radiolysis

International Nuclear Information System (INIS)

Tonge, M.P.; Gilbert, R.G.

1996-01-01

Diffusion-controlled reactions are common in free radical polymerisation reactions, especially in glassy polymer matrices. Such reactions commonly have an important influence on the polymerisation process and final polymer properties. For example, the dominant growth-stopping event (bimolecular termination) is generally diffusion-controlled. In glassy polymer systems, where molecular mobility is very low, the chain growth mechanism (propagation) may become diffusion-controlled. At present, the mechanism for propagation in glassy polymers is poorly understood, but it is expected by the Smoluchowski expression applied to propagation to depend strongly on the diffusion coefficient of monomer. The objective of this study is to measure reliable diffusion coefficients of small tracer molecules in glassy polymers, and compare these with propagation rate coefficients in similar systems, by the prediction above. Samples were initially prepared in a sealed sampled cell containing monomer, inert diluent, and tracer dye. After irradiation for several days, complete conversion of monomer to polymer can be obtained. The diffusion coefficients for two tracer dyes have been measured as a function of weight fraction polymer glassy poly(methyl methacrylate) samples

Determination of the rate coefficients of the CH{sub 4} + O{sub 2} → HO{sub 2}+CH{sub 3} and HCO+O{sub 2} → HO{sub 2} + CO reactions at high temperatures

Energy Technology Data Exchange (ETDEWEB)

Ryu, Si Ok [School of Chemical Engineering, Yeungnam University, Gyeongsan (Korea, Republic of); Shin, Kuan Soo [Dept. of Chemistry, Soongsil University, Seoul (Korea, Republic of); Hwang, Soon Muk [Science Applications International Corp oration, 3000 Aerospace Park way, Brook Park, Ohio (United States)

2017-02-15

Rate coefficients of the title reactions, R1 (CH{sub 4} + O{sub 2} → HO{sub 2}+CH{sub 3}) and R{sub 2} (HCO+O{sub 2} → HO{sub 2} + CO) were obtained over T = 1610 ⁓ 1810 K and T = 200 ⁓ 1760 K, respectively, and at ρ = 7.1 μmol/cm{sup 3}. A lean CH{sub 4}/O{sub 2}/Ar mixture (0.1% CH{sub 4}, ϕ = 0.02) was heated behind reflected shock waves and the temporal OH absorption profiles were measured using a laser absorption spectroscopy. Reaction rate coefficients were elucidated by matching the experimental profiles via optimization of k1 and k2 values in the reaction simulation. The rate coefficient expressions derived are k{sub 1} = 1.46 × 10{sup 14} exp (−26 210 K/T) cm{sup 3}/mol/s, T = 1610 ⁓ 1810 K and k{sub 2} = 1.9 × 10{sup 12} T{sup 0.1{sup 6}} exp (−245 K/T) cm{sup 3}/mol/s, T = 200 ⁓ 1760 K.

Reactions of stabilized Criegee Intermediates

Science.gov (United States)

Vereecken, Luc; Harder, Hartwig; Novelli, Anna

2014-05-01

Carbonyl oxides (Criegee intermediates) were proposed as key intermediates in the gas phase ozonolysis of alkenes in 1975 by Rudolf Criegee. Despite the importance of ozonolysis in atmospheric chemistry, direct observation of these intermediates remained elusive, with only indirect experimental evidence for their role in the oxidation of hydrocarbons, e.g. through scavenging experiments. Direct experimental observation of stabilized CI has only been achieved since 2008. Since then, a concerted effort using experimental and theoretical means is in motion to characterize the chemistry and kinetics of these reactive intermediates. We present the results of theoretical investigations of the chemistry of Criegee intermediates with a series of coreactants which may be of importance in the atmosphere, in experimental setups, or both. This includes the CI+CI cross-reaction, which proceeds with a rate coefficient near the collision limit and can be important in experimental conditions. The CI + alkene reactions show strong dependence of the rate coefficient depending on the coreactants, but is generally found to be rather slow. The CI + ozone reaction is sufficiently fast to occur both in experiment and the free troposphere, and acts as a sink for CI. The reaction of CI with hydroperoxides, ROOH, is complex, and leads both to the formation of oligomers, as to the formation of reactive etheroxides, with a moderately fast rate coefficient. The importance of these reactions is placed in the context of the reaction conditions in different atmospheric environments ranging from unpolluted to highly polluted.

Development of a fiber optic pavement subgrade strain measurement system

Science.gov (United States)

Miller, Craig Emerson

2000-11-01

This dissertation describes the development of a fiber optic sensing system to measure strains within the soil subgrade of highway pavements resulting from traffic loads. The motivation to develop such a device include improvements to: (1)all phases of pavement design, (2)theoretical models used to predict pavement performance, and (3)pavement rehabilitation. The design of the sensing system encompasses selecting an appropriate transducer design as well as the development of optimal optical and demodulation systems. The first is spring based, which attempts to match its spring stiffness to that of the soil-data indicate it is not an optimal transducer design. The second transducer implements anchoring plates attached to two telescoping tubes which allows the soil to be compacted to a desired density between the plates to dictate the transducer's behavior. Both transducers include an extrinsic Fabry- Perot cavity to impose the soil strains onto a phase change of the optical signal propagating through the cavity. The optical system includes a low coherence source and allows phase modulation via path length stretching by adding a second interferometer in series with the transducer, resulting in a path matched differential interferometer. A digitally implemented synthetic heterodyne demodulator based on a four step phase stepping algorithm is used to obtain unambiguous soil strain information from the displacement of the Fabry-Perot cavity. The demodulator is calibrated and characterized by illuminating the transducer with a second long coherence source of different wavelength. The transducer using anchoring plates is embedded within cylindrical soil specimens of varying soil types and soil moisture contents. Loads are applied to the specimen and resulting strains are measured using the embedded fiber optic gage and LVDTs attached to the surface of the specimen. This experimental verification is substantiated using a finite element analysis to predict any differences

Absolute and relative-rate measurement of the rate coefficient for reaction of perfluoro ethyl vinyl ether (C2F5OCF[double bond, length as m-dash]CF2) with OH.

Science.gov (United States)

Srinivasulu, G; Bunkan, A J C; Amedro, D; Crowley, J N

2018-01-31

The rate coefficient (k 1 ) for the reaction of OH radicals with perfluoro ethyl vinyl ether (PEVE, C 2 F 5 OCF[double bond, length as m-dash]CF 2 ) has been measured as a function of temperature (T = 207-300 K) using the technique of pulsed laser photolysis with detection of OH by laser-induced fluorescence (PLP-LIF) at pressures of 50 or 100 Torr N 2 bath gas. In addition, the rate coefficient was measured at 298 K and in one atmosphere of air by the relative-rate technique with loss of PEVE and reference reactant monitored in situ by IR absorption spectroscopy. The rate coefficient has a negative temperature dependence which can be parameterized as: k 1 (T) = 6.0 × 10 -13  exp[(480 ± 38/T)] cm 3 molecule -1 s -1 and a room temperature value of k 1 (298 K) = (3.0 ± 0.3) × 10 -12 cm 3 molecule -1 s -1 . Highly accurate rate coefficients from the PLP-LIF experiments were achieved by optical on-line measurements of PEVE and by performing the measurements at two different apparatuses. The large rate coefficient and the temperature dependence indicate that the reaction proceeds via OH addition to the C[double bond, length as m-dash]C double bond, the high pressure limit already being reached at 50 Torr N 2 . Based on the rate coefficient and average OH levels, the atmospheric lifetime of PEVE was estimated to be a few days.

Determination of the diffusion coefficient of hydrogen ion in hydrogels.

Science.gov (United States)

Schuszter, Gábor; Gehér-Herczegh, Tünde; Szűcs, Árpád; Tóth, Ágota; Horváth, Dezső

2017-05-17

The role of diffusion in chemical pattern formation has been widely studied due to the great diversity of patterns emerging in reaction-diffusion systems, particularly in H + -autocatalytic reactions where hydrogels are applied to avoid convection. A custom-made conductometric cell is designed to measure the effective diffusion coefficient of a pair of strong electrolytes containing sodium ions or hydrogen ions with a common anion. This together with the individual diffusion coefficient for sodium ions, obtained from PFGSE-NMR spectroscopy, allows the determination of the diffusion coefficient of hydrogen ions in hydrogels. Numerical calculations are also performed to study the behavior of a diffusion-migration model describing ionic diffusion in our system. The method we present for one particular case may be extended for various hydrogels and diffusing ions (such as hydroxide) which are relevant e.g. for the development of pH-regulated self-healing mechanisms and hydrogels used for drug delivery.

A review of reaction rates in high temperature air

Science.gov (United States)

Park, Chul

1989-01-01

The existing experimental data on the rate coefficients for the chemical reactions in nonequilibrium high temperature air are reviewed and collated, and a selected set of such values is recommended for use in hypersonic flow calculations. For the reactions of neutral species, the recommended values are chosen from the experimental data that existed mostly prior to 1970, and are slightly different from those used previously. For the reactions involving ions, the recommended rate coefficients are newly chosen from the experimental data obtained more recently. The reacting environment is assumed to lack thermal equilibrium, and the rate coefficients are expressed as a function of the controlling temperature, incorporating the recent multitemperature reaction concept.

An innovative method for determining the diffusion coefficient of product nuclide

Energy Technology Data Exchange (ETDEWEB)

Chen, Chih Lung [Dept. of Nuclear Back-end Management, Taiwan Power Company, Taipei (China); Wang, Tsing Hai [Dept. Biomedical Engineering and Environment Sciences, National Tsing Hua University, Hsinchu (China)

2017-08-15

Diffusion is a crucial mechanism that regulates the migration of radioactive nuclides. In this study, an innovative numerical method was developed to simultaneously calculate the diffusion coefficient of both parent and, afterward, series daughter nuclides in a sequentially reactive through-diffusion model. Two constructed scenarios, a serial reaction (RN{sub 1} → RN{sub 2} → RN{sub 3}) and a parallel reaction (RN{sub 1} → RN{sub 2}A + RN{sub 2}B), were proposed and calculated for verification. First, the accuracy of the proposed three-member reaction equations was validated using several default numerical experiments. Second, by applying the validated numerical experimental concentration variation data, the as-determined diffusion coefficient of the product nuclide was observed to be identical to the default data. The results demonstrate the validity of the proposed method. The significance of the proposed numerical method will be particularly powerful in determining the diffusion coefficients of systems with extremely thin specimens, long periods of diffusion time, and parent nuclides with fast decay constants.

Asymptotic normalization coefficients from proton transfer reactions and astrophysical S factors for the CNO 13C(p,gamma)14N radiative capture prosess

Czech Academy of Sciences Publication Activity Database

Mukhamedzhanov, A. M.; Azhari, A.; Burjan, Václav; Gagliardi, C. A.; Kroha, Václav; Sattarov, A.; Tang, X.; Trache, L.; Tribble, R. E.

2003-01-01

Roč. 725, č. 725 (2003), s. 279-294 ISSN 0375-9474 R&D Projects: GA ČR GA202/01/0709; GA MŠk ME 385 Institutional research plan: CEZ:AV0Z1048901 Keywords : radiative capture reaction * asymptotic normalization coefficient Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.761, year: 2003

Asymptotic normalization coefficients from proton transfer reactions and astrophysical S factors for the (CNOC)-C-13(p, gamma)N-14 radiative capture process

Czech Academy of Sciences Publication Activity Database

Mukhamedzhanov, A. M.; Azhari, A.; Burjan, Václav; Gagliardi, C. A.; Kroha, Václav; Sattarov, A.; Tang, X.; Trache, L.; Tribble, R. E.

2003-01-01

Roč. 725, č. 22 (2003), s. 279-294 ISSN 0375-9474 R&D Projects: GA ČR GA202/01/0709; GA MŠk ME 385 Institutional research plan: CEZ:AV0Z1048901 Keywords : radiative capture reaction * asymptotic normalization coefficient Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 1.761, year: 2003

Global minimum profile error (GMPE) - a least-squares-based approach for extracting macroscopic rate coefficients for complex gas-phase chemical reactions.

Science.gov (United States)

Duong, Minh V; Nguyen, Hieu T; Mai, Tam V-T; Huynh, Lam K

2018-01-03

Master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) has shown to be a powerful framework for modeling kinetic and dynamic behaviors of a complex gas-phase chemical system on a complicated multiple-species and multiple-channel potential energy surface (PES) for a wide range of temperatures and pressures. Derived from the ME time-resolved species profiles, the macroscopic or phenomenological rate coefficients are essential for many reaction engineering applications including those in combustion and atmospheric chemistry. Therefore, in this study, a least-squares-based approach named Global Minimum Profile Error (GMPE) was proposed and implemented in the MultiSpecies-MultiChannel (MSMC) code (Int. J. Chem. Kinet., 2015, 47, 564) to extract macroscopic rate coefficients for such a complicated system. The capability and limitations of the new approach were discussed in several well-defined test cases.

Effect of chemical reaction on unsteady MHD free convective two ...

African Journals Online (AJOL)

The effect of flow parameters on the coefficient of skin friction, Nusselt number and Sherwood number are also tabulated and discussed appropriately. It was observed that the increase in chemical reaction coefficient/parameter suppresses both velocity and concentration profiles. Keywords: Chemical Reaction, MHD, ...

Determination of the reaction rate coefficient of sulphide mine tailings deposited under water.

Science.gov (United States)

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

Modified two-body potential approach to the peripheral direct capture astrophysical a+A->B+γ reaction and asymptotic normalization coefficients

International Nuclear Information System (INIS)

Igamov, S.B.; Yarmukhamedov, R.

2007-01-01

A modified two-body potential approach is proposed for determination of both the asymptotic normalization coefficient (ANC) (or the respective nuclear vertex constant (NVC)) for the A+a->B (for the virtual decay B->A+a) from an analysis of the experimental S-factor for the peripheral direct capture a+A->B+γ reaction and the astrophysical S-factor, S(E), at low experimentally inaccessible energy regions. The approach proposed involves two additional conditions which verify the peripheral character of the considered reaction and expresses S(E) in terms of the ANC. The connection between NVC (ANC) and the effective range parameters for Aa-scattering is derived. To test this approach we reanalyse the precise experimental astrophysical S-factors for t+α->Li7+γ reaction at energies E= Li7(g.s.), α+t->Li7(0.478 MeV) and of S(E) at E=<50 keV. These ANC values have been used for getting information about the ''indirect'' measured values of the effective range parameters and the p-wave phase shift for αt-scattering in the energy range of 100-bar E-bar 180 keV

Reaction Equilibrium of the ω-Transamination of (S)-Phenylethylamine

DEFF Research Database (Denmark)

Voges, Matthias; Abu, Rohana; Deslauriers, Maria Gundersen

2017-01-01

This work focuses on the thermodynamic equilibrium of the ω-transaminase-catalyzed reaction of (S)-phenylethylamine with cyclohexanone to acetophenone and cyclohexylamine in aqueous solution. For this purpose, the equilibrium concentrations of the reaction were experimentally investigated under...... varying reaction conditions. It was observed that the temperature (30 and 37 °C), the pH (between pH 7 and pH 9), as well as the initial reactant concentrations (between 5 and 50 mmol·kg-1) influenced the equilibrium position of the reaction. The position of the reaction equilibrium was moderately shifted...... position to the reactant side. In order to explain these effects, the activity coefficients of the reacting agents were calculated and the activity-based thermodynamic equilibrium constant Kth of the reaction was determined. For this purpose, the activity coefficients of the reacting agents were modeled...

Kinetic studies of elementary chemical reactions

Energy Technology Data Exchange (ETDEWEB)

Durant, J.L. Jr. [Sandia National Laboratories, Livermore, CA (United States)

1993-12-01

This program concerning kinetic studies of elementary chemical reactions is presently focussed on understanding reactions of NH{sub x} species. To reach this goal, the author is pursuing experimental studies of reaction rate coefficients and product branching fractions as well as using electronic structure calculations to calculate transition state properties and reaction rate calculations to relate these properties to predicted kinetic behavior. The synergy existing between the experimental and theoretical studies allow one to gain a deeper insight into more complex elementary reactions.

Transport Properties of a Kinetic Model for Chemical Reactions without Barriers

International Nuclear Information System (INIS)

Alves, Giselle M.; Kremer, Gilberto M.; Soares, Ana Jacinta

2011-01-01

A kinetic model of the Boltzmann equation for chemical reactions without energy barrier is considered here with the aim of evaluating the reaction rate and characterizing the transport coefficient of shear viscosity for the reactive system. The Chapman-Enskog solution of the Boltzmann equation is used to compute the chemical reaction effects, in a flow regime for which the reaction process is close to the final equilibrium state. Some numerical results are provided illustrating that the considered chemical reaction without energy barrier can induce an appreciable influence on the reaction rate and on the transport coefficient of shear viscosity.

Simple Closed-Form Expression for Penning Reaction Rate Coefficients for Cold Molecular Collisions by Non-Hermitian Time-Independent Adiabatic Scattering Theory.

Science.gov (United States)

Pawlak, Mariusz; Ben-Asher, Anael; Moiseyev, Nimrod

2018-01-09

We present a simple expression and its derivation for reaction rate coefficients for cold anisotropic collision experiments based on adiabatic variational theory and time-independent non-Hermitian scattering theory. We demonstrate that only the eigenenergies of the resulting one-dimensional Schrödinger equation for different complex adiabats are required. The expression is applied to calculate the Penning ionization rate coefficients of an excited metastable helium atom with molecular hydrogen in an energy range spanning from hundreds of kelvins down to the millikelvin regime. Except for trivial quantities like the masses of the nuclei and the bond length of the diatomic molecule participating in the collision, one needs as input data only the complex potential energy surface (CPES). In calculations, we used recently obtained ab initio CPES by D. Bhattacharya et al. ( J. Chem. Theory Comput. 2017 , 13 , 1682 - 1690 ) without fitting parameters. The results show good accord with current measurements ( Nat. Phys. 2017 , 13 , 35 - 38 ).

State-to-state quantum mechanical calculations of rate coefficients for the D+ + H2 → HD + H+ reaction at low temperature.

Science.gov (United States)

Honvault, P; Scribano, Y

2013-10-03

The dynamics of the D(+) + H2 → HD + H(+) reaction on a recent ab initio potential energy surface (Velilla, L.; Lepetit, B.; Aguado, A.; Beswick, J. A.; Paniagua, M. J. Chem. Phys. 2008, 129, 084307) has been investigated by means of a time-independent quantum mechanical approach. Cross-sections and rate coefficients are calculated, respectively, for collision energies below 0.1 eV and temperatures up to 100 K for astrophysical application. An excellent accord is found for collision energy above 5 meV, while a disagreement between theory and experiment is observed below this energy. We show that the rate coefficients reveal a slightly temperature-dependent behavior in the upper part of the temperature range considered here. This is in agreement with the experimental data above 80 K, which give a temperature independent value. However, a significant decrease is found at temperatures below 20 K. This decrease can be related to quantum effects and the decay back to the reactant channel, which are not considered by simple statistical approaches, such as the Langevin model. Our results have been fitted to appropriate analytical expressions in order to be used in astrochemical and cosmological models.

Numerical analysis for Darcy-Forchheimer flow in presence of homogeneous-heterogeneous reactions

Directory of Open Access Journals (Sweden)

Muhammad Ijaz Khan

Full Text Available A mathematical study is presented to investigate the influences of homogeneous and heterogeneous reactions in local similar flow caused by stretching sheet with a non-linear velocity and variable thickness. Porous medium effects are characterized by using Darcy-Forchheimer porous-media. A simple isothermal model of homogeneous-heterogeneous reactions is used. The multiphysical boundary value problem is dictated by ten thermophysical parameters: ratio of mass diffusion coefficients, Prandtl number, local inertia coefficient parameter, inverse Darcy number, shape parameter, surface thickness parameter, Hartman number, Homogeneous heat reaction, strength of homogeneous-heterogeneous reactions and Schmidt number. Resulting systems are computed by Runge-Kutta-Fehlberg method. Different shapes of velocity are noticed for n > 1 and n < 1. Keywords: Homogeneous-heterogeneous reactions, Non Darcy porous medium, Variable sheet thickness, Homogeneous heat reaction with stoichiometric coefficient, Runge-Kutta-Fehlberg method

CH3CO + O2 + M (M = He, N2) Reaction Rate Coefficient Measurements and Implications for the OH Radical Product Yield.

Science.gov (United States)

Papadimitriou, Vassileios C; Karafas, Emmanuel S; Gierczak, Tomasz; Burkholder, James B

2015-07-16

The gas-phase CH3CO + O2 reaction is known to proceed via a chemical activation mechanism leading to the formation of OH and CH3C(O)OO radicals via bimolecular and termolecular reactive channels, respectively. In this work, rate coefficients, k, for the CH3CO + O2 reaction were measured over a range of temperature (241-373 K) and pressure (0.009-600 Torr) with He and N2 as the bath gas and used to characterize the bi- and ter-molecular reaction channels. Three independent experimental methods (pulsed laser photolysis-laser-induced fluorescence (PLP-LIF), pulsed laser photolysis-cavity ring-down spectroscopy (PLP-CRDS), and a very low-pressure reactor (VLPR)) were used to characterize k(T,M). PLP-LIF was the primary method used to measure k(T,M) in the high-pressure regime under pseudo-first-order conditions. CH3CO was produced by PLP, and LIF was used to monitor the OH radical bimolecular channel reaction product. CRDS, a complementary high-pressure method, measured k(295 K,M) over the pressure range 25-600 Torr (He) by monitoring the temporal CH3CO radical absorption following its production via PLP in the presence of excess O2. The VLPR technique was used in a relative rate mode to measure k(296 K,M) in the low-pressure regime (9-32 mTorr) with CH3CO + Cl2 used as the reference reaction. A kinetic mechanism analysis of the combined kinetic data set yielded a zero pressure limit rate coefficient, kint(T), of (6.4 ± 4) × 10(-14) exp((820 ± 150)/T) cm(3) molecule(-1) s(-1) (with kint(296 K) measured to be (9.94 ± 1.3) × 10(-13) cm(3) molecule(-1) s(-1)), k0(T) = (7.39 ± 0.3) × 10(-30) (T/300)(-2.2±0.3) cm(6) molecule(-2) s(-1), and k∞(T) = (4.88 ± 0.05) × 10(-12) (T/300)(-0.85±0.07) cm(3) molecule(-1) s(-1) with Fc = 0.8 and M = N2. A He/N2 collision efficiency ratio of 0.60 ± 0.05 was determined. The phenomenological kinetic results were used to define the pressure and temperature dependence of the OH radical yield in the CH3CO + O2 reaction. The

Determination of the asymptotic normalization coefficients for C-14 + n - C-15,the C-14(n,gamma)C-15 reaction rate, and evaluation of a new method to determine spectroscopic factors

Czech Academy of Sciences Publication Activity Database

McCleskey, M.; Mukhamedzhanov, A. M.; Trache, L.; Tribble, R. E.; Banu, A.; Eremenko, V.; Goldberg, V. Z.; Lui, Y. W.; McCleskey, E.; Roeder, B. T.; Spiridon, A.; Carstoiu, F.; Burjan, Václav; Hons, Zdeněk; Thompson, I. J.

2014-01-01

Roč. 89, č. 4 (2014), 044605 ISSN 0556-2813 R&D Projects: GA MŠk(CZ) LH11001 Institutional support: RVO:61389005 Keywords : capture reactions * cross-section * asymptotic normalization coefficient Subject RIV: BG - Nuclear, Atomic and Molecular Physics, Colliders Impact factor: 3.733, year: 2014

Determination of absolute internal conversion coefficients using the SAGE spectrometer

Energy Technology Data Exchange (ETDEWEB)

Sorri, J., E-mail: juha.m.t.sorri@jyu.fi [University of Jyvaskyla, Department of Physics, P.O. Box 35, FI-40014 University of Jyvaskyla (Finland); Greenlees, P.T.; Papadakis, P.; Konki, J. [University of Jyvaskyla, Department of Physics, P.O. Box 35, FI-40014 University of Jyvaskyla (Finland); Cox, D.M. [University of Jyvaskyla, Department of Physics, P.O. Box 35, FI-40014 University of Jyvaskyla (Finland); Department of Physics, University of Liverpool, Oxford Street, Liverpool L69 7ZE (United Kingdom); Auranen, K.; Partanen, J.; Sandzelius, M.; Pakarinen, J.; Rahkila, P.; Uusitalo, J. [University of Jyvaskyla, Department of Physics, P.O. Box 35, FI-40014 University of Jyvaskyla (Finland); Herzberg, R.-D. [Department of Physics, University of Liverpool, Oxford Street, Liverpool L69 7ZE (United Kingdom); Smallcombe, J.; Davies, P.J.; Barton, C.J.; Jenkins, D.G. [Department of Physics, University of York, Heslington, York YO10 5DD (United Kingdom)

2016-03-11

A non-reference based method to determine internal conversion coefficients using the SAGE spectrometer is carried out for transitions in the nuclei of {sup 154}Sm, {sup 152}Sm and {sup 166}Yb. The Normalised-Peak-to-Gamma method is in general an efficient tool to extract internal conversion coefficients. However, in many cases the required well-known reference transitions are not available. The data analysis steps required to determine absolute internal conversion coefficients with the SAGE spectrometer are presented. In addition, several background suppression methods are introduced and an example of how ancillary detectors can be used to select specific reaction products is given. The results obtained for ground-state band E2 transitions show that the absolute internal conversion coefficients can be extracted using the methods described with a reasonable accuracy. In some cases of less intense transitions only an upper limit for the internal conversion coefficient could be given.

Determination of absolute internal conversion coefficients using the SAGE spectrometer

International Nuclear Information System (INIS)

Sorri, J.; Greenlees, P.T.; Papadakis, P.; Konki, J.; Cox, D.M.; Auranen, K.; Partanen, J.; Sandzelius, M.; Pakarinen, J.; Rahkila, P.; Uusitalo, J.; Herzberg, R.-D.; Smallcombe, J.; Davies, P.J.; Barton, C.J.; Jenkins, D.G.

2016-01-01

A non-reference based method to determine internal conversion coefficients using the SAGE spectrometer is carried out for transitions in the nuclei of "1"5"4Sm, "1"5"2Sm and "1"6"6Yb. The Normalised-Peak-to-Gamma method is in general an efficient tool to extract internal conversion coefficients. However, in many cases the required well-known reference transitions are not available. The data analysis steps required to determine absolute internal conversion coefficients with the SAGE spectrometer are presented. In addition, several background suppression methods are introduced and an example of how ancillary detectors can be used to select specific reaction products is given. The results obtained for ground-state band E2 transitions show that the absolute internal conversion coefficients can be extracted using the methods described with a reasonable accuracy. In some cases of less intense transitions only an upper limit for the internal conversion coefficient could be given.

Determination of the photolysis rate coefficient of monochlorodimethyl sulfide (MClDMS) in the atmosphere and its implications for the enhancement of SO2 production from the DMS + Cl2 reaction.

Science.gov (United States)

Copeland, G; Lee, E P F; Williams, R G; Archibald, A T; Shallcross, D E; Dyke, J M

2014-01-01

In this work, the photolysis rate coefficient of CH3SCH2Cl (MClDMS) in the lower atmosphere has been determined and has been used in a marine boundary layer (MBL) box model to determine the enhancement of SO2 production arising from the reaction DMS + Cl2. Absorption cross sections measured in the 28000-34000 cm(-1) region have been used to determine photolysis rate coefficients of MClDMS in the troposphere at 10 solar zenith angles (SZAs). These have been used to determine the lifetimes of MClDMS in the troposphere. At 0° SZA, a photolysis lifetime of 3-4 h has been obtained. The results show that the photolysis lifetime of MClDMS is significantly smaller than the lifetimes with respect to reaction with OH (≈ 4.6 days) and with Cl atoms (≈ 1.2 days). It has also been shown, using experimentally derived dissociation energies with supporting quantum-chemical calculations, that the dominant photodissocation route of MClDMS is dissociation of the C-S bond to give CH3S and CH2Cl. MBL box modeling calculations show that buildup of MClDMS at night from the Cl2 + DMS reaction leads to enhanced SO2 production during the day. The extra SO2 arises from photolysis of MClDMS to give CH3S and CH2Cl, followed by subsequent oxidation of CH3S.

Metabolic control analysis of biochemical pathways based on a thermokinetic description of reaction rates

DEFF Research Database (Denmark)

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...... that the elasticity coefficients can be calculated directly from the pool levels of metabolites at steady state. The only requirement is that one thermodynamic parameter be known, namely the reaction affinity at the intercept of the tangent in the inflection point of the curve of reaction rate against reaction...... of the thermokinetic description of reaction rates to include the influence of effecters. Here the reaction rate is written as a linear function of the logarithm of the metabolite concentrations. With this type of rate function it is shown that the approach of Delgado and Liao [Biochem. J. (1992) 282, 919-927] can...

Automatic estimation of pressure-dependent rate coefficients.

Science.gov (United States)

Allen, Joshua W; Goldsmith, C Franklin; Green, William H

2012-01-21

A general framework is presented for accurately and efficiently estimating the phenomenological pressure-dependent rate coefficients for reaction networks of arbitrary size and complexity using only high-pressure-limit information. Two aspects of this framework are discussed in detail. First, two methods of estimating the density of states of the species in the network are presented, including a new method based on characteristic functional group frequencies. Second, three methods of simplifying the full master equation model of the network to a single set of phenomenological rates are discussed, including a new method based on the reservoir state and pseudo-steady state approximations. Both sets of methods are evaluated in the context of the chemically-activated reaction of acetyl with oxygen. All three simplifications of the master equation are usually accurate, but each fails in certain situations, which are discussed. The new methods usually provide good accuracy at a computational cost appropriate for automated reaction mechanism generation.

Automatic estimation of pressure-dependent rate coefficients

KAUST Repository

Allen, Joshua W.; Goldsmith, C. Franklin; Green, William H.

2012-01-01

A general framework is presented for accurately and efficiently estimating the phenomenological pressure-dependent rate coefficients for reaction networks of arbitrary size and complexity using only high-pressure-limit information. Two aspects of this framework are discussed in detail. First, two methods of estimating the density of states of the species in the network are presented, including a new method based on characteristic functional group frequencies. Second, three methods of simplifying the full master equation model of the network to a single set of phenomenological rates are discussed, including a new method based on the reservoir state and pseudo-steady state approximations. Both sets of methods are evaluated in the context of the chemically-activated reaction of acetyl with oxygen. All three simplifications of the master equation are usually accurate, but each fails in certain situations, which are discussed. The new methods usually provide good accuracy at a computational cost appropriate for automated reaction mechanism generation. This journal is © the Owner Societies.

Determination of the gas-to-membrane mass transfer coefficient in a catalytic membrane reactor

NARCIS (Netherlands)

Veldsink, J.W.; Versteeg, G.F.; Swaaij, W.P.M. van

1995-01-01

A novel method to determine the external mass transfer coefficient in catalytic membrane reactors (Sloot et al., 1992a, b) was presented in this study. In a catalytically active membrane reactor, in which a very fast reaction occurs, the external transfer coefficient can conveniently be measured by

Random incidence absorption coefficients of porous absorbers based on local and extended reaction models

DEFF Research Database (Denmark)

Jeong, Cheol-Ho

2011-01-01

resistivity and the absorber thickness on the difference between the two surface reaction models are examined and discussed. For a porous absorber backed by a rigid surface, the local reaction models give errors of less than 10% if the thickness exceeds 120 mm for a flow resistivity of 5000 Nm-4s. As the flow...... incidence acoustical characteristics of typical building elements made of porous materials assuming extended and local reaction. For each surface reaction, five well-established wave propagation models, the Delany-Bazley, Miki, Beranek, Allard-Champoux, and Biot model, are employed. Effects of the flow...... resistivity doubles, a decrease in the required thickness by 25 mm is observed to achieve the same amount of error. For an absorber backed by an air gap, the thickness ratio between the material and air cavity is important. If the absorber thickness is approximately 40% of the cavity depth, the local reaction...

Measurement of distribution coefficients of U series radionuclides on soils under shallow land environment (2). pH dependence of distribution coefficients

International Nuclear Information System (INIS)

Sakamoto, Yoshiaki; Takebe, Shinichi; Ogawa, Hiromichi; Inagawa, Satoshi; Sasaki, Tomozou

2001-01-01

In order to study sorption behavior of U series radionuclides (Pb, Ra, Th, Ac, Pa and U) under aerated zone environment (loam-rain water system) and aquifer environment (sand-groundwater system) for safety assessment of U bearing waste, pH dependence of distribution coefficients of each element has been obtained. The pH dependence of distribution coefficients of Pb, Ra, Th, Ac and U was analyzed by model calculation based on aqueous speciation of each element and soil surface charge characteristics, which is composed of a cation exchange capacity and surface hydroxyl groups. From the model calculation, the sorption behavior of Pb, Ra, Th, Ac and U could be described by a combination of cation exchange reaction and surface-complexation model. (author)

Reaction Mechanism Generator: Automatic construction of chemical kinetic mechanisms

Science.gov (United States)

Gao, Connie W.; Allen, Joshua W.; Green, William H.; West, Richard H.

2016-06-01

Reaction Mechanism Generator (RMG) constructs kinetic models composed of elementary chemical reaction steps using a general understanding of how molecules react. Species thermochemistry is estimated through Benson group additivity and reaction rate coefficients are estimated using a database of known rate rules and reaction templates. At its core, RMG relies on two fundamental data structures: graphs and trees. Graphs are used to represent chemical structures, and trees are used to represent thermodynamic and kinetic data. Models are generated using a rate-based algorithm which excludes species from the model based on reaction fluxes. RMG can generate reaction mechanisms for species involving carbon, hydrogen, oxygen, sulfur, and nitrogen. It also has capabilities for estimating transport and solvation properties, and it automatically computes pressure-dependent rate coefficients and identifies chemically-activated reaction paths. RMG is an object-oriented program written in Python, which provides a stable, robust programming architecture for developing an extensible and modular code base with a large suite of unit tests. Computationally intensive functions are cythonized for speed improvements.

Lattice cell diffusion coefficients. Definitions and comparisons

International Nuclear Information System (INIS)

Hughes, R.P.

1980-01-01

Definitions of equivalent diffusion coefficients for regular lattices of heterogeneous cells have been given by several authors. The paper begins by reviewing these different definitions and the unification of their derivation. This unification makes clear how accurately each definition (together with appropriate cross-section definitions to preserve the eigenvalue) represents the individual reaction rates within the cell. The approach can be extended to include asymmetric cells and whereas before, the buckling describing the macroscopic flux shape was real, here it is found to be complex. A neutron ''drift'' coefficient as well as a diffusion coefficient is necessary to produce the macroscopic flux shape. The numerical calculation of the various different diffusion coefficients requires the solutions of equations similar to the ordinary transport equation for an infinite lattice. Traditional reactor physics codes are not sufficiently flexible to solve these equations in general. However, calculations in certain simple cases are presented and the theoretical results quantified. In difficult geometries, Monte Carlo techniques can be used to calculate an effective diffusion coefficient. These methods relate to those already described provided that correlation effects between different generations of neutrons are included. Again, these effects are quantified in certain simple cases. (author)

Transformation formulas for legendre coefficients of double-differential cross sections

International Nuclear Information System (INIS)

Shi Xiangjun; Zhang Jingshang

1989-01-01

Approximate analytical formulas have been derived for the transformation of Legendre coefficients of double-differential continuum cross sections of two-body nuclear reactions from the center-of-mass to the laboratory system. This transformation differs from that of elastic-scattering angular distribution coefficients on its accuracy which depends not only upon the target mass, but also upon outgoing energies. A fast code has been written to transform Legendre coefficients of neutron inelastic scattering cross-sections. The calculations have been carried out using a recently introduced numerical integration method for more complicated problems in which the energy spectrum is either an evaporation spectrum or a spectrum obtained from a (pre-)compound model. The results are quite satisfactory provided that the target mass or the outgoing energy is not sufficiently low

Experimental and theoretical data on ion-molecule-reactions relevant for plasma modelling

International Nuclear Information System (INIS)

Hansel, A.; Praxmarer, C.; Lindinger, W.

1995-01-01

Despite the fact that the rate coefficients of hundreds of ion-molecule-reactions have been published in the literature, much more data are required for the purpose of plasma modelling. Many ion molecule reactions have rate coefficients, k, as large as the collisional limiting value, k c , i.e. the rate coefficients k c at which ion-neutral collision complexes are formed are close to the actual rate coefficients observed. In the case of the interaction of an ion with a non polar molecule, k c , is determined by the Langevin limiting value k L being typically 10 -9 cm 3 s -1 . However, when ions react with polar molecules k c is predicted by the average dipole orientation (ADO) theory. These classical theories yield accurate rate coefficients at thermal and elevated temperatures for practically all proton transfer as well as for many charge transfer and hydrogen abstraction reactions. The agreement between experimental and calculated values is usually better than ±20% and in the case of proton transfer reactions the agreement seems to be even better as recent investigations have shown. Even the interaction of the permanent ion dipole with non polar and polar neutrals can be taken into account to predict reaction rate coefficients as has been shown very recently in reactions of the highly polar ion ArH 3 + with various neutrals

Derivation of the chemical-equilibrium rate coefficient using scattering theory

Science.gov (United States)

Mickens, R. E.

1977-01-01

Scattering theory is applied to derive the equilibrium rate coefficient for a general homogeneous chemical reaction involving ideal gases. The reaction rate is expressed in terms of the product of a number of normalized momentum distribution functions, the product of the number of molecules with a given internal energy state, and the spin-averaged T-matrix elements. An expression for momentum distribution at equilibrium for an arbitrary molecule is presented, and the number of molecules with a given internal-energy state is represented by an expression which includes the partition function.

Non-equilibrium reaction rates in chemical kinetic equations

Science.gov (United States)

Gorbachev, Yuriy

2018-05-01

Within the recently proposed asymptotic method for solving the Boltzmann equation for chemically reacting gas mixture, the chemical kinetic equations has been derived. Corresponding one-temperature non-equilibrium reaction rates are expressed in terms of specific heat capacities of the species participate in the chemical reactions, bracket integrals connected with the internal energy transfer in inelastic non-reactive collisions and energy transfer coefficients. Reactions of dissociation/recombination of homonuclear and heteronuclear diatomic molecules are considered. It is shown that all reaction rates are the complex functions of the species densities, similarly to the unimolecular reaction rates. For determining the rate coefficients it is recommended to tabulate corresponding bracket integrals, additionally to the equilibrium rate constants. Correlation of the obtained results with the irreversible thermodynamics is established.

RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

KAUST Repository

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.

RPMDrate: Bimolecular chemical reaction rates from ring polymer molecular dynamics

KAUST Repository

Suleimanov, Yu.V.; Allen, J.W.; Green, W.H.

2013-01-01

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.

Simulation codes to evcaluate dose conversion coefficients for hadrons over 10 GeV

International Nuclear Information System (INIS)

Sato, T.; Tsuda, S.; Sakamoto, Y.; Yamaguchi, Y.; Niita, K.

2002-01-01

The conversion coefficients from fluence to effective dose for high energy hadrons are indispensable for various purposes such as accelerator shielding design and dose evaluation in space mission. Monte Carlo calculation code HETC-3STEP was used to evaluate dose conversion coefficients for neutrons and protons up to 10 GeV with an anthropomorphic model. The scaling model was incorporated in the code for simulation of high energy nuclear reactions. However, the secondary particle energy spectra predicted by the model were not smooth for nuclear reactions over several GeV. We attempted, therefore, to simulate transportation of such high energy particles by two newly developed Monte Carlo simulation codes: one is HETC-3STEP including the model used in EVENTQ instead of the scaling model, and the other is NMTC/JAM. By comparing calculated cross sections by these codes with experimental data for high energy nuclear reactions, it was found that NMTC/JAM had a better agreement with the data. We decided, therefore, to adopt NMTC/JAM for evaluation of dose conversion coefficients for hadrons with energies over 10 GeV. The effective dose conversion coefficients for high energy neutrons and protons evaluated by NMTC/JAM were found to be close to those by the FLUKA code

A Kinetic Study of the Gas-Phase Reaction of OH with Br2

Science.gov (United States)

Bryukov, Mikhail G.; Dellinger, Barry; Knyazev, Vadim D.

2011-01-01

An experimental, temperature-dependent kinetic study of the gas-phase reaction of the hydroxyl radical with molecular bromine (reaction 1) has been performed using a pulsed laser photolysis/pulsed-laser-induced fluorescence technique over a wide temperature range of 297 – 766 K, and at pressures between 6.68 and 40.29 kPa of helium. The experimental rate coefficients for reaction 1 demonstrate no correlation with pressure and exhibit a negative temperature dependence with a slight negative curvature in the Arrhenius plot. A non-linear least-squares fit with two floating parameters of the temperature dependent k1(T) data set using an equation of the form k1(T) = ATn yields the recommended expression k1(T) = 1.85×10−9T − 0.66 cm3 molecule−1 s−1 for the temperature dependence of the reaction 1 rate coefficient. The potential energy surface (PES) of reaction 1 was investigated using quantum chemistry methods. The reaction proceeds through formation of a weakly bound OH···Br2 complex and a PES saddle point with an energy below that of the reactants. Temperature dependence of the reaction rate coefficient was modeled using the RRKM method on the basis of the calculated PES. PMID:16854030

CHEMICAL REACTIONS ON ADSORBING SURFACE: KINETIC LEVEL OF DESCRIPTION

Directory of Open Access Journals (Sweden)

P.P.Kostrobii

2003-01-01

Full Text Available Based on the effective Hubbard model we suggest a statistical description of reaction-diffusion processes for bimolecular chemical reactions of gas particles adsorbed on the metallic surface. The system of transport equations for description of particles diffusion as well as reactions is obtained. We carry out the analysis of the contributions of all physical processes to the formation of diffusion coefficients and chemical reactions constants.

Experimental Study on the Feasibility of Using Water Glass and Aluminum Sulfate to Treat Complications in High Liquid Limit Soil Subgrade

Directory of Open Access Journals (Sweden)

Wen-hui Zhang

2015-01-01

Full Text Available The feasibility of using water glass and aluminum sulfate to treat high liquid limit soil subgrade diseases is studied through laboratory experiments, and the following results were observed. After improving the high liquid limit clay with water glass and aluminum sulfate, the liquid limit decreases, the plastic limit increases, and the plasticity index decreases. Compared with untreated soil, the clay content of the improved soil decreases, while the silt and coarse contents increase. The absolute and relative expansion rates of the improved soil are both lower than those of the untreated soil. With the same number of dry and wet cycles, the decreased degrees of cohesion and internal friction angle of the improved soil are, respectively, one-half and one-third of those of the untreated soil. After three dry and wet cycles, the California bearing ratio (CBR of the untreated soil does not meet the requirements of specifications. However, after being cured for seven days and being subjected to three dry and wet cycles, the CBR of the improved soil, with 4% water glass solution and 0.4% aluminum sulfate, meets the requirements of specifications.

Vapor Pressure and Evaporation Coefficient of Silicon Monoxide over a Mixture of Silicon and Silica

Science.gov (United States)

Ferguson, Frank T.; Nuth, Joseph A., III

2012-01-01

The evaporation coefficient and equilibrium vapor pressure of silicon monoxide over a mixture of silicon and vitreous silica have been studied over the temperature range (1433 to 1608) K. The evaporation coefficient for this temperature range was (0.007 plus or minus 0.002) and is approximately an order of magnitude lower than the evaporation coefficient over amorphous silicon monoxide powder and in general agreement with previous measurements of this quantity. The enthalpy of reaction at 298.15 K for this reaction was calculated via second and third law analyses as (355 plus or minus 25) kJ per mol and (363.6 plus or minus 4.1) kJ per mol respectively. In comparison with previous work with the evaporation of amorphous silicon monoxide powder as well as other experimental measurements of the vapor pressure of silicon monoxide gas over mixtures of silicon and silica, these systems all tend to give similar equilibrium vapor pressures when the evaporation coefficient is correctly taken into account. This provides further evidence that amorphous silicon monoxide is an intimate mixture of small domains of silicon and silica and not strictly a true compound.

Transitions in genetic toggle switches driven by dynamic disorder in rate coefficients

International Nuclear Information System (INIS)

Chen, Hang; Thill, Peter; Cao, Jianshu

2016-01-01

In biochemical systems, intrinsic noise may drive the system switch from one stable state to another. We investigate how kinetic switching between stable states in a bistable network is influenced by dynamic disorder, i.e., fluctuations in the rate coefficients. Using the geometric minimum action method, we first investigate the optimal transition paths and the corresponding minimum actions based on a genetic toggle switch model in which reaction coefficients draw from a discrete probability distribution. For the continuous probability distribution of the rate coefficient, we then consider two models of dynamic disorder in which reaction coefficients undergo different stochastic processes with the same stationary distribution. In one, the kinetic parameters follow a discrete Markov process and in the other they follow continuous Langevin dynamics. We find that regulation of the parameters modulating the dynamic disorder, as has been demonstrated to occur through allosteric control in bistable networks in the immune system, can be crucial in shaping the statistics of optimal transition paths, transition probabilities, and the stationary probability distribution of the network.

Transitions in genetic toggle switches driven by dynamic disorder in rate coefficients

Energy Technology Data Exchange (ETDEWEB)

Chen, Hang, E-mail: hangchen@mit.edu; Thill, Peter; Cao, Jianshu [Department of Chemistry, Massachusetts Institute of Technology, Cambridge, Massachusetts 02139 (United States)

2016-05-07

In biochemical systems, intrinsic noise may drive the system switch from one stable state to another. We investigate how kinetic switching between stable states in a bistable network is influenced by dynamic disorder, i.e., fluctuations in the rate coefficients. Using the geometric minimum action method, we first investigate the optimal transition paths and the corresponding minimum actions based on a genetic toggle switch model in which reaction coefficients draw from a discrete probability distribution. For the continuous probability distribution of the rate coefficient, we then consider two models of dynamic disorder in which reaction coefficients undergo different stochastic processes with the same stationary distribution. In one, the kinetic parameters follow a discrete Markov process and in the other they follow continuous Langevin dynamics. We find that regulation of the parameters modulating the dynamic disorder, as has been demonstrated to occur through allosteric control in bistable networks in the immune system, can be crucial in shaping the statistics of optimal transition paths, transition probabilities, and the stationary probability distribution of the network.

Co-solvent effects on reaction rate and reaction equilibrium of an enzymatic peptide hydrolysis.

Science.gov (United States)

Wangler, A; Canales, R; Held, C; Luong, T Q; Winter, R; Zaitsau, D H; Verevkin, S P; Sadowski, G

2018-04-25

This work presents an approach that expresses the Michaelis constant KaM and the equilibrium constant Kth of an enzymatic peptide hydrolysis based on thermodynamic activities instead of concentrations. This provides KaM and Kth values that are independent of any co-solvent. To this end, the hydrolysis reaction of N-succinyl-l-phenylalanine-p-nitroanilide catalysed by the enzyme α-chymotrypsin was studied in pure buffer and in the presence of the co-solvents dimethyl sulfoxide, trimethylamine-N-oxide, urea, and two salts. A strong influence of the co-solvents on the measured Michaelis constant (KM) and equilibrium constant (Kx) was observed, which was found to be caused by molecular interactions expressed as activity coefficients. Substrate and product activity coefficients were used to calculate the activity-based values KaM and Kth for the co-solvent free reaction. Based on these constants, the co-solvent effect on KM and Kx was predicted in almost quantitative agreement with the experimental data. The approach presented here does not only reveal the importance of understanding the thermodynamic non-ideality of reactions taking place in biological solutions and in many technological applications, it also provides a framework for interpreting and quantifying the multifaceted co-solvent effects on enzyme-catalysed reactions that are known and have been observed experimentally for a long time.

Determination of the side-reaction coefficient of desferrioxamine B in trace-metal-free seawater

Directory of Open Access Journals (Sweden)

Johan Schijf

2016-07-01

Full Text Available Electrochemical techniques like adsorptive cathodic stripping voltammetry with competitive ligand equilibration (ACSV-CLE can determine total concentrations of marine organic ligands and their conditional binding constants for specific metals, but cannot identify them. Individual organic ligands, isolated from microbial cultures or biosynthesized through genomics, can be structurally characterized via NMR and tandem MS analysis, but this is tedious and time-consuming. A complementary approach is to compare known properties of natural ligands, particularly their conditional binding constants, with those of model organic ligands, measured under suitable conditions. Such comparisons cannot be meaningfully interpreted unless the side-reaction coefficient (SRC of the model ligand in seawater is thoroughly evaluated.We conducted series of potentiometric titrations, in non-coordinating medium at seawater ionic strength (0.7 M NaClO4 over a range of metal:ligand molar ratios, to study complexation of the siderophore desferrioxamine B (DFOB with Mg and Ca, for which it has the highest affinity among the major seasalt cations. From similar titrations of acetohydroxamic acid in the absence and presence of methanesulfonate (mesylate, it was determined that Mg and Ca binding to this common DFOB counter-ion is not strong enough to interfere with the DFOB titrations. Stability constants were measured for all DFOB complexes with Mg and Ca including, for the first time, the bidentate complexes. No evidence was found for Mg and Ca coordination with the DFOB terminal amine. From the improved DFOB speciation, we calculated five SRCs for each of the five (deprotonated forms of DFOB in trace-metal-free seawater, yet we also present a more convenient definition of a single SRC that allows adjustment of all DFOB stability constants to seawater conditions, no matter which of these forms is selected as the 'component' (reference species. An example of Cd speciation in

Resilient modulus prediction of soft low-plasticity Piedmont residual soil using dynamic cone penetrometer

Directory of Open Access Journals (Sweden)

S. Hamed Mousavi

2018-04-01

Full Text Available Dynamic cone penetrometer (DCP has been used for decades to estimate the shear strength and stiffness properties of the subgrade soils. There are several empirical correlations in the literature to predict the resilient modulus values at only a specific stress state from DCP data, corresponding to the predefined thicknesses of pavement layers (a 50 mm asphalt wearing course, a 100 mm asphalt binder course and a 200 mm aggregate base course. In this study, field-measured DCP data were utilized to estimate the resilient modulus of low-plasticity subgrade Piedmont residual soil. Piedmont residual soils are in-place weathered soils from igneous and metamorphic rocks, as opposed to transported or compacted soils. Hence the existing empirical correlations might not be applicable for these soils. An experimental program was conducted incorporating field DCP and laboratory resilient modulus tests on “undisturbed” soil specimens. The DCP tests were carried out at various locations in four test sections to evaluate subgrade stiffness variation laterally and with depth. Laboratory resilient modulus test results were analyzed in the context of the mechanistic-empirical pavement design guide (MEPDG recommended universal constitutive model. A new approach for predicting the resilient modulus from DCP by estimating MEPDG constitutive model coefficients (k1, k2 and k3 was developed through statistical analyses. The new model is capable of not only taking into account the in situ soil condition on the basis of field measurements, but also representing the resilient modulus at any stress state which addresses a limitation with existing empirical DCP models and its applicability for a specific case. Validation of the model is demonstrated by using data that were not used for model development, as well as data reported in the literature. Keywords: Dynamic cone penetrometer (DCP, Resilient modulus, Mechanistic-empirical pavement design guide (MEPDG, Residual

Collisional Dissociation of CO: ab initio Potential Energy Surfaces and Quasiclassical Trajectory Rate Coefficients

Science.gov (United States)

Schwenke, David W.; Jaffe, Richard L.; Chaban, Galina M.

2016-01-01

We have generated accurate global potential energy surfaces for CO+Ar and CO+O that correlate with atom-diatom pairs in their ground electronic states based on extensive ab initio electronic structure calculations and used these potentials in quasi-classical trajectory nuclear dynamics calculations to predict the thermal dissociation rate coefficients over 5000- 35000 K. Our results are not compatible with the 20-45 year old experimental results. For CO + Ar we obtain fairly good agreement with the experimental rate coefficients of Appleton et al. (1970) and Mick and Roth (1993), but our computed rate coefficients exhibit a stronger temperature dependence. For CO + O our dissociation rate coefficient is in close agreement with the value from the Park model, which is an empirical adjustment of older experimental results. However, we find the rate coefficient for CO + O is only 1.5 to 3.3 times larger than CO + Ar over the temperature range of the shock tube experiments (8000-15,000 K). The previously accepted value for this rate coefficient ratio is 15, independent of temperature. We also computed the rate coefficient for the CO + O ex- change reaction which forms C + O2. We find this reaction is much faster than previously believed and is the dominant process in the removal of CO at temperatures up to 16,000 K. As a result, the dissociation of CO is accomplished in two steps (react to form C+O2 and then O2 dissociates) that are endothermic by 6.1 and 5.1 eV, instead of one step that requires 11.2 eV to break the CO bond.

Indirect Techniques in Nuclear Astrophysics. Asymptotic Normalization Coefficient and Trojan Horse

International Nuclear Information System (INIS)

Mukhamedzhanov, A.M.; Blokhintsev, L.D.; Brown, S.

2007-01-01

We address two important indirect techniques, the asymptotic normalization coefficient (ANC) and the Trojan Horse (TH) methods. We discuss the application of the ANC technique to determine the astrophysical factor for the 13 C(α, n) 16 O reaction which is one of the neutron generators for the s processes in AGB stars. The TH method is a unique indirect technique allowing one to measure astrophysical S factors for rearrangement reactions down to astrophysically relevant energies. We derive equations connecting the cross sections for the binary direct and resonant reactions determined from the indirect TH reactions to direct cross sections measurements

Reformulation and solution of the master equation for multiple-well chemical reactions.

Science.gov (United States)

Georgievskii, Yuri; Miller, James A; Burke, Michael P; Klippenstein, Stephen J

2013-11-21

We consider an alternative formulation of the master equation for complex-forming chemical reactions with multiple wells and bimolecular products. Within this formulation the dynamical phase space consists of only the microscopic populations of the various isomers making up the reactive complex, while the bimolecular reactants and products are treated equally as sources and sinks. This reformulation yields compact expressions for the phenomenological rate coefficients describing all chemical processes, i.e., internal isomerization reactions, bimolecular-to-bimolecular reactions, isomer-to-bimolecular reactions, and bimolecular-to-isomer reactions. The applicability of the detailed balance condition is discussed and confirmed. We also consider the situation where some of the chemical eigenvalues approach the energy relaxation time scale and show how to modify the phenomenological rate coefficients so that they retain their validity.

Conservatism Accountancy, Profit Persistence and Systematic Risk Towards The Earnings Responses Coefficient

Directory of Open Access Journals (Sweden)

Sri Agustina Basuki

2017-09-01

Full Text Available The purpose of this research is to understand the influence of investor reaction towards profit that measured by the earning response coefficient with the variable of conservatism accountancy, persistence of profit and the systematic risk at the company, which have high market capitalization and listed in the LQ 45 index.  Population in the research are companies, which are listed in the LQ 45 index from the period of 2011 to 2015 that have complete financial information, and have financial notation in the form of Rupiah and excluded from the banking sector. The analysis method that being used is multiple linier regressions analysis and the result shows that conservatism accountancy partially significant affecting the Earning Response Coefficient. It shows that there is an investor reaction towards companies in the Index LQ 45, which applies conservatism accountancy in gaining profit.  Profit persistence and the systematic risk is not significantly affecting earnings response coefficient.

A computer program incorporating Pitzer's equations for calculation of geochemical reactions in brines

Science.gov (United States)

Plummer, Niel; Parkhurst, D.L.; Fleming, G.W.; Dunkle, S.A.

1988-01-01

The program named PHRQPITZ is a computer code capable of making geochemical calculations in brines and other electrolyte solutions to high concentrations using the Pitzer virial-coefficient approach for activity-coefficient corrections. Reaction-modeling capabilities include calculation of (1) aqueous speciation and mineral-saturation index, (2) mineral solubility, (3) mixing and titration of aqueous solutions, (4) irreversible reactions and mineral water mass transfer, and (5) reaction path. The computed results for each aqueous solution include the osmotic coefficient, water activity , mineral saturation indices, mean activity coefficients, total activity coefficients, and scale-dependent values of pH, individual-ion activities and individual-ion activity coeffients , and scale-dependent values of pH, individual-ion activities and individual-ion activity coefficients. A data base of Pitzer interaction parameters is provided at 25 C for the system: Na-K-Mg-Ca-H-Cl-SO4-OH-HCO3-CO3-CO2-H2O, and extended to include largely untested literature data for Fe(II), Mn(II), Sr, Ba, Li, and Br with provision for calculations at temperatures other than 25C. An extensive literature review of published Pitzer interaction parameters for many inorganic salts is given. Also described is an interactive input code for PHRQPITZ called PITZINPT. (USGS)

Communication: Equilibrium rate coefficients from atomistic simulations: The O(3P) + NO(2Π) → O2(X3Σg−) + N(4S) reaction at temperatures relevant to the hypersonic flight regime

International Nuclear Information System (INIS)

Castro-Palacio, Juan Carlos; Bemish, Raymond J.; Meuwly, Markus

2015-01-01

The O( 3 P) + NO( 2 Π) → O 2 (X 3 Σ g − ) + N( 4 S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20 000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions

Communication: Equilibrium rate coefficients from atomistic simulations: The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction at temperatures relevant to the hypersonic flight regime.

Science.gov (United States)

Castro-Palacio, Juan Carlos; Bemish, Raymond J; Meuwly, Markus

2015-03-07

The O((3)P) + NO((2)Π) → O2(X(3)Σg(-)) + N((4)S) reaction is among the N- and O- involving reactions that dominate the energetics of the reactive air flow around spacecraft during hypersonic atmospheric re-entry. In this regime, the temperature in the bow shock typically ranges from 1000 to 20,000 K. The forward and reverse rate coefficients for this reaction derived directly from trajectory calculations over this range of temperature are reported in this letter. Results compare well with the established equilibrium constants for the same reaction from thermodynamic quantities derived from spectroscopy in the gas phase which paves the way for large-scale in silico investigations of equilibrium rates under extreme conditions.

Polarization transfer in (d-vector,n-vector) reactions

International Nuclear Information System (INIS)

Walter, R.L.; Tornow, W.

1986-01-01

The status of the measurements and the role of polarization transfer coefficients for (d/sup →/,n/sup →/) reactions is reviewed. Emphasis is given to reactions, involving light-nuclei systems. The importance of (d/sup →/,n/sup →/) reactions as sources of polarized neutrons is pointed out

THE BASING OF STABILIZATION PARAMETERS OF A FORTIFIED RAILWAY BED

Directory of Open Access Journals (Sweden)

V. D. Petrenko

2014-12-01

Full Text Available Purpose. The article is devoted to stabilization parameters determination of reinforced railway bed. At the present time, the railway plays the leading role in transport system to ensure the needs of freight and passenger traffic. In modern conditions railway operation concentrates on ensuring the necessary level of track reliability, including the roadbed, this is one of the main elements of road structures. The purpose of this article is the determination of basic parameters of stress-strain state to stabilize the soil subgrade embankment by reinforced materials. Methodology. To achieve this goal the following tasks of researches were solved: the effect of reinforcing layer of geomaterial on deformation properties of soil subgrade in various design of strengthening was investigated, the distributions of stresses in the subgrade were determined, reinforced of geomaterials under state load. Experimental studies to explore the nature of the deformation model subgrade at various degrees of stress were carried out. Findings. The analysis of the results of performed experimental and theoretical studies permitted to do the following conclusions. In conducting researches determined the distribution of stresses in the subgrade reinforced geomaterials under static load. The complex of experimental studies allows exploring the nature of the deformation model subgrade at various degrees of stress. Originality. On the basis of the theoretical studies have been regarded the problem of determining the stress-strain state of subgrade reinforced geomaterials by measuring stresses in its application for step loads. Practical value. The practical value was presented by the results of evaluating the effect of reinforcing way for changing the stress-strain state of subgrade.

Effects of variable sticking coefficients on the stability of reactive sputtering process

International Nuclear Information System (INIS)

Li Chuan; Hsieh Janghsing

2004-01-01

In reactive sputtering, the introduction of a reactive gas can lead to a hysteresis transition from metal to compounds in both the target and substrate. The hysteresis transition is characterized by a sudden change in partial pressure, sputtering rate, fraction of compound formation, etc. Therefore, stability is an important issue in the process control. In this paper, a mathematical model with variable sticking coefficients based on surface kinetics is used to study the stability of the process. The variable sticking coefficient represents different mechanisms for surface reactions from the Langmuir to precursor type. In order to facilitate the analysis, several nondimensional parameters are identified and used for formulation. Results show that an unsteady system converges to a steady state relatively fast at low inflow rates. With an eigenvalue analysis, the range of positive eigenvalues is consistent with the presence of a hysteresis loop. It is also found that when the chemical reaction on the substrate is moderate, a higher sputter yield of the compound leads to a more stable steady state at lower inflow rates. Regarding the sticking mechanism, for the type of precursors with the parameter k < 1, the compound is easier to form and saturate on the surface due to the higher default sticking coefficient and the lower operating conditions for the hysteresis transition

Reaction diffusion in chromium-zircaloy-2 system

International Nuclear Information System (INIS)

Xiang Wenxin; Ying Shihao

2001-01-01

Reaction diffusion in the chromium-zircaloy-2 diffusion couples is investigated in the temperature range of 1023 - 1123 K. Scanning electron microscope (SEM) and energy dispersive spectrum (EDS) were used to measure the thickness of the reaction layer and to determine the Zr, Fe and Cr concentration penetrate profile in reaction layer, respectively. The growth kinetics of reaction layer has been studied and the results show that the growth of intermetallic compound is controlled by the process of volume diffusion as the layer growth approximately obeys the parabolic law. Interdiffusion coefficients were calculated using Boltzmann-Matano-Heumann model. Calculated interdiffusion coefficients were compared with those obtained on the condition that Cr dissolves in Zr and merely forms dilute solid solution. The comparison indicates that Cr diffuses in dilute solid solution is five orders of magnitude faster than in Zr(Fe, Cr) 2 intermetallic compound

Transmission Coefficients for Chemical Reactions with Multiple States: Role of Quantum Decoherence

Czech Academy of Sciences Publication Activity Database

de la Lande, A.; Řezáč, Jan; Lévy, B.; Sanders, B. C.; Salahub, D. R.

2011-01-01

Roč. 133, č. 11 (2011), s. 3883-3894 ISSN 0002-7863 Institutional research plan: CEZ:AV0Z40550506 Keywords : decoherence * transition state theory * nonadiabatic reactions Subject RIV: CC - Organic Chemistry Impact factor: 9.907, year: 2011

Reevaluation of the O+(2P) reaction rate coefficients derived from atmosphere explorer C observations

International Nuclear Information System (INIS)

Chang, T.; Torr, D.G.; Richards, P.G.; Solomon, S.C.

1993-01-01

O + ( 2 P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 angstrom can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N 2 reaction rates which are needed to determine the major sinks of O + ( 2 P). The reaction rates that are generally used were determined from aeronomic data by Rusch et al. but there is evidence that several important inputs that they used should be changed. The authors have recalculated the O and N 2 reaction rates for O + ( 2 P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N 2 reaction rate of 3.4 ± 1.5 x 10 -10 cm 3 s -1 is close to the value obtained by Rusch et al., but the new O reaction rate of 4.0 ± 1.9 x 10 -10 cm 3 s -1 is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al. and they are in reasonable agreement with data from five additional orbits that are used in this study. The authors have also examined the effect of uncertainties in the solar EUV flux on the derived reaction rates and found that 15% uncertainties in the solar flux could cause additional uncertainties of up to a factor of 1.5 in the O quenching rate. 19 refs., 4 figs., 8 tabs

Effective reaction rates in diffusion-limited phosphorylation-dephosphorylation cycles

Science.gov (United States)

Szymańska, Paulina; Kochańczyk, Marek; Miekisz, Jacek; Lipniacki, Tomasz

2015-02-01

We investigate the kinetics of the ubiquitous phosphorylation-dephosphorylation cycle on biological membranes by means of kinetic Monte Carlo simulations on the triangular lattice. We establish the dependence of effective macroscopic reaction rate coefficients as well as the steady-state phosphorylated substrate fraction on the diffusion coefficient and concentrations of opposing enzymes: kinases and phosphatases. In the limits of zero and infinite diffusion, the numerical results agree with analytical predictions; these two limits give the lower and the upper bound for the macroscopic rate coefficients, respectively. In the zero-diffusion limit, which is important in the analysis of dense systems, phosphorylation and dephosphorylation reactions can convert only these substrates which remain in contact with opposing enzymes. In the most studied regime of nonzero but small diffusion, a contribution linearly proportional to the diffusion coefficient appears in the reaction rate. In this regime, the presence of opposing enzymes creates inhomogeneities in the (de)phosphorylated substrate distributions: The spatial correlation function shows that enzymes are surrounded by clouds of converted substrates. This effect becomes important at low enzyme concentrations, substantially lowering effective reaction rates. Effective reaction rates decrease with decreasing diffusion and this dependence is more pronounced for the less-abundant enzyme. Consequently, the steady-state fraction of phosphorylated substrates can increase or decrease with diffusion, depending on relative concentrations of both enzymes. Additionally, steady states are controlled by molecular crowders which, mostly by lowering the effective diffusion of reactants, favor the more abundant enzyme.

Reevaluation of the O(+)(2P) reaction rate coefficients derived from Atmosphere Explorer C observations

Science.gov (United States)

Chang, T.; Torr, D. G.; Richards, P. G.; Solomon, S. C.

1993-01-01

O(+)(2P) is an important species for studies of the ionosphere and thermosphere: its emission at 7320 A can be used as a diagnostic of the thermospheric atomic oxygen density. Unfortunately, there are no laboratory measurements of the O and N2 reaction rates which are needed to determine the major sinks of (O+)(2p). We have recalculated the O and N2 reaction rates for O(+) (2P) using recent improvements in the solar EUV flux, cross sections, and photoelectron fluxes. For the standard solar EUV flux, the new N2 reaction rate of 3.4 +/- 1.5 x 10 exp -10 cu cm/s is close to the value obtained by Rusch et al. (1977), but the new O reaction rate of 4.0 +/- 1.9 x 10 exp -10 cu cm/sec is about 8 times larger. These new reaction rates are derived using neutral densities, electron density, and solar EUV fluxes measured by Atmosphere Explorer C in 1974 during solar minimum. The new theoretical emission rates are in good agreement with the data for the two orbits studied by Rusch et al.

Kinetics of Hydrogen Abstraction and Addition Reactions of 3-Hexene by ȮH Radicals.

Science.gov (United States)

Yang, Feiyu; Deng, Fuquan; Pan, Youshun; Zhang, Yingjia; Tang, Chenglong; Huang, Zuohua

2017-03-09

Rate coefficients of H atom abstraction and H atom addition reactions of 3-hexene by the hydroxyl radicals were determined using both conventional transition-state theory and canonical variational transition-state theory, with the potential energy surface (PES) evaluated at the CCSD(T)/CBS//BHandHLYP/6-311G(d,p) level and quantum mechanical effect corrected by the compounded methods including one-dimensional Wigner method, multidimensional zero-curvature tunneling method, and small-curvature tunneling method. Results reveal that accounting for approximate 70% of the overall H atom abstractions occur in the allylic site via both direct and indirect channels. The indirect channel containing two van der Waals prereactive complexes exhibits two times larger rate coefficient relative to the direct one. The OH addition reaction also contains two van der Waals complexes, and its submerged barrier results in a negative temperature coefficient behavior at low temperatures. In contrast, The OH addition pathway dominates only at temperatures below 450 K whereas the H atom abstraction reactions dominate overwhelmingly at temperature over 1000 K. All of the rate coefficients calculated with an uncertainty of a factor of 5 were fitted in a quasi-Arrhenius formula. Analyses on the PES, minimum reaction path and activation free Gibbs energy were also performed in this study.

Reaction of O+, CO+, and CH+ ions with atomic hydrogen

International Nuclear Information System (INIS)

Federer, W.; Villinger, H.; Howorka, F.; Lindinger, W.; Tosis, P.; Bassi, D.; Ferguson, E.

1984-01-01

Rate coefficients for reactions of the ions O + , CO + , and CH + with atomic hydrogen have been measured for the first time at 300 K. This provides basic data for the ion chemistry of planetary atmospheres, cometary atmospheres, and interstellar molecular clouds. The O + +H measurement supports quantal calculations of this reaction. The CO + +H reaction provides an example of partial spin nonconservation in a charge-transfer reaction occurring in a deep potential well. Reactions of the same ions with H 2 that have been measured elsewhere are also reported

Solubility and diffusion coefficient of oxygen in silicon

International Nuclear Information System (INIS)

Itoh, Yoshiko; Nozaki, Tadashi

1985-01-01

The solubility and diffusion coefficient of oxygen in silicon between 1000 0 C and 1375 0 C were examined by charged particle activation analysis with the 16 O( 3 He,p) 18 F reaction, in which oxygen was activated with an equal probability over the depth of up to 250μm by a specially devised apparatus. Silicon wafers of known histories were heated in oxygen or argon for 12 to 473 hours, and the resultant oxygen depth profiles were determined by the activation, subsequent stepwise etching and 18 F activity measurement. The solubility thus obtained is given as 9.3 x 10 21 exp[-27.6kcal mol -1 /RT] at.cm -3 ; the diffusion coefficient has been found to be approximated as 3.2 exp[-67.1kcal mol -1 /RT] cm 2 s -1 over 1150 0 C, under which the apparent activation energy seems to decrease with decrease of temperature. (author)

A shock tube study of the reactions of the hydroxyl radical with combustion species

Energy Technology Data Exchange (ETDEWEB)

Cohen, N.; Koffend, J.B. [The Aerospace Corporation, Los Angeles, CA (United States)

1993-12-01

To extend the semi-empirical techniques of Benson and coworkers, and to extend the database of reliable high temperature measurements of OH radicals with hydrocarbons and other fuels and their decomposition products, the authors undertook a research program with both experimental and computational tasks. The experimental goal was to design a procedure for measuring, at combustion temperatures, the reaction rate coefficients of OH radicals with fuels and other species of importance in combustion or propulsion systems. The computational effort was intended to refine the semi-empirical transition-state-theory procedures for extrapolating rate coefficients of reactions of OH with combustion species of interest, for predicting rate coefficients for species not studied in the laboratory, and to examine the ability of the theory to predict rate coefficients for different pathways in the case the reagent possessed more than one nonequivalent H atoms.

Discharge Coefficient of Rectangular Short-Crested Weir with Varying Slope Coefficients

Directory of Open Access Journals (Sweden)

Yuejun Chen

2018-02-01

Full Text Available Rectangular short-crested weirs are widely used for simple structure and high discharge capacity. As one of the most important and influential factors of discharge capacity, side slope can improve the hydraulic characteristics of weirs at special conditions. In order to systemically study the effects of upstream and downstream slope coefficients S1 and S2 on overflow discharge coefficient in a rectangular short-crested weir the Volume of Fluid (VOF method and the Renormalization Group (RNG κ-ε turbulence model are used. In this study, the slope coefficient ranges from V to 3H:1V and each model corresponds to five total energy heads of H0 ranging from 8.0 to 24.0 cm. Comparisons of discharge coefficients and free surface profiles between simulated and laboratory results display a good agreement. The simulated results show that the difference of discharge coefficients will decrease with upstream slopes and increase with downstream slopes as H0 increases. For a given H0, the discharge coefficient has a convex parabolic relation with S1 and a piecewise linearity relation with S2. The maximum discharge coefficient is always obtained at S2 = 0.8. There exists a difference between upstream and downstream slope coefficients in the influence range of free surface curvatures. Furthermore, a proposed discharge coefficient equation by nonlinear regression is a function of upstream and downstream slope coefficients.

The solubility and diffusion coefficient of helium in uranium dioxide

International Nuclear Information System (INIS)

Nakajima, Kunihisa; Serizawa, Hiroyuki; Shirasu, Noriko; Haga, Yoshinori; Arai, Yasuo

2011-01-01

Highlights: ► The solubility and diffusivity of He in single-crystal UO 2 were determined. ► The determined He solubility lay within the scatter of the available data. ► The determined He diffusivity was in good agreement with recent experimental data. ► The He behavior was analyzed in terms of a simple interstitial diffusion mechanism. ► The experimental diffusivity was much lower than that analyzed theoretically. - Abstract: The solubility and diffusion coefficient of helium in the single-crystal UO 2 samples were determined by a Knudsen-effusion mass-spectrometric method. The measured helium solubilities were found to lie within the scatter of the available data, but to be much lower than those for the polycrystalline samples. The diffusion analysis was conducted based on a hypothetical equivalent sphere model and the simple Fick’s law. The helium diffusion coefficient was determined by using the pre-exponential factor and activation energy as the fitting parameters for the measured and calculated fractional releases of helium. The optimized diffusion coefficients were in good agreement with those obtained by a nuclear reaction method reported in the past. It was also found that the pre-exponential factors of the determined diffusion coefficients were much lower than those analyzed in terms of a simple interstitial diffusion mechanism.

Laboratory Study of the OH + Permethylsiloxane (L2, L3, D3, and D4) Reaction Rate Coefficients Between 240 and 370 K

Science.gov (United States)

Burkholder, J. B.; Bernard, F.; Papadimitriou, V. C.

2016-12-01

The atmospheric chemistry of organosiloxanes has recently been implicated in the formation of new particles as well as regional and indoor air quality. Methylsiloxanes with Sitextiles, health care and household products and in industrial applications as solvents and lubricants. They are released into the atmosphere during manufacturing, use, and disposal and have been observed in the atmosphere in ppb levels in certain locations. However, the fundamental chemical properties of this class of compounds, particularly their reactivity with the OH radical, are presently not fully characterized. In this work, the temperature dependence of the rate coefficients for the OH radical reaction with the simplest linear (L2 and L3) and cyclic (D3 and D4) siloxanes were measured: OH + (CH3)3SiOSi(CH3)3 = Products L2OH + [(CH3)3SiO]2Si(CH3)2 = Products L3OH + [-Si(CH3)2O-]3 = Products D3OH + [-Si(CH3)2O-]4 = Products D4OH rate coefficients were measured under pseudo-first conditions in OH over the temperature range 240-370 K using a pulsed laser photolysis-laser induced fluorescence (PLP-LIF) technique and at 296 K using a relative rate method. The present results are compared with available literature data where possible and discrepancies are discussed. The results from this work will be discussed in terms of the atmospheric lifetimes of these methylsiloxanes and the reactivity trends for this class of compound.

Minimum Thickness of Concrete Pavement for the F-15 and C-17 Aircraft

Science.gov (United States)

2013-07-01

laboratory compaction according to modified Proctor ASTM D1557 are summarized in Figure 15, which shows the clay moisture- density curve. Laboratory...16  Figure 15. Moisture- density curve for clay subgrade (ASTM 1557...subgrade. Figure 15. Moisture- density curve for clay subgrade (ASTM 1557). ERDC/GSL TR-13-34 17 Figure 16. Relationship for strength as

Measurement of cooling coil film heat transfer coefficient with polymer reaction proceeding in a stirred batch reactor; Jugo sonai ni okeru hanno shinko ni tomonau reikyaku coil no kyomaku netsudentatsu keisu no keiji henka

Energy Technology Data Exchange (ETDEWEB)

Yamamoto, K [Soken Chemical and Engineering Co. Ltd., Saitama (Japan); Nishi, K; Kaminoyama, M; Kamiwano, M [Yokohama National University, Yokohama (Japan). Faculty of Engineering

1996-09-10

In radical additional solution polymerization, the viscosity increases with reaction progress. It is important to evaluate beforehand the cooling capacity of the reactor, which worsens with the process. In this study, a stirred batch reactor with both a paddle and a helical screw impeller were studied, and measurements were made for the dynamic changes of the film heat transfer coefficient of the cooling coil with progress of the polymer reaction. We found the change could be evaluated by the calculating heat balance of the generated heat, the viscous dissipation energy and the sensible heat change under conditions of monomer conversion and changing viscosity. 11 refs., 7 figs.

Nuclear data for the calculation of thermal reactor reactivity coefficients

International Nuclear Information System (INIS)

1989-01-01

On its 15th meeting in Vienna, 16-20 June 1986, the International Nuclear Data Committee (INDC) considered it important to review the accuracy with which changes in thermal reactor reactivity resulting from changes in temperature and coolant density can be predicted. It was noted that reactor physicists in several countries had to adjust the thermal neutron cross-section data base in order to reproduce measured reactivity coefficients. Consequently, it appeared to be essential to examine the consistency of the integral and differential cross-section data and to make all the information available which has a bearing on reactivity coefficient prediction. Following the recommendation of the INDC, the Nuclear Data Section of the International Atomic Energy Agency, therefore, convened the Advisory Group Meeting on Nuclear Data for the Calculation of Thermal Reaction Reactivity Coefficients, in Vienna, Austria, 7-10 Dec. 1987. The Conclusions and Recommendations of the meeting together with the papers presented, are submitted in the present document. A separate abstract was prepared for each of these 12 papers. Refs, figs and tabs

Use of code DTF-4 for determining the coefficient of back-reflection of the neutron within the thermonuclear plasma of a thermonuclear reactor controlled by the rate of the fission reactions. Pt. 1

International Nuclear Information System (INIS)

Cristea, G.

1975-01-01

The neutron problems are discussed of the thermonuclear reactor controlled by the rate of the fission reactions. The results obtained by rolling the DTF-4 program in a spherical geometry in the case of an ''external source'' problem permit to draw conclusions concerning the problems of the neutronics system of this thermonuclear reactor type. A relation is deduced for estimating the coefficient of back-reflection of the neutrons within the thermonuclear plasma and the focussion system is discussed of the neutronics of this reactor type

Multilayer Network Analysis of Nuclear Reactions

Science.gov (United States)

Zhu, Liang; Ma, Yu-Gang; Chen, Qu; Han, Ding-Ding

2016-08-01

The nuclear reaction network is usually studied via precise calculation of differential equation sets, and much research interest has been focused on the characteristics of nuclides, such as half-life and size limit. In this paper, however, we adopt the methods from both multilayer and reaction networks, and obtain a distinctive view by mapping all the nuclear reactions in JINA REACLIB database into a directed network with 4 layers: neutron, proton, 4He and the remainder. The layer names correspond to reaction types decided by the currency particles consumed. This combined approach reveals that, in the remainder layer, the β-stability has high correlation with node degree difference and overlapping coefficient. Moreover, when reaction rates are considered as node strength, we find that, at lower temperatures, nuclide half-life scales reciprocally with its out-strength. The connection between physical properties and topological characteristics may help to explore the boundary of the nuclide chart.

Stellar reaction rate for 22Mg+p→23Al from the asymptotic normalization coefficient in the mirror nuclear system 22Ne+n→23Ne

International Nuclear Information System (INIS)

Al-Abdullah, T.; Carstoiu, F.; Chen, X.; Clark, H. L.; Fu, C.; Gagliardi, C. A.; Lui, Y.-W.; Mukhamedzhanov, A.; Tabacaru, G.; Tokimoto, Y.; Trache, L.; Tribble, R. E.

2010-01-01

The production of 22 Na in ONe novae can be influenced by the 22 Mg(p,γ) 23 Al reaction. To investigate this reaction rate at stellar energies, we have determined the asymptotic normalization coefficient (ANC) for 22 Mg+p→ 23 Al through measurements of the ANCs in the mirror nuclear system 22 Ne+n→ 23 Ne. The peripheral neutron-transfer reactions 13 C( 12 C, 13 C) 12 C and 13 C( 22 Ne, 23 Ne) 12 C were studied. The identical entrance and exit channels of the first reaction make it possible to extract independently the ground-state ANC in 13 C. Our experiment gives C p 1/2 2 ( 13 C)=2.24±0.11 fm -1 , which agrees with the value obtained from several previous measurements. The weighted average for all the obtained C p 1/2 2 is 2.31±0.08 fm -1 . This value is adopted to be used in obtaining the ANCs in 23 Ne. The differential cross sections for the reaction 13 C( 22 Ne, 23 Ne) 12 C leading to the J π =5/2 + and 1/2 + states in 23 Ne have been measured at 12 MeV/u. Optical model parameters for use in the DWBA calculations were obtained from measurements of the elastic scatterings 22 Ne+ 13 C and 22 Ne+ 12 C. The extracted ANC for the ground state in 23 Ne, C d 5/2 2 =0.86±0.08±0.12 fm -1 , is converted to its corresponding value in 23 Al using mirror symmetry to give C d 5/2 2 ( 23 Al)=(4.63±0.77)x10 3 fm -1 . The astrophysical S factor S(0) for the 22 Mg(p,γ) reaction was determined to be 0.96±0.11 keV b. The consequences for nuclear astrophysics are discussed.

Thermodynamically based constraints for rate coefficients of large biochemical networks.

Science.gov (United States)

Vlad, Marcel O; Ross, John

2009-01-01

Wegscheider cyclicity conditions are relationships among the rate coefficients of a complex reaction network, which ensure the compatibility of kinetic equations with the conditions for thermodynamic equilibrium. The detailed balance at equilibrium, that is the equilibration of forward and backward rates for each elementary reaction, leads to compatibility between the conditions of kinetic and thermodynamic equilibrium. Therefore, Wegscheider cyclicity conditions can be derived by eliminating the equilibrium concentrations from the conditions of detailed balance. We develop matrix algebra tools needed to carry out this elimination, reexamine an old derivation of the general form of Wegscheider cyclicity condition, and develop new derivations which lead to more compact and easier-to-use formulas. We derive scaling laws for the nonequilibrium rates of a complex reaction network, which include Wegscheider conditions as a particular case. The scaling laws for the rates are used for clarifying the kinetic and thermodynamic meaning of Wegscheider cyclicity conditions. Finally, we discuss different ways of using Wegscheider cyclicity conditions for kinetic computations in systems biology.

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi; Giri, Binod; Szőri, Milá n; Mai, Tam V.-T.; Huynh, Lam K.; Farooq, Aamir

2017-01-01

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning's augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

Determination of the rate coefficient for the N2/+/ + O reaction in the ionosphere

Science.gov (United States)

Torr, D. G.; Torr, M. R.; Orsini, N.; Hanson, W. B.; Hoffman, J. H.; Walker, J. C. G.

1977-01-01

Using approximately 400 simultaneous measurements of ion and neutral densities and temperatures, and the spectrum of the solar flux measured by the Atmosphere Explorer C satellite, we have determined the rate constant k1 for the reaction between N2(+) and O in the ionosphere for ion temperatures between 600 and 700 K. We find that k1 = 1.1 x 10 to the minus 10th power cu cm per sec, with a standard deviation of + or - 15%. If we use the temperature dependence for this reaction determined in the laboratory then at 300 K we find excellent agreement with the recommended laboratory value.

Methyl-perfluoroheptene-ethers (CH3OC7F13): measured OH radical reaction rate coefficients for several isomers and enantiomers and their atmospheric lifetimes and global warming potentials.

Science.gov (United States)

Jubb, Aaron M; Gierczak, Tomasz; Baasandorj, Munkhbayar; Waterland, Robert L; Burkholder, James B

2014-05-06

Mixtures of methyl-perfluoroheptene-ethers (CH3OC7F13, MPHEs) are currently in use as replacements for perfluorinated alkanes (PFCs) and poly-ether heat transfer fluids, which are persistent greenhouse gases with lifetimes >1000 years. At present, the atmospheric processing and environmental impact from the use of MPHEs is unknown. In this work, rate coefficients at 296 K for the gas-phase reaction of the OH radical with six key isomers (including stereoisomers and enantiomers) of MPHEs used commercially were measured using a relative rate method. Rate coefficients for the six MPHE isomers ranged from ∼ 0.1 to 2.9 × 10(-12) cm(3) molecule(-1) s(-1) with a strong stereoisomer and -OCH3 group position dependence; the (E)-stereoisomers with the -OCH3 group in an α- position relative to the double bond had the greatest reactivity. Rate coefficients measured for the d3-MPHE isomer analogues showed decreased reactivity consistent with a minor contribution of H atom abstraction from the -OCH3 group to the overall reactivity. Estimated atmospheric lifetimes for the MPHE isomers range from days to months. Atmospheric lifetimes, radiative efficiencies, and global warming potentials for these short-lived MPHE isomers were estimated based on the measured OH rate coefficients along with measured and theoretically calculated MPHE infrared absorption spectra. Our results highlight the importance of quantifying the atmospheric impact of individual components in an isomeric mixture.

Clinical assessment of dynamic coefficient of friction effects in shoe-sole trituration of patients with drop foot.

Science.gov (United States)

Nima, Jamshidi; Firooz, Salami

2012-06-01

The aim of this study was examining the effect of human factors such as plantar friction, contact period time, and impulse on shoe-sole trituration of drop foot patients. Twenty-five patients with drop foot and twenty normal subjects were recruited in the study. The force plate and its related software's recorded human factor (coefficient of friction, ground reaction force, time of stance phase) as time dependent parameters. Dynamic coefficient of friction patterns were categorized based on their magnitude versus time when the longitudinal axis of the sole was plotted as the Y-axis and the transverse axis of the sole as X-axis during stance phase. The result of this research indicated that the average coefficient of friction among drop foot patients is 77.53 % (p value <0.05) lower than the normal subjects. Also the time of stance phase among drop foot patients is 7.56 % (p value <0.05) greater than normal subjects. There is no difference in the peaks, of vertical ground reaction force between normal and control group. The findings of this research revealed that the time of stance phase has a key role in shoe-sole trituration of patients with drop foot.

Flow-Injection Responses of Diffusion Processes and Chemical Reactions

DEFF Research Database (Denmark)

Andersen, Jens Enevold Thaulov

2000-01-01

tool of automated analytical chemistry. The need for an even lower consumption of chemicals and for computer analysis has motivated a study of the FIA peak itself, that is, a theoretical model was developed, that provides detailed knowledge of the FIA profile. It was shown that the flow in a FIA...... manifold may be characterised by a diffusion coefficient that depends on flow rate, denoted as the kinematic diffusion coefficient. The description was applied to systems involving species of chromium, both in the case of simple diffusion and in the case of chemical reactions. It is suggested that it may...... be used in the resolution of FIA profiles to obtain information about the content of interference’s, in the study of chemical reaction kinetics and to measure absolute concentrations within the FIA-detector cell....

Determination of the apparent transfer coefficient for CO oxidation on Pt(poly), Pt(111), Pt(665) and Pt(332) using a potential modulation technique.

Science.gov (United States)

Wang, Han-Chun; Ernst, Siegfried; Baltruschat, Helmut

2010-03-07

The apparent transfer coefficient, which gives the magnitude of the potential dependence of the electrochemical reaction rates, is the key quantity for the elucidation of electrochemical reaction mechanisms. We introduce the application of an ac method to determine the apparent transfer coefficient alpha' for the oxidation of pre-adsorbed CO at polycrystalline and single-crystalline Pt electrodes in sulfuric acid. The method allows to record alpha' quasi continuously as a function of potential (and time) in cyclic voltammetry or at a fixed potential, with the reaction rate varying with time. At all surfaces (Pt(poly), Pt(111), Pt(665), and Pt(332)) we clearly observed a transition of the apparent transfer coefficient from values around 1.5 at low potentials to values around 0.5 at higher potentials. Changes of the apparent transfer coefficients for the CO oxidation with potential were observed previously, but only from around 0.7 to values as low as 0.2. In contrast, our experimental findings completely agree with the simulation by Koper et al., J. Chem. Phys., 1998, 109, 6051-6062. They can be understood in the framework of a Langmuir-Hinshelwood mechanism. The transition occurs when the sum of the rate constants for the forward reaction (first step: potential dependent OH adsorption, second step: potential dependent oxidation of CO(ad) with OH(ad)) exceeds the rate constant for the back-reaction of the first step. We expect that the ac method for the determination of the apparent transfer coefficient, which we used here, will be of great help also in many other cases, especially under steady conditions, where the major limitations of the method are avoided.

Blijvend vlakke wegen - CROW-werkgroep integraal wegontwerp - evaluatie van schadecases uit de praktijk

NARCIS (Netherlands)

Egmond-Weijburg, C.; Galjaard, P.J.; Van Gurp, C.A.P.M.

2008-01-01

This report presents an inquiry into cases of pavement design, construction and maintenance in which distress has been observed instigated by deeper subgrade or by inadequate attention for the interaction between subgrade and pavement structure. Almost all cases are situated in areas with subgrade

Computation of Clebsch-Gordan and Gaunt coefficients using binomial coefficients

International Nuclear Information System (INIS)

Guseinov, I.I.; Oezmen, A.; Atav, Ue

1995-01-01

Using binomial coefficients the Clebsch-Gordan and Gaunt coefficients were calculated for extremely large quantum numbers. The main advantage of this approach is directly calculating these coefficients, instead of using recursion relations. Accuracy of the results is quite high for quantum numbers l 1 , and l 2 up to 100. Despite direct calculation, the CPU times are found comparable with those given in the related literature. 11 refs., 1 fig., 2 tabs

Measurement and calculation of polarization transfer coefficients in the reaction {sup 2}H(p,p){sup 2}H at E{sub p}=22.5 MeV

Energy Technology Data Exchange (ETDEWEB)

Clajus, M.; Albert, J.; Bruno, M.; Egun, P.M.; Glockle, W.; Glombik, A.; Gruebler, W.; Hautle, P.; Kretschmer, W.; Rauscher, A.; Schmelzbach, P.A.; Slaus, I.; Weidmann, R.; Witala, H. [Inst. fuer Mittelenergiephys., Eidgenoessische Tech. Hochschule, Zurich (Switzerland)

1995-10-01

The polarization transfer coefficients K{sub x}{sup x}', K{sub y}{sup y}' and K{sub z}{sup x}' in the reaction {sup 2}H(p,p){sup 2}H have been measured at an incident proton energy of 22.5 MeV. The results are compared to predictions from Faddeev calculations using various nucleon-nucleon potential models. The overall agreement is rather good. The comparison in more detail shows a pronounced sensitivity of the results, especially for K{sub y}{sup y}', to the {sup 3}S{sub 1}-{sup 3}D{sub 1} and {sup 1}P{sub 1} NN force components. As in nucleon-nucleon scattering, however, these two parameters are correlated, thus hampering definite conclusions. (author)

Bottom Extreme-Ultraviolet-Sensitive Coating for Evaluation of the Absorption Coefficient of Ultrathin Film

Science.gov (United States)

Hijikata, Hayato; Kozawa, Takahiro; Tagawa, Seiichi; Takei, Satoshi

2009-06-01

A bottom extreme-ultraviolet-sensitive coating (BESC) for evaluation of the absorption coefficients of ultrathin films such as extreme ultraviolet (EUV) resists was developed. This coating consists of a polymer, crosslinker, acid generator, and acid-responsive chromic dye and is formed by a conventional spin-coating method. By heating the film after spin-coating, a crosslinking reaction is induced and the coating becomes insoluble. A typical resist solution can be spin-coated on a substrate covered with the coating film. The evaluation of the linear absorption coefficients of polymer films was demonstrated by measuring the EUV absorption of BESC substrates on which various polymers were spin-coated.

Dynamic absorption coefficients of chemically amplified resists and nonchemically amplified resists at extreme ultraviolet

Science.gov (United States)

Fallica, Roberto; Stowers, Jason K.; Grenville, Andrew; Frommhold, Andreas; Robinson, Alex P. G.; Ekinci, Yasin

2016-07-01

The dynamic absorption coefficients of several chemically amplified resists (CAR) and non-CAR extreme ultraviolet (EUV) photoresists are measured experimentally using a specifically developed setup in transmission mode at the x-ray interference lithography beamline of the Swiss Light Source. The absorption coefficient α and the Dill parameters ABC were measured with unprecedented accuracy. In general, the α of resists match very closely with the theoretical value calculated from elemental densities and absorption coefficients, whereas exceptions are observed. In addition, through the direct measurements of the absorption coefficients and dose-to-clear values, we introduce a new figure of merit called chemical sensitivity to account for all the postabsorption chemical reaction ongoing in the resist, which also predicts a quantitative clearing volume and clearing radius, due to the photon absorption in the resist. These parameters may help provide deeper insight into the underlying mechanisms of the EUV concepts of clearing volume and clearing radius, which are then defined and quantitatively calculated.

Evaluation of the difference in the rate coefficients of F2 + NOx (x = 1 or 2) → F + FNOx by the stereochemical arrangement using the density functional theory.

Science.gov (United States)

Tajima, Satomi; Hayashi, Toshio; Hori, Masaru

2015-02-26

The rate coefficient of F2 + NO → F + FNO is 2 to 5 orders of magnitude higher than that of F2 + NO2 → F + FNO2 even though bond energies of FNO and FNO2 only differ by ∼0.2 eV. To understand the cause of having different rate coefficients of these two reactions, the change in total energies was calculated by varying the stereochemical arrangement of F2 with respect to NOx (x = 1 or 2) by the density functional theory (DFT), using CAM-B3LYP/6-311 G+(d) in the Gaussian program. The permitted approaching angle between the x-axis and the plane consisting of O, N, F, and ϕ plays a key role to restrict the reaction of NO2 and F2 compared to the reaction of NO and F2. This restriction in the reaction space is considered to be the main cause of different rate coefficients depending on the selection of x = 1 or 2 of the reaction of F2 + NOx → F + FNOx, which was also confirmed by the difference in Si etch rate using the F formed by those reactions.

Off-diagonal coefficients of the DeWitt-Schwinger and Hadamard representations of the Feynman propagator

International Nuclear Information System (INIS)

Decanini, Yves; Folacci, Antoine

2006-01-01

Having in mind applications to gravitational wave theory (in connection with the radiation reaction problem), stochastic semiclassical gravity (in connection with the regularization of the noise kernel) and quantum field theory in higher-dimensional curved spacetime (in connection with the Hadamard regularization of the stress-energy tensor), we improve the DeWitt-Schwinger and Hadamard representations of the Feynman propagator of a massive scalar field theory defined on an arbitrary gravitational background by deriving higher-order terms for the covariant Taylor series expansions of the geometrical coefficients--i.e., the DeWitt and Hadamard coefficients--that define them

Raman spectroscopic study of reaction dynamics

Science.gov (United States)

MacPhail, R. A.

1990-12-01

The Raman spectra of reacting molecules in liquids can yield information about various aspects of the reaction dynamics. The author discusses the analysis of Raman spectra for three prototypical unimolecular reactions, the rotational isomerization of n-butane and 1,2-difluoroethane, and the barrierless exchange of axial and equatorial hydrogens in cyclopentane via pseudorotation. In the first two cases the spectra are sensitive to torsional oscillations of the gauche conformer, and yield estimates of the torsional solvent friction. In the case of cyclopentane, the spectra can be used to discriminate between different stochastic models of the pseudorotation dynamics, and to determine the relevant friction coefficients.

Proposed higher order continuum-based models for an elastic ...

African Journals Online (AJOL)

Three new variants of continuum-based models for an elastic subgrade are proposed. The subgrade is idealized as a homogenous, isotropic elastic layer of thickness H overlying a firm stratum. All components of the stress tensor in the subgrade are taken into account. Reasonable assumptions are made regarding the ...

Characterization of ionic liquid‐based biocatalytic two‐phase reaction system for production of biodiesel

DEFF Research Database (Denmark)

Prabhavathi Devi, Bethala Lakshmi Anu; Guo, Zheng; Xu, Xuebing

2011-01-01

The property of a variety of ionic liquids (ILs) as reaction media was evaluated for the production of biodiesel by enzymatic methanolysis of rapeseed oil. The IL Ammoeng 102, containing tetraaminum cation with C18 acyl and oligoethyleneglycol units, was found to be capable of forming oil....../IL biphasic reaction system by mixing with substrates, which is highly effective for the production of biodiesel with more than 98% biodiesel yield and nearly 100% conversion of oil. Conductor‐like screening model for real solvent (COSMO‐RS) in silico prediction of substrate solubility and simulation...... of partition coefficient change vs. reaction evolution indicated that the amphiphilic property of Ammoeng 102 might be responsible for creating efficient interaction of immiscible substrates; while big difference of partition coefficients of generated biodiesel and glycerol between the two phases suggests...

A combined high-temperature experimental and theoretical kinetic study of the reaction of dimethyl carbonate with OH radicals

KAUST Repository

Khaled, Fathi

2017-02-08

The reaction kinetics of dimethyl carbonate (DMC) and OH radicals were investigated behind reflected shock waves over the temperature range of 872-1295 K and at pressures near 1.5 atm. Reaction progress was monitored by detecting OH radicals at 306.69 nm using a UV laser absorption technique. The rate coefficients for the reaction of DMC with OH radicals were extracted using a detailed kinetic model developed by Glaude et al. (Proc. Combust. Inst. 2005, 30(1), 1111-1118). The experimental rate coefficients can be expressed in Arrhenius form as: kexpt\\'l = 5.15 × 10(13) exp(-2710.2/T) cm(3) mol(-1) s(-1). To explore the detailed chemistry of the DMC + OH reaction system, theoretical kinetic analyses were performed using high-level ab initio and master equation/Rice-Ramsperger-Kassel-Marcus (ME/RRKM) calculations. Geometry optimization and frequency calculations were carried out at the second-order Møller-Plesset (MP2) perturbation level of theory using Dunning\\'s augmented correlation consistent-polarized valence double-ζ basis set (aug-cc-pVDZ). The energy was extrapolated to the complete basis set using single point calculations performed at the CCSD(T)/cc-pVXZ (where X = D, T) level of theory. For comparison purposes, additional ab initio calculations were also carried out using composite methods such as CBS-QB3, CBS-APNO, G3 and G4. Our calculations revealed that the H-abstraction reaction of DMC by OH radicals proceeds via an addition elimination mechanism in an overall exothermic process, eventually forming dimethyl carbonate radicals and H2O. Theoretical rate coefficients were found to be in excellent agreement with those determined experimentally. Rate coefficients for the DMC + OH reaction were combined with literature rate coefficients of four straight chain methyl ester + OH reactions to extract site-specific rates of H-abstraction from methyl esters by OH radicals.

Study of oxygen mass transfer coefficient and oxygen uptake rate in a stirred tank reactor for uranium ore bioleaching

International Nuclear Information System (INIS)

Zokaei-Kadijani, S.; Safdari, J.; Mousavian, M.A.; Rashidi, A.

2013-01-01

Highlights: ► Mass transfer coefficient does not depend on biomass concentration. ► The pulp density has a negative effect on mass transfer coefficient. ► The pulp density is the unique factor that affects maximum OUR. ► In this work, Neale’s correlation is corrected for prediction of mass transfer coefficient. ► Biochemical reaction is a limiting factor in the uranium bioleaching process. - Abstract: In this work, the volumetric oxygen mass transfer coefficient and the oxygen uptake rate (OUR) were studied for uranium ore bioleaching process by Acidthiobacillus ferrooxidans in a stirred tank reactor. The Box-Bohnken design method was used to study the effect of operating parameters on the oxygen mass transfer coefficient. The investigated factors were agitation speed (rpm), aeration rate (vvm) and pulp density (% weight/volume) of the stirred tank reactor. Analysis of experimental results showed that the oxygen mass transfer coefficient had low dependence on biomass concentration but had higher dependence on the agitation speed, aeration rate and pulp density. The obtained biological enhancement factors were equal to ones in experiments. On the other hand, the obtained values for Damkohler number (Da < 0.468) indicated that the process was limited by the biochemical reaction rate. Experimental results obtained for oxygen mass transfer coefficient were correlated with the empirical relations proposed by Garcia-Ochoa and Gomez (2009) and Neale and Pinches (1994). Due to the high relative error in the correlation of Neale and Pinches, that correlation was corrected and the coefficient of determination was calculated to be 89%. The modified correlation has been obtained based on a wide range of operating conditions, which can be used to determine the mass transfer coefficient in a bioreactor

Calculation of the mass transfer coefficient for the combustion of a carbon particle

Energy Technology Data Exchange (ETDEWEB)

Scala, Fabrizio [Istituto di Ricerche sulla Combustione - CNR, P.le Tecchio 80, 80125 Napoli (Italy)

2010-01-15

In this paper we address the calculation of the mass transfer coefficient around a burning carbon particle in an atmosphere of O{sub 2}, N{sub 2}, CO{sub 2}, CO, and H{sub 2}O. The complete set of Stefan-Maxwell equations is analytically solved under the assumption of no homogeneous reaction in the boundary layer. An expression linking the oxygen concentration and the oxygen flux at the particle surface (as a function of the bulk gas composition) is derived which can be used to calculate the mass transfer coefficient. A very simple approximate explicit expression is also given for the mass transfer coefficient, that is shown to be valid in the low oxygen flux limit or when the primary combustion product is CO{sub 2}. The results are given in terms of a correction factor to the equimolar counter-diffusion mass transfer coefficient, which is typically available in the literature for specific geometries and/or fluid-dynamic conditions. The significance of the correction factor and the accuracy of the different available expressions is illustrated for several cases of practical interest. Results show that under typical combustion conditions the use of the equimolar counter-diffusion mass transfer coefficient can lead to errors up to 10%. Larger errors are possible in oxygen-enriched conditions, while the error is generally low in oxy-combustion. (author)

Coefficient estimates of negative powers and inverse coefficients for ...

Indian Academy of Sciences (India)

and the inequality is sharp for the inverse of the Koebe function k(z) = z/(1 − z)2. An alternative approach to the inverse coefficient problem for functions in the class S has been investigated by Schaeffer and Spencer [27] and FitzGerald [6]. Although, the inverse coefficient problem for the class S has been completely solved ...

Reaction layer growth and reaction heat of U-Mo/Al dispersion fuels using centrifugally atomized powders

International Nuclear Information System (INIS)

Ryu, Ho Jin; Han, Young Soo; Park, Jong Man; Park, Soon Dal; Kim, Chang Kyu

2003-01-01

The growth behavior of reaction layers and heat generation during the reaction between U-Mo powders and the Al matrix in U-Mo/Al dispersion fuels were investigated. Annealing of 10 vol.% U-10Mo/Al dispersion fuels at temperatures from 500 to 550 deg. C was carried out for 10 min to 36 h to measure the growth rate and the activation energy for the growth of reaction layers. The concentration profiles of reaction layers between the U-10Mo vs. Al diffusion couples were measured and the integrated interdiffusion coefficients were calculated for the U and Al in the reaction layers. Heat generation of U-Mo/Al dispersion fuels with 10-50 vol.% of U-Mo fuel during the thermal cycle from room temperature to 700 deg. C was measured employing the differential scanning calorimetry. Exothermic heat from the reaction between U-Mo and the Al matrix is the largest when the volume fraction of U-Mo fuel is about 30 vol.%. The unreacted fraction in the U-Mo powders increases as the volume fraction of U-Mo fuel increases from 30 to 50 vol.%

Preparation of computer codes for analyzing sensitivity coefficients of burnup characteristics (2) (Contract research, translated document)

International Nuclear Information System (INIS)

Hanaki, Hiroshi; Sanda, Toshio; Ohashi, Masahisa

2008-10-01

To develop nuclear design of LMFBR cores, they are important subjects of research and development to improve the accuracy in nuclear design of large LMFBR cores and to design highly efficient core more rationally. The adjusted nuclear cross-sections library has been made by being reflected the result of critical experiment of the JUPITER, etc. effectively as much as possible. And the distinct improvement of the accuracy in nuclear design of large LMFBR cores has been achieved. In the design of large LMFBR cores, however, it is important to accurately estimate not only nuclear characteristics, for example, reaction rate distribution and control rod worth but also burnup characteristics, for example, burnup reactivity loss, breeding ratio and so on. Therefore, it is thought to improve the prediction accuracy for burnup characteristics using many burnup data of 'Joyo' effectively. It is thought the best way to adjust cross sections using sensitivity coefficients of burnup characteristics to utilize burnup data of 'Joyo'. It is able to know the accuracy quantitatively for burnup characteristics of large LMFBR by analyzing the sensitivity coefficients. Therefore in this work computer codes for analyzing sensitivity coefficients of burnup characteristics had been prepared since 1992. In 1992 cross-section adjustment was done by using the data of 'Joyo' and the effect was studied. In this year the adequacy of the codes was studied with a view of applying of design of large LMFBR cores. The results are as follows: (1) The computer codes which could analyze sensitivity coefficients of burnup characteristics taking into consideration plural cycles and refueling were prepared, therefore it came of be able to adjust cross sections using burnup data and to estimate the accuracy for design of large LMFBR cores. The characteristics are not only burnup reactivity loss, breeding ratio but also number density, criticality, reactivity worth, reaction rate ratio, and reaction rate

Improvement of the Assignment Methodology of the Approach Embankment Design to Highway Structures in Difficult Conditions

Science.gov (United States)

Chistyy, Y.; Kuzakhmetova, E.; Fazilova, Z.; Tsukanova, O.

2018-03-01

Design issues of junction of bridges and overhead road with approach embankment are studied. The reasons for the formation of deformations in the road structure are indicated. Activities to ensure sustainability and acceleration of the shrinkage of a weak subgrade approach embankment are listed. The necessity of taking into account the man-made impact of the approach embankment on the subgrade behavior is proved. Modern stabilizing agents to improve the properties of used soils in the embankment and the subgrade are suggested. Clarified methodology for determining an active zone of compression in the subgrade under load from the weight of the embankment is described. As an additional condition to the existing methodology for establishing the lower bound of the active zone of compression it is offered to accept the accuracy of evaluation of soil compressibility and determine shrinkage.

Laboratory Measurements for H3+ Deuteration Reactions

Science.gov (United States)

Bowen, Kyle; Hillenbrand, Pierre-Michel; Urbain, Xavier; Savin, Daniel Wolf

2018-06-01

Deuterated molecules are important chemical tracers of protostellar cores. At the ~106 cm-3 particle densities and ~20 K temperatures typical for protostellar cores, most molecules freeze onto dust grains. A notable exception is H3+ and its isotopologues. These become important carriers of positive charge in the gas, can couple to any ambient magnetic field, and can thereby alter the cloud dynamics. Knowing the total abundance of H3+ and its isotopologues is important for studying the evolution of protostellar cores. However, H3+ and D3+ have no dipole moment. They lack a pure rotational spectrum and are not observable at protostellar core temperatures. Fortunately H2D+ and D2H+ have dipole moments and a pure rotational spectrum that can be excited in protostellar cores. Observations of these two molecules, combined with astrochemical models, provide information about the total abundance of H3+ and all its isotopologues. The inferred abundances, though, rely on accurate astrochemical data for the deuteration of H3+ and its isotopologues.Here we present laboratory measurements of the rate coefficients for three important deuterating reactions, namely D + H3+/H2D+/D2H+ → H + H2D+/ D2H+/D3+. Astrochemical models currently rely on rate coefficients from classical (Langevin) or semi-classical methods for these reactions, as fully quantum-mechanical calculations are beyond current computational capabilities. Laboratory studies are the most tractable means of providing the needed data. For our studies we used our novel dual-source, merged fast-beams apparatus, which enables us to study reactions of neutral atoms and molecular ions. Co-propagating beams allow us to measure experimental rate coefficients as a function of collision energy. We extract cross section data from these results, which we then convolve with a Maxwell-Boltzmann distribution to generate thermal rate coefficients. Here we present our results for these three reactions and discuss some implications.

Study of ODE limit problems for reaction-diffusion equations

Directory of Open Access Journals (Sweden)

Jacson Simsen

2018-01-01

Full Text Available In this work we study ODE limit problems for reaction-diffusion equations for large diffusion and we study the sensitivity of nonlinear ODEs with respect to initial conditions and exponent parameters. Moreover, we prove continuity of the flow and weak upper semicontinuity of a family of global attractors for reaction-diffusion equations with spatially variable exponents when the exponents go to 2 in \\(L^{\\infty}(\\Omega\\ and the diffusion coefficients go to infinity.

Sustainable development of roadways in Africa

OpenAIRE

Akindeji-Oladeji, O.; Awomeso, J. A.; Taiwo, A. M.; Abu, S.

2012-01-01

Dallas Roadway Products (DRP) soil stabilization technology can effectively improve road foundation construction and with it the strength of roadway sub-grades and sub-bases. Soil samples were collected from roads in Nigeria’s six geo-political regions. DRP LS-40 (lignate sulfonate) and DRP SA-44 (sulfuric acid) were added to the soil materials. The mixture precipitated a non-reversible chemical reaction that involved a permanent change in the soil structure. The chemicals reacted with th...

Sustainable development of roadways in Africa

OpenAIRE

Akindeji-Oladeji, O.; Awomeso, J. A.; Taiwo, A. M.; Abu, S.

2012-01-01

Dallas Roadway Products (DRP) soil stabilization technology can effectively improve road foundation construction and with it the strength of roadway sub-grades and sub-bases. Soil samples were collected from roads in Nigeria’s six geo-political regions. DRP LS-40 (lignate sulfonate) and DRP SA-44 (sulfuric acid) were added to the soil materials. The mixture precipitated a non-reversible chemical reaction that involved a permanent change in the soil structure. The chemicals reacted with the cl...

Compilation report of VHTRC temperature coefficient benchmark calculations

Energy Technology Data Exchange (ETDEWEB)

Yasuda, Hideshi; Yamane, Tsuyoshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

1995-11-01

A calculational benchmark problem has been proposed by JAERI to an IAEA Coordinated Research Program, `Verification of Safety Related Neutronic Calculation for Low-enriched Gas-cooled Reactors` to investigate the accuracy of calculation results obtained by using codes of the participating countries. This benchmark is made on the basis of assembly heating experiments at a pin-in block type critical assembly, VHTRC. Requested calculation items are the cell parameters, effective multiplication factor, temperature coefficient of reactivity, reaction rates, fission rate distribution, etc. Seven institutions from five countries have joined the benchmark works. Calculation results are summarized in this report with some remarks by the authors. Each institute analyzed the problem by applying the calculation code system which was prepared for the HTGR development of individual country. The values of the most important parameter, k{sub eff}, by all institutes showed good agreement with each other and with the experimental ones within 1%. The temperature coefficient agreed within 13%. The values of several cell parameters calculated by several institutes did not agree with the other`s ones. It will be necessary to check the calculation conditions again for getting better agreement. (J.P.N.).

Effective Diffusion Coefficients in Coal Chars

DEFF Research Database (Denmark)

Johnsson, Jan Erik; Jensen, Anker

2001-01-01

Knowledge of effective diffusion coefficients in char particles is important when interpreting experimental reactivity measurements and modeling char combustion or NO and N2O reduction. In this work, NO and N2O reaction with a bituminous coal char was studied in a fixed-bed quartz glass reactor....... In the case of strong pore diffusion limitations, the error in the interpretation of experimental results using the mean pore radius could be a factor of 5 on the intrinsic rate constant. For an average coal char reacting with oxygen at 1300 K, this would be the case for particle sizes larger than about 50...

Laboratory studies of low temperature rate coefficients: The atmospheric chemistry of the outer planets

Science.gov (United States)

Leone, Stephen R.

1995-01-01

The objectives of the research are to measure low temperature laboratory rate coefficients for key reactions relevant to the atmospheres of Titan and Saturn. These reactions are, for example, C2H + H2, CH4, C2H2, and other hydrocarbons which need to be measured at low temperatures, down to approximately 150 K. The results of this work are provided to NASA specialists who study modeling of the hydrocarbon chemistry of the outer planets. The apparatus for this work consists of a pulsed laser photolysis system and a tunable F-center probe laser to monitor the disappearance of C2H. A low temperature cell with a cryogenic circulating fluid in the outer jacket provides the gas handling system for this work. These elements have been described in detail in previous reports. Several new results are completed and the publications are just being prepared. The reaction of C2H with C2H2 has been measured with an improved apparatus down to 154 K. An Arrhenius plot indicates a clear increase in the rate coefficient at the lowest temperatures, most likely because of the long-lived (C4H3) intermediate. The capability to achieve the lowest temperatures in this work was made possible by construction of a new cell and addition of a multipass arrangement for the probe laser, as well as improvements to the laser system.

Accelerated load testing of geosynthetic base reinforced pavement test sections.

Science.gov (United States)

2011-02-01

The main objective of this research is to evaluate the benefits of geosynthetic stabilization and reinforcement of subgrade/base aggregate layers in flexible pavements built on weak subgrades and the effect of pre-rut pavement sections, prior to the ...

The rate of the reaction between CN and C2H2 at interstellar temperatures

Science.gov (United States)

Woon, D. E.; Herbst, E.

1997-01-01

The rate coefficient for the important interstellar reaction between CN and C2H2 has been calculated as a function of temperature between 10 and 300 K. The potential surface for this reaction has been determined through ab initio quantum chemical techniques; the potential exhibits no barrier in the entrance channel but does show a small exit channel barrier, which lies below the energy of reactants. Phase-space calculations for the reaction dynamics, which take the exit channel barrier into account, show the same unusual temperature dependence as determined by experiment, in which the rate coefficient at first increases as the temperature is reduced below room temperature and then starts to decrease as the temperature drops below 50-100 K. The agreement between theory and experiment provides strong confirmation that the reaction occurs appreciably at cool interstellar temperatures.

Instrumentation and analysis of frost heave mitigation on WY-70, Encampment, WY.

Science.gov (United States)

2014-05-01

This project investigated a novel procedure to reduce or prevent subgrade freezing non-destructively by injecting a two-part polymer foam at : the top of the subgrade. Controlled injection of Uretek Star, expanding structural polymer foam, created a ...

Comparison of field-measured radon diffusion coefficients with laboratory-measured coefficients

International Nuclear Information System (INIS)

Lepel, E.A.; Silker, W.B.; Thomas, V.W.; Kalkwarf, D.R.

1983-04-01

Experiments were conducted to compare radon diffusion coefficients determined for 0.1-m depths of soils by a steady-state method in the laboratory and diffusion coefficients evaluated from radon fluxes through several-fold greater depths of the same soils covering uranium-mill tailings. The coefficients referred to diffusion in the total pore volume of the soils and are equivalent to values for the quantity, D/P, in the Generic Environmental Impact Statement on Uranium Milling prepared by the US Nuclear Regulatory Commission. Two soils were tested: a well-graded sand and an inorganic clay of low plasticity. For the flux evaluations, radon was collected by adsorption on charcoal following passive diffusion from the soil surface and also from air recirculating through an aluminum tent over the soil surface. An analysis of variance in the flux evaluations showed no significant difference between these two collection methods. Radon diffusion coefficients evaluated from field data were statistically indistinguishable, at the 95% confidence level, from those measured in the laboratory; however, the low precision of the field data prevented a sensitive validation of the laboratory measurements. From the field data, the coefficients were calculated to be 0.03 +- 0.03 cm 2 /s for the sand cover and 0.0036 +- 0.0004 cm 2 /s for the clay cover. The low precision in the coefficients evaluated from field data was attributed to high variation in radon flux with time and surface location at the field site

A shock tube study of the branching ratios of propene + OH reaction

KAUST Repository

Badra, Jihad

2014-12-01

Absolute rate coefficients for the reaction of the OH radical with propene (C3H6) and five deuterated isotopes, propene-1-D1 (CDHCHCH3), propene-1,1-D2 (CD2CHCH3), propene-1,1,2-D3 (CD2CDCH3), propene-3,3,3-D3 (CH2CHCD3), and propene-D6 (C3D6), were measured behind reflected shock waves over the temperature range of 818-1460 K and pressures near 1 atm. The reaction progress was followed by monitoring the OH radical near 306.7 nm using UV laser absorption. Kinetic isotope effects in the measured rate coefficients are discussed and rationalized for the site-specific H-abstraction by the OH radical. The first experimental measurements for the branching ratio of the title reaction are reported and compared with transition state theory calculations. The allylic H-atom abstraction of propene by OH radicals was found to be the most dominant reaction pathway followed by propen-1-yl and propen-2-yl channels over the entire temperature range of this study. The derived Arrhenius expressions for various site-specific rate coefficients over 818-1442 K are (the subscript in the rate coefficient identifies the position of H or D atom according to the IUPAC nomenclature of alkenes):k3,H = 2.32 × 10-11 exp(-2341 K/T) cm3 molecule-1 s-1k3,D = 1.96 × 10-11 exp(-2420 K/T) cm3 molecule-1 s-1k1,H = 1.39 × 10-11 exp(-2270 K/T) cm3 molecule-1 s-1k1,D = 1.95 × 10-11 exp(-2868 K/T) cm3 molecule-1 s-1k2,H = 7.2 × 10-12 exp(-2282 K/T) cm3 molecule-1 s-1k2,D = 7.69 × 10-12 exp(-2575 K/T) cm3 molecule-1 s-1 This journal is

Recent results on the 3-loop heavy flavor Wilson coefficients in deep-inelastic scattering

Energy Technology Data Exchange (ETDEWEB)

Bluemlein, J.; Freitas A. de; Raab, C.; Wissbrock, F. [Deutsches Elektronen-Synchrotron (DESY), Zeuthen (Germany); Ablinger, J.; Hasselhuhn, A.; Round, M.; Schneider, C. [Johannes Kepler Univ., Linz (Austria). Research Inst. for Symbolic Computation; Manteuffel, A. von [Mainz Univ. (Germany). PRISMA Cluster of Excellence; Mainz Univ. (Germany). Inst. fuer Physik

2013-07-15

We report on recent progress in the calculation of the 3-loop massive Wilson coefficients in deep-inelastic scattering at general values of N for neutral and charged current reactions in the asymptotic region Q{sup 2}>>m{sup 2}.

Determination of S17 from the 7Be(d,n)8B reaction

International Nuclear Information System (INIS)

Ogata, Kazuyuki; Kamimura, Masayasu; Yahiro, Masanobu; Iseri, Yasunori

2003-01-01

The astrophysical factor S 17 for 7 Be(p,γ) 8 B reaction is reliably extracted from the transfer reaction 7 Be(d,n) 8 B at E=7.5 MeV with the asymptotic normalization coefficient method. The transfer reaction is accurately analyzed with CDCC based on a three-body model. This analysis is free from uncertainties of the optical potentials having been crucial in the previous DWBA analyses

Development of database on the distribution coefficient. 1. Collection of the distribution coefficient data

Energy Technology Data Exchange (ETDEWEB)

Takebe, Shinichi; Abe, Masayoshi [Japan Atomic Energy Research Inst., Tokai, Ibaraki (Japan). Tokai Research Establishment

2001-03-01

The distribution coefficient is very important parameter for environmental impact assessment on the disposal of radioactive waste arising from research institutes. The literature survey in the country was mainly carried out for the purpose of selecting the reasonable distribution coefficient value on the utilization of this value in the safety evaluation. This report was arranged much informations on the distribution coefficient for inputting to the database for each literature, and was summarized as a literature information data on the distribution coefficient. (author)

Benchmark calculations of thermal reaction rates. I - Quantal scattering theory

Science.gov (United States)

Chatfield, David C.; Truhlar, Donald G.; Schwenke, David W.

1991-01-01

The thermal rate coefficient for the prototype reaction H + H2 yields H2 + H with zero total angular momentum is calculated by summing, averaging, and numerically integrating state-to-state reaction probabilities calculated by time-independent quantum-mechanical scattering theory. The results are very carefully converged with respect to all numerical parameters in order to provide high-precision benchmark results for confirming the accuracy of new methods and testing their efficiency.

A new methodology for determining dispersion coefficient using ordinary and partial differential transport equations.

Science.gov (United States)

Cho, Kyung Hwa; Lee, Seungwon; Ham, Young Sik; Hwang, Jin Hwan; Cha, Sung Min; Park, Yongeun; Kim, Joon Ha

2009-01-01

The present study proposes a methodology for determining the effective dispersion coefficient based on the field measurements performed in Gwangju (GJ) Creek in South Korea which is environmentally degraded by the artificial interferences such as weirs and culverts. Many previous works determining the dispersion coefficient were limited in application due to the complexity and artificial interferences in natural stream. Therefore, the sequential combination of N-Tank-In-Series (NTIS) model and Advection-Dispersion-Reaction (ADR) model was proposed for evaluating dispersion process in complex stream channel in this study. The series of water quality data were intensively monitored in the field to determine the effective dispersion coefficient of E. coli in rainy day. As a result, the suggested methodology reasonably estimates the dispersion coefficient for GJ Creek with 1.25 m(2)/s. Also, the sequential combined method provided Number of tank-Velocity-Dispersion coefficient (NVD) curves for convenient evaluation of dispersion coefficient of other rivers or streams. Comparing the previous studies, the present methodology is quite general and simple for determining the effective dispersion coefficients which are applicable for other rivers and streams.

Recurrence relations between transformation coefficients of hyperspherical harmonics and their application to Moshinsky coefficients

International Nuclear Information System (INIS)

Raynal, J.

1976-01-01

Closed formulae and recurrence relations for the transformation of a two-body harmonic oscillator wave function to the hyperspherical formalism are given. With them Moshinsky or Smirnov coefficients are obtained from the transformation coefficients of hyperspheric harmonics. For these coefficients the diagonalization method of Talman and Lande reduces to simple recurrence relations which can be used directly to compute them. New closed formulae for these coefficients are also derived: they are needed to compute the two simplest coefficients which determine the sign for the recurrence relation. (Auth.)

Competitive cation binding computations of proton balance for reactions of the phosphagen and glycolytic energy systems within skeletal muscle

Science.gov (United States)

2017-01-01

Limited research and data has been published for the H+ coefficients for the metabolites and reactions involved in non-mitochondrial energy metabolism. The purpose of this investigation was to compute the fractional binding of H+, K+, Na+ and Mg2+ to 21 metabolites of skeletal muscle non-mitochondrial energy metabolism, resulting in 104 different metabolite-cation complexes. Fractional binding of H+ to these metabolite-cation complexes were applied to 17 reactions of skeletal muscle non-mitochondrial energy metabolism, and 8 conditions of the glycolytic pathway based on the source of substrate (glycogen vs. glucose), completeness of glycolytic flux, and the end-point of pyruvate vs. lactate. For pH conditions of 6.0 and 7.0, respectively, H+ coefficients (-‘ve values = H+ release) for the creatine kinase, adenylate kinase, AMP deaminase and ATPase reactions were 0.8 and 0.97, -0.13 and -0.02, 1.2 and 1.09, and -0.01 and -0.66, respectively. The glycolytic pathway is net H+ releasing, regardless of lactate production, which consumes 1 H+. For glycolysis fueled by glycogen and ending in either pyruvate or lactate, H+ coefficients for pH 6.0 and 7.0 were -3.97 and -2.01 (pyruvate), and -1.96 and -0.01 (lactate), respectively. When starting with glucose, the same conditions result in H+ coefficients of -3.98 and -2.67, and -1.97 and –0.67, respectively. The most H+ releasing reaction of glycolysis is the glyceraldehyde-3-phosphate dehydrogenase reaction, with H+ coefficients for pH 6.0 and 7.0 of -1.58 and -0.76, respectively. Incomplete flux of substrate through glycolysis would increase net H+ release due to the absence of the pyruvate kinase and lactate dehydrogenase reactions, which collectively result in H+ coefficients for pH 6.0 and 7.0 of 1.35 and 1.88, respectively. The data presented provide an extensive reference source for academics and researchers to accurately profile the balance of protons for all metabolites and reactions of non-mitochondrial energy

Competitive cation binding computations of proton balance for reactions of the phosphagen and glycolytic energy systems within skeletal muscle.

Science.gov (United States)

Robergs, Robert Andrew

2017-01-01

Limited research and data has been published for the H+ coefficients for the metabolites and reactions involved in non-mitochondrial energy metabolism. The purpose of this investigation was to compute the fractional binding of H+, K+, Na+ and Mg2+ to 21 metabolites of skeletal muscle non-mitochondrial energy metabolism, resulting in 104 different metabolite-cation complexes. Fractional binding of H+ to these metabolite-cation complexes were applied to 17 reactions of skeletal muscle non-mitochondrial energy metabolism, and 8 conditions of the glycolytic pathway based on the source of substrate (glycogen vs. glucose), completeness of glycolytic flux, and the end-point of pyruvate vs. lactate. For pH conditions of 6.0 and 7.0, respectively, H+ coefficients (-'ve values = H+ release) for the creatine kinase, adenylate kinase, AMP deaminase and ATPase reactions were 0.8 and 0.97, -0.13 and -0.02, 1.2 and 1.09, and -0.01 and -0.66, respectively. The glycolytic pathway is net H+ releasing, regardless of lactate production, which consumes 1 H+. For glycolysis fueled by glycogen and ending in either pyruvate or lactate, H+ coefficients for pH 6.0 and 7.0 were -3.97 and -2.01 (pyruvate), and -1.96 and -0.01 (lactate), respectively. When starting with glucose, the same conditions result in H+ coefficients of -3.98 and -2.67, and -1.97 and -0.67, respectively. The most H+ releasing reaction of glycolysis is the glyceraldehyde-3-phosphate dehydrogenase reaction, with H+ coefficients for pH 6.0 and 7.0 of -1.58 and -0.76, respectively. Incomplete flux of substrate through glycolysis would increase net H+ release due to the absence of the pyruvate kinase and lactate dehydrogenase reactions, which collectively result in H+ coefficients for pH 6.0 and 7.0 of 1.35 and 1.88, respectively. The data presented provide an extensive reference source for academics and researchers to accurately profile the balance of protons for all metabolites and reactions of non-mitochondrial energy

Competitive cation binding computations of proton balance for reactions of the phosphagen and glycolytic energy systems within skeletal muscle.

Directory of Open Access Journals (Sweden)

Robert Andrew Robergs

Full Text Available Limited research and data has been published for the H+ coefficients for the metabolites and reactions involved in non-mitochondrial energy metabolism. The purpose of this investigation was to compute the fractional binding of H+, K+, Na+ and Mg2+ to 21 metabolites of skeletal muscle non-mitochondrial energy metabolism, resulting in 104 different metabolite-cation complexes. Fractional binding of H+ to these metabolite-cation complexes were applied to 17 reactions of skeletal muscle non-mitochondrial energy metabolism, and 8 conditions of the glycolytic pathway based on the source of substrate (glycogen vs. glucose, completeness of glycolytic flux, and the end-point of pyruvate vs. lactate. For pH conditions of 6.0 and 7.0, respectively, H+ coefficients (-'ve values = H+ release for the creatine kinase, adenylate kinase, AMP deaminase and ATPase reactions were 0.8 and 0.97, -0.13 and -0.02, 1.2 and 1.09, and -0.01 and -0.66, respectively. The glycolytic pathway is net H+ releasing, regardless of lactate production, which consumes 1 H+. For glycolysis fueled by glycogen and ending in either pyruvate or lactate, H+ coefficients for pH 6.0 and 7.0 were -3.97 and -2.01 (pyruvate, and -1.96 and -0.01 (lactate, respectively. When starting with glucose, the same conditions result in H+ coefficients of -3.98 and -2.67, and -1.97 and -0.67, respectively. The most H+ releasing reaction of glycolysis is the glyceraldehyde-3-phosphate dehydrogenase reaction, with H+ coefficients for pH 6.0 and 7.0 of -1.58 and -0.76, respectively. Incomplete flux of substrate through glycolysis would increase net H+ release due to the absence of the pyruvate kinase and lactate dehydrogenase reactions, which collectively result in H+ coefficients for pH 6.0 and 7.0 of 1.35 and 1.88, respectively. The data presented provide an extensive reference source for academics and researchers to accurately profile the balance of protons for all metabolites and reactions of non

Reactions of the CN Radical with Benzene and Toluene: Product Detection and Low-Temperature Kinetics

Energy Technology Data Exchange (ETDEWEB)

Trevitt, Adam J.; Goulay, Fabien; Taatjes, Craig A.; Osborn, David L.; Leone, Stephen R.

2009-12-23

Low temperature rate coefficients are measured for the CN + benzene and CN + toluene reactions using the pulsed Laval nozzle expansion technique coupled with laser-induced fluorescence detection. The CN + benzene reaction rate coefficient at 105, 165 and 295 K is found to be relatively constant over this temperature range, 3.9 - 4.9 x 10-10 cm3 molecule-1 s-1. These rapid kinetics, along with the observed negligible temperature dependence, are consistent with a barrierless reaction entrance channel and reaction efficiencies approaching unity. The CN + toluene reaction is measured to have a slower rate coefficient of 1.3 x 10-10 cm3 molecule-1 s-1 at 105 K. At room temperature, non-exponential decay profiles are observed for this reaction that may suggest significant back-dissociation of intermediate complexes. In separate experiments, the products of these reactions are probed at room temperature using synchrotron VUV photoionization mass spectrometry. For CN + benzene, cyanobenzene (C6H5CN) is the only product recorded with no detectable evidence for a C6H5 + HCN product channel. In the case of CN + toluene, cyanotoluene (NCC6H4CH3) constitutes the only detected product. It is not possible to differentiate among the ortho, meta and para isomers of cyanotoluene because of their similar ionization energies and the ~;; 40 meV photon energy resolution of the experiment. There is no significant detection of benzyl radicals (C6H5CH2) that would suggest a H-abstraction or a HCN elimination channel is prominent at these conditions. As both reactions are measured to be rapid at 105 K, appearing to have barrierless entrance channels, it follows that they will proceed efficiently at the temperatures of Saturn?s moon Titan (~;;100 K) and are also likely to proceed at the temperature of interstellar clouds (10-20 K).

Hot wire radicals and reactions

International Nuclear Information System (INIS)

Zheng Wengang; Gallagher, Alan

2006-01-01

Threshold ionization mass spectroscopy is used to measure radical (and stable gas) densities at the substrate of a tungsten hot wire (HW) reactor. We report measurements of the silane reaction probability on the HW and the probability of Si and H release from the HW. We describe a model for the atomic H release, based on the H 2 dissociation model. We note major variations in silicon-release, with dependence on prior silane exposure. Measured radical densities versus silane pressure yield silicon-silane and H-silane reaction rate coefficients, and the dominant radical fluxes to the substrate

A library of prompt detonation reaction zone data

Energy Technology Data Exchange (ETDEWEB)

Souers, P. C., LLNL

1998-06-01

Tables are given listing literature data that allows calculation of sonic reaction zones at or near steady-state for promptly detonating explosive cylinders. The data covers homogeneous, heterogeneous, composite, inorganic and binary explosives and allows comparison across the entire explosive field. Table 1 lists detonation front curvatures. Table 2 lists Size Effect data, i.e. the change of detonation velocity with cylinder radius. Table 3 lists failure radii and detonation velocities. Table 4 lists explosive compositions. A total of 51 references dating back into the 1950`s are given. Calculated reaction zones, radii of curvature and growth rate coefficients are listed.

The reactions of oxygen and hydrogen with liquid sodium

International Nuclear Information System (INIS)

Ullmann, H.

1981-01-01

Results so far available as to the reactions and chemical equilibrium of oxygen and hydrogen with liquid sodium have been analyzed critically. The enthalpy values of the reactions have been discussed and supplemented on the basis of corresponding BORN-HABER cycles. The concentration and temperature functions of the hydrogen equilibrium pressure were deduced from experimental results. In relation to the solubility data the solid phases coexisting with liquid sodium in the ternary system Na-O-H have been discussed. The reaction of oxygen with hydrogen in diluted solution in liquid sodium has been investigated in more detail. Interaction coefficients, and the temperature functions of the free energy of formation and the equilibrium constant have been determined. (orig.)

Temperature Dependent Rate Coefficients for the Gas-Phase Reaction of the OH Radical with Linear (L2, L3) and Cyclic (D3, D4) Permethylsiloxanes.

Science.gov (United States)

Bernard, François; Papanastasiou, Dimitrios K; Papadimitriou, Vassileios C; Burkholder, James B

2018-04-19

Permethylsiloxanes are emitted into the atmosphere during production and use as personal care products, lubricants, and cleaning agents. The predominate atmospheric loss process for permethylsiloxanes is expected to be via gas-phase reaction with the OH radical. In this study, rate coefficients, k(T), for the OH radical gas-phase reaction with the two simplest linear and cyclic permethylsiloxanes were measured using a pulsed laser photolysis-laser induced fluorescence technique over the temperature range of 240-370 K and a relative rate method at 294 K: hexamethyldisiloxane ((CH 3 ) 3 SiOSi(CH 3 ) 3 , L 2 ), k 1 ; octamethyltrisiloxane ([(CH 3 ) 3 SiO] 2 Si(CH 3 ) 2 , L 3 ), k 2 ; hexamethylcyclotrisiloxane ([-Si(CH 3 ) 2 O-] 3 , D 3 ), k 3 ; and octamethylcyclotetrasiloxane ([-Si(CH 3 ) 2 O-] 4 , D 4 ), k 4 . The obtained k(294 K) values and temperature-dependence expressions for the 240-370 K temperature range are (cm 3 molecule -1 s -1 , 2σ absolute uncertainties): k 1 (294 K) = (1.28 ± 0.08) × 10 -12 , k 1 ( T) = (1.87 ± 0.18) × 10 -11 exp(-(791 ± 27)/ T); k 2 (294 K) = (1.72 ± 0.10) × 10 -12 , k 2 ( T) = 1.96 × 10 -13 (T/298) 4.34 exp(657/ T); k 3 (294 K) = (0.82 ± 0.05) × 10 -12 , k 3 ( T) = (1.29 ± 0.19) × 10 -11 exp(-(805 ± 43)/ T); and k 4 (294 K) = (1.12 ± 0.10) × 10 -12 , k 4 ( T) = (1.80 ± 0.26) × 10 -11 exp(-(816 ± 43)/ T). The cyclic molecules were found to be less reactive than the analogous linear molecule with the same number of -CH 3 groups, while the linear and cyclic permethylsiloxane reactivity both increase with the increasing number of CH 3 - groups. The present results are compared with previous rate coefficient determinations where available. The permethylsiloxanes included in this study are atmospherically short-lived compounds with estimated atmospheric lifetimes of 11, 8, 17, and 13 days, respectively.

Resilient behavior characterization of geomaterials for pavement design

CSIR Research Space (South Africa)

Anochie-Boateng, Joseph

2010-08-01

Full Text Available in the laboratory on the subgrade samples to obtain MR and CBR data to develop the empirical models. The results suggest that constitutive models obtained directly from laboratory test data would be more appropriate to characterize the resilient behavior of subgrade...

Engineering Properties of Bentonite Stabilized with Lime and Phosphogypsum

Directory of Open Access Journals (Sweden)

Kumar Sujeet

2014-12-01

Full Text Available Engineering properties such as compaction, unconfined compressive strength, consistency limits, percentage swell, free swell index, the California bearing ratio and the consolidation of bentonite stabilized with lime and phosphogypsum are presented in this paper. The content of the lime and phosphogypsum varied from 0 to 10 %. The results reveal that the dry unit weight and optimum moisture content of bentonite + 8 % lime increased with the addition of 8 % phosphogypsum. The percentage of swell increased and the free swell index decreased with the addition of 8 % phosphogypsum to the bentonite + 8 % lime mix. The unconfined compressive strength of the bentonite + 8 % lime increased with the addition of 8 % phosphogypsum as well as an increase in the curing period up to 14 days. The liquid limit and plastic limit of the bentonite + 8 % lime increased, whereas the plasticity index remained constant with the addition of 8 % phosphogypsum. The California bearing ratio, modulus of subgrade reaction, and secant modulus increased for the bentonite stabilized with lime and phosphogypsum. The coefficient of the consolidation of the bentonite increased with the addition of 8 % lime and no change with the addition of 8 % phosphogypsum.

Absorption coefficients for water vapor at 193 nm from 300 to 1073 K

Science.gov (United States)

Kessler, W. J.; Carleton, K. L.; Marinelli, W. J.

1993-01-01

Measurements of the water absorption coefficient at 193 nm from 300 to 1073 K are reported. The measurements were made using broadband VUV radiation and a monochromator-based detection system. The water vapor was generated by a saturator and metered into a flowing, 99 cm absorption cell via a water vapor mass flow meter. The 193 nm absorption coefficient measurements are compared to room temperature and high temperature shock tube measurements with good agreement. The absorption can be parameterized by a nu3 vibrational mode reaction coordinate and the thermal population of the nu3 mode.

Effect of heat and mass transfer coefficients on the performance of automotive catalytic converters

Energy Technology Data Exchange (ETDEWEB)

Shamim, T. [Michigan Univ., Dept. of Mechanical Engineering, Dearborn, MI (United States)

2003-06-01

This paper numerically investigates the role of heat and mass transfer coefficients on the performance of automotive catalytic converters, which are employed to reduce engine exhaust emissions. The pollutant conversion performance of a converter is influenced by a number of physical and chemical processes that take place in gaseous and solid phases as the exhaust gases flow through the catalyst. A quantitative predictive understanding of these complex catalyst processes involving flow dynamics, heterogeneous surface reactions and heat and mass transport mechanisms is important in improving the converter design. The role of convective transport phenomena becomes important at high temperature when the mass transfer becomes rate-limiting to an increasing extent. The objective of the present study is to elucidate the influence of convective heat and mass transfer coefficients (mechanisms). The mathematical model considers the conservation of mass, momentum and energy in both gaseous and solid phases. In addition to the heterogeneous surface reactions, the model also takes into account the adsorption/desorption of oxygen in the catalyst during non-stoichiometric composition of air/fuel mixtures. The governing equations are solved by an implicit scheme using a successive line under a relaxation method. The converter performance under the transient conditions as simulated by the US Federal Test Procedure (US-FTP) is analysed. (Author)

Kinetics of nitrosamine and amine reactions with NO3 radical and ozone related to aqueous particle and cloud droplet chemistry

Science.gov (United States)

Weller, Christian; Herrmann, Hartmut

2015-01-01

Aqueous phase reactivity experiments with the amines dimethylamine (DMA), diethanolamine (DEA) and pyrrolidine (PYL) and their corresponding nitrosamines nitrosodimethylamine (NDMA), nitrosodiethanolamine (NDEA) and nitrosopyrrolidine (NPYL) have been performed. NO3 radical reaction rate coefficients for DMA, DEA and PYL were measured for the first time and are 3.7 × 105, 8.2 × 105 and 8.7 × 105 M-1 s-1, respectively. Rate coefficients for NO3 + NDMA, NDEA and NPYL are 1.2 × 108, 2.3 × 108 and 2.4 × 108 M-1 s-1. Compared to OH radical rate coefficients for reactions with amines, the NO3 radical will most likely not be an important oxidant but it is a potential nighttime oxidant for nitrosamines in cloud droplets or deliquescent particles. Ozone is unreactive towards amines and nitrosamines and upper limits of rate coefficients suggest that aqueous ozone reactions are not important in atmospheric waters.

Model for competitive binary and ternary ion-molecule reactions

International Nuclear Information System (INIS)

Herbst, E.

1985-01-01

A mechanism by which competitive binary and ternary ion-molecule reactions can occur is proposed. Calculations are undertaken for the specific system CH3(+) + NH3 + He which has been studied in the laboratory by Smith and Adams (1978), and the potential surface of which has been studied theoretically by Nobes and Radom (1983). It is shown that a potential-energy barrier in the exit channel prevents the rapid dissociation of collision complexes with large amounts of angular momentum and thereby allows collisional stabilization of the complexes. The calculated ternary-reaction rate coefficient is in good agreement with the experimental value, but a plot of the effective two-body rate coefficient of the ternary channel vs helium density does not quite show the observed saturation. 21 references

(4+2) Cycloaddition reactions with inverse electron demand of nitrogen bearing, heteroaromatic cations

International Nuclear Information System (INIS)

Ritzberger-Baumgartner, W.

1996-06-01

Three cationic, heteroaromatic diene-systems (1, 2, 3, 4-tetramethoxycarbonyl-quinolizinium-tetrafluoroborate (M), 8, 9, 10, 11-tetrarnethoxycarbonylpyrido[2,1-a]-isoquinolinium-TFB and triazolo[1,5-b]isoquinolinium-TFBs) and a cationic, non-aromatic diene (2,5,5-trimethyl-3-oxo-1, 2, 4-triazolium-TFB) were synthesized. The dienes were employed successfully in cycloaddition reactions with a number ofconjugated dienophiles (including norbornene). The mechanism underlying these cycloaddition reactions was discussed in the theoretical section. At first quantumchemical calculations of the frontier orbital energies provided the proof, that the reactions followed the pattern of reactions with inverse electron demand. Calculation of the charge distribution and of the orbital coefficients led to the conclusion, that these reactions are mainly orbital controlled. Two mechanistic variants were in discussion. Either the reactions proceed in a concerted manner resembling the Diels-Alder reaction with inverse electron demand or in two distinct steps with the formation of a cationic intermediate following the attack of the heterodienes acting as weak electrophiles at the dienophiles being weak nucleophiles. Calculations of a possible transition state of these cycloaddition reactions revealed a pronounced preference for the formation of the bond between the logical reaction centers in the first step of a two-step reaction. However, experimental and theoretical findings led to the conviction, that cationic polar cycloaddition reactions proceed exactly along the crossroad between a concerted and a two-step mechanism and depending on the electrophilic strength of the diene and the nucleophilic strength of the dienophile these reactions show more characteristics of one of the two mechanistic possibilities. The high regioselectivity as well as the high stereoselectivity could be explained satisfactory with the help of the calculated orbital coefficients. (author)

A Method for the Determination of Bi-substrate Kinetic Coefficients: the Example of the b-D-glucose- NAD-GDH Enzymatic Reaction

Directory of Open Access Journals (Sweden)

Jean BERTHIER

2015-08-01

Full Text Available Colorimetric detection of glucose in sample liquids such as human plasma is made by using enzymatic reactions. Either glucose oxidase (GOX or glucose dehydrogenase (GDH can be used to convert glucose. In the multi reactional scheme, the first enzymatic reaction is determinant. We focused here on the study of the enzyme GDH together with the enzymatic cofactor NAD (nicotinamide adenine dinucleotide. This reaction falls in the category of ternary enzymatic reactions. Such reactions depend on four parameters. A method to determine these four parameters is presented in this work, based on a comparison between a series of experiments and the theory. The best values of the parameters are indicated.

Translation into Portuguese and validation of the Blood Donation Reactions Inventory

Directory of Open Access Journals (Sweden)

Ana Carolina Garcia Braz

2014-04-01

Full Text Available Background: the Blood Donation Reactions Inventory (BDRI scale was proposed as part of a study about the predictors of psychological reactions in volunteer blood donors, as uncomfortable reactions are associated with a lower probability to return for further donations. Objective: to translate the Inventory into Brazilian Portuguese and evaluate its psychometric properties (validity and reliability. The inventory has 11 items, but the literature suggests that shorter inventories, of four or six items, should be used. Methods: this study was carried out at the blood center of Franca, Brazil. Three people with knowledge of English and familiarity with medical terms translated the Blood Donation Reactions Inventory into Brazilian Portuguese. Aiming to evaluate the objectivity and relevance of the items of the translated instrument, its content was independently evaluated by a panel of eight assessors. After this, data on 1,001 blood donors was collected. Internal consistency was assessed by Cronbach's alpha coefficient. An exploratory factor analysis with varimax rotation was used to analyze the measure for construct validity. Results: the sample consisted of 65.8% men, and 27.3% first time donors. Internal consistency determined by Cronbach's alpha coefficient was satisfactory for the 11, 6 and 4-item scales. Considering the factor analysis, the 11-item scale seems to measure more than one construct as three factors were identified with eigenvalues greater than 1. These factors correspond to 'vasovagal adverse reactions', 'fear' and 'anxiety/excitation'. Conclusion: the Portuguese version of the Blood Donation Reactions Inventory is a valid and reliable instrument for collecting information regarding systemic reactions experienced by blood donors. The 6-item scale seems to be useful when the objective is to measure only vasovagal adverse reactions.

An experimental approach of decoupling Seebeck coefficient and electrical resistivity

Science.gov (United States)

Muhammed Sabeer N., A.; Paulson, Anju; Pradyumnan, P. P.

2018-04-01

The Thermoelectrics (TE) has drawn increased attention among renewable energy technologies. The performance of a thermoelectric material is quantified by a dimensionless thermoelectric figure of merit, ZT=S2σT/κ, where S and σ vary inversely each other. Thus, improvement in ZT is not an easy task. So, researchers have been trying different parameter variations during thin film processing to improve TE properties. In this work, tin nitride (Sn3N4) thin films were deposited on glass substrates by reactive RF magnetron sputtering and investigated its thermoelectric response. To decouple the covariance nature of Seebeck coefficient and electrical resistivity for the enhancement of power factor (S2σ), the nitrogen gas pressure during sputtering was reduced. Reduction in nitrogen gas pressure reduced both sputtering pressure and amount of nitrogen available for reaction during sputtering. This experimental approach of combined effect introduced preferred orientation and stoichiometric variations simultaneously in the sputtered Sn3N4 thin films. The scattering mechanism associated with these variations enhanced TE properties by independently drive the Seebeck coefficient and electrical resistivity parameters.

A shock tube study of the branching ratios of propene + OH reaction

KAUST Repository

Badra, Jihad; Khaled, Fathi; Giri, Binod Raj; Farooq, Aamir

2014-01-01

coefficients are discussed and rationalized for the site-specific H-abstraction by the OH radical. The first experimental measurements for the branching ratio of the title reaction are reported and compared with transition state theory calculations. The allylic

Theoretical investigation of exchange and recombination reactions in O(3P)+NO(2Π) collisions

International Nuclear Information System (INIS)

Ivanov, M. V.; Zhu, H.; Schinke, R.

2007-01-01

We present a detailed dynamical study of the kinetics of O( 3 P)+NO( 2 Π) collisions including O atom exchange reactions and the recombination of NO 2 . The classical trajectory calculations are performed on the lowest 2 A ' and 2 A '' potential energy surfaces, which were calculated by ab initio methods. The calculated room temperature exchange reaction rate coefficient, k ex , is in very good agreement with the measured one. The high-pressure recombination rate coefficient, which is given by the formation rate coefficient and to a good approximation equals 2k ex , overestimates the experimental data by merely 20%. The pressure dependence of the recombination rate, k r , is described within the strong-collision model by assigning a stabilization probability to each individual trajectory. The measured falloff curve is well reproduced over five orders of magnitude by a single parameter, i.e., the strong-collision stabilization frequency. The calculations also yield the correct temperature dependence, k r ∝T -1.5 , of the low-pressure recombination rate coefficient. The dependence of the rate coefficients on the oxygen isotopes are investigated by incorporating the difference of the zero-point energies between the reactant and product NO radicals, Δ ZPE , into the potential energy surface. Similar isotope effects as for ozone are predicted for both the exchange reaction and the recombination. Finally, we estimate that the chaperon mechanism is not important for the recombination of NO 2 , which is in accord with the overall T -1.4 dependence of the measured recombination rate even in the low temperature range

Measuring of heat transfer coefficient

DEFF Research Database (Denmark)

Henningsen, Poul; Lindegren, Maria

Subtask 3.4 Measuring of heat transfer coefficient Subtask 3.4.1 Design and setting up of tests to measure heat transfer coefficient Objective: Complementary testing methods together with the relevant experimental equipment are to be designed by the two partners involved in order to measure...... the heat transfer coefficient for a wide range of interface conditions in hot and warm forging processes. Subtask 3.4.2 Measurement of heat transfer coefficient The objective of subtask 3.4.2 is to determine heat transfer values for different interface conditions reflecting those typically operating in hot...

Electron-transport, ionization, attachment, and dissociation coefficients in SF6 and its mixtures

International Nuclear Information System (INIS)

Phelps, A.V.; Van Brunt, R.J.

1988-01-01

An improved set of electron-collision cross sections is derived for SF 6 and used to calculate transport, ionization, attachment, and dissociation coefficients for pure SF 6 and mixtures of SF 6 with N 2 , O 2 , and Ne. The SF 6 cross sections differ from previously published sets primarily at very low and high electron energies. At energies below 0.03 eV the attachment cross section is adjusted to fit recent electron swarm experiments, while the elastic momentum transfer cross section is increased to the theoretical limit. At high energies an allowance is made for the excitation of highly excited levels as observed in electron beam experiments. The cross-section sets used for the admixed gases have previously been published. Electron kinetic energy distributions computed from numerical solutions of the electron-transport (Boltzmann) equation using the two-term, spherical harmonic expansion approximation were used to obtain electron-transport and reaction coefficients as functions of E/N and the fractional concentration of SF 6 . Here E is the electric field strength and N is the gas number density. Attachment rate data for low concentrations of SF 6 in N 2 are used to test the attachment cross sections. Particular attention is given to the calculation of transport and reaction coefficients at the critical E/N = (E/N)/sub c/ at which the ionization and attachment rates are equal

Nuclear Data Uncertainty Propagation to Reactivity Coefficients of a Sodium Fast Reactor

Science.gov (United States)

Herrero, J. J.; Ochoa, R.; Martínez, J. S.; Díez, C. J.; García-Herranz, N.; Cabellos, O.

2014-04-01

The assessment of the uncertainty levels on the design and safety parameters for the innovative European Sodium Fast Reactor (ESFR) is mandatory. Some of these relevant safety quantities are the Doppler and void reactivity coefficients, whose uncertainties are quantified. Besides, the nuclear reaction data where an improvement will certainly benefit the design accuracy are identified. This work has been performed with the SCALE 6.1 codes suite and its multigroups cross sections library based on ENDF/B-VII.0 evaluation.

Temperature dependence of three-body ion-molecule reactions

International Nuclear Information System (INIS)

Boehringer, H.; Arnold, F.

1983-01-01

The temperature dependence of the ion-molecule association reactions (i) N 2 + + N 2 + M → N 4 + + M (M=N 2 , He), (ii) O 2 + + O 2 + M → O 4 + + M (M=O 2 , He) and (iii) He + + 2He → He 2 + + He have been studied over an extended temperature range to temperatures as low as 30K with a recently constructed liquid helium-cooled ion drift tube. Over most of the temperature range the threebody reaction rate coefficients show an inverse temperature dependence proportional to Tsup(-n) with n in the range 0.6 to 2.9. This temperature dependence is quite consistent with current theories of ion molecule association. At low temperatures, however, a deviation from the Tsup(-n) dependence was observed for the association reactions (ii). For reactions (i) different temperature dependences were obtained for N 2 and He third bodies indicating an additional temperature dependence of the collisional stabilisation process. (Authors)

Rate Coefficient for the (4)Heμ + CH4 Reaction at 500 K: Comparison between Theory and Experiment.

Science.gov (United States)

Arseneau, Donald J; Fleming, Donald G; Li, Yongle; Li, Jun; Suleimanov, Yury V; Guo, Hua

2016-03-03

The rate constant for the H atom abstraction reaction from methane by the muonic helium atom, Heμ + CH4 → HeμH + CH3, is reported at 500 K and compared with theory, providing an important test of both the potential energy surface (PES) and reaction rate theory for the prototypical polyatomic CH5 reaction system. The theory used to characterize this reaction includes both variational transition-state (CVT/μOMT) theory (VTST) and ring polymer molecular dynamics (RPMD) calculations on a recently developed PES, which are compared as well with earlier calculations on different PESs for the H, D, and Mu + CH4 reactions, the latter, in particular, providing for a variation in atomic mass by a factor of 36. Though rigorous quantum calculations have been carried out for the H + CH4 reaction, these have not yet been extended to the isotopologues of this reaction (in contrast to H3), so it is important to provide tests of less rigorous theories in comparison with kinetic isotope effects measured by experiment. In this regard, the agreement between the VTST and RPMD calculations and experiment for the rate constant of the Heμ + CH4 reaction at 500 K is excellent, within 10% in both cases, which overlaps with experimental error.

Ion-neutral gas reactions in a collision/reaction cell in inductively coupled plasma mass spectrometry: Correlation of ion signal decrease to kinetic rate constants

Energy Technology Data Exchange (ETDEWEB)

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.

Stabilisasi Tanah Liat Dengan Kapur Pada Konstruksi Badan Jalan Hutan Di Pulau Laut

OpenAIRE

Suparto, Rahardjo S; Sutopo, S

1984-01-01

Subgrade construction is an important part in forest road building, Subgrade soils with a high clay content could not be used satisfactorily as forest road construction material unless it is treated to increase its stability. The improvement of the physical characteristics of clay soils related to subgrade construction can be achieved by mixing lime of certain proportion into the soil. The purpose of this investigation is to determine the amount of lime required for s...

Quantifying atom addition reactions on amorphous solid water: a review of recent laboratory advances

Science.gov (United States)

He, Jiao; Vidali, Gianfranco

2018-06-01

Complex organic molecules found in space are mostly formed on and in the ice mantle covering interstellar dust grains. In clouds where ionizing irradiation is insignificant, chemical reactions on the ice mantle are dominated by thermal processes. Modeling of grain surface chemistry requires detailed information from the laboratory, including sticking coefficients, binding energies, diffusion energy barriers, mechanism of reaction, and chemical desorption rates. In this talk, recent laboratory advances in obtaining these information would be reviewed. Specifically, this talk will focus on the efforts in our group in: 1) Determining the mechanism of atomic hydrogen addition reactions on amorphous solid water (ASW); 2) Measuring the chemical desorption coefficient of H+O3-->O2+OH using the time-resolved scattering technique; and 3) Measuring the diffusion energy barrier of volatile molecules on ASW. Further laboratory studies will be suggested.This research was supported by NSF Astronomy & Astrophysics Research Grant #1615897.

Form of multicomponent Fickian diffusion coefficients matrix

International Nuclear Information System (INIS)

Wambui Mutoru, J.; Firoozabadi, Abbas

2011-01-01

Highlights: → Irreversible thermodynamics establishes form of multicomponent diffusion coefficients. → Phenomenological coefficients and thermodynamic factors affect sign of diffusion coefficients. → Negative diagonal elements of diffusion coefficients matrix can occur in non-ideal mixtures. → Eigenvalues of the matrix of Fickian diffusion coefficients may not be all real. - Abstract: The form of multicomponent Fickian diffusion coefficients matrix in thermodynamically stable mixtures is established based on the form of phenomenological coefficients and thermodynamic factors. While phenomenological coefficients form a symmetric positive definite matrix, the determinant of thermodynamic factors matrix is positive. As a result, the Fickian diffusion coefficients matrix has a positive determinant, but its elements - including diagonal elements - can be negative. Comprehensive survey of reported diffusion coefficients data for ternary and quaternary mixtures, confirms that invariably the determinant of the Fickian diffusion coefficients matrix is positive.

Synchronization criteria for generalized reaction-diffusion neural networks via periodically intermittent control.

Science.gov (United States)

Gan, Qintao; Lv, Tianshi; Fu, Zhenhua

2016-04-01

In this paper, the synchronization problem for a class of generalized neural networks with time-varying delays and reaction-diffusion terms is investigated concerning Neumann boundary conditions in terms of p-norm. The proposed generalized neural networks model includes reaction-diffusion local field neural networks and reaction-diffusion static neural networks as its special cases. By establishing a new inequality, some simple and useful conditions are obtained analytically to guarantee the global exponential synchronization of the addressed neural networks under the periodically intermittent control. According to the theoretical results, the influences of diffusion coefficients, diffusion space, and control rate on synchronization are analyzed. Finally, the feasibility and effectiveness of the proposed methods are shown by simulation examples, and by choosing different diffusion coefficients, diffusion spaces, and control rates, different controlled synchronization states can be obtained.

The correlation schemes in calculations of the rate constants of some radiation chemical reactions

International Nuclear Information System (INIS)

Zagorets, P.A.; Shostenko, A.G.; Kim, V.

1983-01-01

The various correlation relationships of the evaluation of the rate constants of radiation chemical reactions of addition, abstraction and isomerization were considered. It was shown that neglection of the influence of solvent can result in errors in calculations of rate constants equalling two orders in magnitude. Several examples of isokinetic relationship are given. The methods of calculation of transmission coefficient of reaction addition have been discussed. (author)

Transport Coefficients of Fluids

CERN Document Server

Eu, Byung Chan

2006-01-01

Until recently the formal statistical mechanical approach offered no practicable method for computing the transport coefficients of liquids, and so most practitioners had to resort to empirical fitting formulas. This has now changed, as demonstrated in this innovative monograph. The author presents and applies new methods based on statistical mechanics for calculating the transport coefficients of simple and complex liquids over wide ranges of density and temperature. These molecular theories enable the transport coefficients to be calculated in terms of equilibrium thermodynamic properties, and the results are shown to account satisfactorily for experimental observations, including even the non-Newtonian behavior of fluids far from equilibrium.

Investigation of coulomb and pairing effects using new developed empirical formulas for proton-induced reaction cross sections

International Nuclear Information System (INIS)

Tel, E.; Aydin, E. G.; Aydin, A.; Kaplan, A.; Boeluekdemir, M. H.; Okuducu, S.

2010-01-01

We have investigated Coulomb and pairing effects by using new empirical formulas including the new coefficients for (p, α) at 17.9 MeV, (p, np) at 22.3 MeV, and (p, nα) at 24.8 and 28.5 MeV energies. A new formula is obtained by adjusting Levkovskii's original asymmetry parameter formula and also Tel et al. formula for proton-induced reactions. The new coefficients by using least-squares fitting method for the reactions are determined. In addition, the findings of the present study are compared with the available experimental data.

Infectious uveitis in immunocompromised patients and the diagnostic value of polymerase chain reaction and Goldmann-Witmer coefficient in aqueous analysis.

Science.gov (United States)

Westeneng, Arnaud C; Rothova, Aniki; de Boer, Joke H; de Groot-Mijnes, Jolanda D F

2007-11-01

To establish the causes of uveitis in immunocompromised patients and to determine the contribution of polymerase chain reaction (PCR) and Goldmann-Witmer coefficient (GWC) analysis of aqueous humor in patients with an infectious etiology. Retrospective case series of 56 consecutive immunocompromised patients with uveitis. All patients underwent full ophthalmologic examination and laboratory blood analysis for uveitis. Aqueous humor analyses were performed using PCR and GWC for cytomegalovirus (CMV), herpes simplex virus (HSV), varicella zoster virus (VZV), and Toxoplasma gondii. Of 56 immunocompromised patients, 43 (77%), all posterior and panuveitis, had intraocular infections. Twenty-one (49%) had CMV, three (7%) had VZV, 11 (26%) had T. gondii, six (14%) had Treponema pallidum, and one (2%) each had Aspergillus and Candida. In AIDS patients, CMV was the most common cause. A strong correlation between AIDS and ocular syphilis was also observed (P = .007). In nonAIDS immunocompromised patients, T. gondii was most frequently detected. Twenty-seven patients were examined by both PCR and GWC; five (18.5%) were positive by both assays, 15 (55.5%) were positive by PCR alone and seven (26%) by GWC alone. Viral infections were detected by PCR in 16 of 17 (94%) cases; T. gondii in four of 10 (40%) patients. Using GWC, a viral infection was diagnosed in three of 17 (18%) and T. gondii in nine of 10 (90%) cases. In immunocompromised patients, PCR is superior in diagnosing viral infections. Analysis of intraocular antibody production played a decisive role in the diagnosis of ocular toxoplasmosis.

Investigation of heterogeneous reactions of NO2 on aqueous surfaces

International Nuclear Information System (INIS)

Mertes, S.

1992-01-01

A microjet apparatus was developed for the purpose of measuring the loss in the gaseous phase and the uptake in the liquid phase of nitrogen on the basis of heterogeneous processes on a liquid surface. The measurements were to provide information on the mass accomodation coefficient α and on assumed surface reactions of NO 2 . (orig./BBR) [de

Variational RRKM calculation of thermal rate constant for C–H bond fission reaction of nitro methane

Directory of Open Access Journals (Sweden)

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.

Dose conversion coefficients for high-energy photons, electrons, neutrons and protons

International Nuclear Information System (INIS)

Sakamoto, Yukio

2005-01-01

Dose conversion coefficients for photons, electrons and neutrons based on new ICRP recommendations were cited in the ICRP Publication 74, but the energy ranges of these data were limited and there are no data for high energy radiations produced in accelerator facilities. For the purpose of designing the high intensity proton accelerator facilities at JAERI, the dose evaluation code system of high energy radiations based on the HERMES code was developed and the dose conversion coefficients of effective dose were evaluated for photons, neutrons and protons up to 10 GeV, and electrons up to 100 GeV. The dose conversion coefficients of effective dose equivalent were also evaluated using quality factors to consider the consistency between radiation weighting factors and Q-L relationship. The effective dose conversion coefficients obtained in this work were in good agreement with those recently evaluated by using FLUKA code for photons and electrons with all energies, and neutrons and protons below 500 MeV. There were some discrepancy between two data owing to the difference of cross sections in the nuclear reaction models. The dose conversion coefficients of effective dose equivalents for high energy radiations based on Q-L relation in ICRP Publication 60 were evaluated only in this work. The previous comparison between effective dose and effective dose equivalent made it clear that the radiation weighting factors for high energy neutrons and protons were overestimated and the modification was required. (author)

Asymptotic normalization coefficients, nuclear vertex constants and nuclear astrophysics problems

International Nuclear Information System (INIS)

Yarmukhamedov, R.; Artemov, S.V.; Igamov, S.B.; Burtebaev, N.; Peterson, R.J.

2007-01-01

Full text: We will review the results of a comprehensive analysis of the experimental astrophysical S- factors S(E) for the t(α, γ ) 7 Li, 3 He(α, γ) 7 Be, 7 Be(p, γ) 8 B, 12 C(p , γ) 13 N and 13 C(p,γ) 14 N reactions at extremely low energies, performed within a three-sided collaboration (Uzbekistan-Kazakhstan-USA). In the analysis, the new experimental data for the 12 C(p, γ) 13 N reaction are also included, as measured with the accelerator UKP-2-1 at the Institute of Nuclear Physics in Kazakhstan. The analysis is carried out within the framework of a new two-body potential approach and the R-matrix method, taking into account information about the asymptotic normalization coefficient (ANC) (or the respective nuclear vertex constant for virtual decay of the residual nuclei into two fragments of the initial states of the aforesaid reactions, which belong to the fundamental nuclear constants). Nowadays ANC's are obtained from analysis of peripheral one nucleon transfer reactions by method combining dispersion theory and DWBA (CM). It is shown that ANC can be also reliably obtained from analysis of proton capture reactions at astrophysical energies by new modified two-body potential method where the CM is used. A comparative analysis of the results obtained by different authors in the framework of different methods is also done

Comparison of different methods to extract the required coefficient of friction for level walking.

Science.gov (United States)

Chang, Wen-Ruey; Chang, Chien-Chi; Matz, Simon

2012-01-01

The required coefficient of friction (RCOF) is an important predictor for slip incidents. Despite the wide use of the RCOF there is no standardised method for identifying the RCOF from ground reaction forces. This article presents a comparison of the outcomes from seven different methods, derived from those reported in the literature, for identifying the RCOF from the same data. While commonly used methods are based on a normal force threshold, percentage of stance phase or time from heel contact, a newly introduced hybrid method is based on a combination of normal force, time and direction of increase in coefficient of friction. Although no major differences were found with these methods in more than half the strikes, significant differences were found in a significant portion of strikes. Potential problems with some of these methods were identified and discussed and they appear to be overcome by the hybrid method. No standard method exists for determining the required coefficient of friction (RCOF), an important predictor for slipping. In this study, RCOF values from a single data set, using various methods from the literature, differed considerably for a significant portion of strikes. A hybrid method may yield improved results.

Cross-section and rate coefficient calculation for electron impact excitation, ionisation and dissociation of H2 and OH molecules

International Nuclear Information System (INIS)

Riahi, R.; Ben Lakhdar, Z.; Teulet, Ph.; Gleizes, A.

2006-01-01

The weighted total cross-sections (WTCS) theory is used to calculate electron impact excitation, ionization and dissociation cross-sections and rate coefficients of OH, H 2 , OH + , H 2 + , OH - and H 2 - diatomic molecules in the temperature range 1500-15000 K. Calculations are performed for H 2 (X, B, C), OH(X, A, B), H 2 + (X), OH + (X, a, A, b, c), H 2 - (X) and OH - (X) electronic states for which Dunham coefficients are available. Rate coefficients are calculated from WTCS assuming Maxwellian energy distribution functions for electrons and heavy particles. One and 2 temperatures (θ e and θ g respectively for electron and heavy particles kinetic temperatures) results are presented and fitting parameters (a, b and c) are given for each reaction rate coefficient: k(θ) a(θ b )exp(-c/θ). (authors)

Research on friction coefficient of nuclear Reactor Vessel Internals Hold Down Spring: Stress coefficient test analysis method

International Nuclear Information System (INIS)

Linjun, Xie; Guohong, Xue; Ming, Zhang

2016-01-01

Graphical abstract: HDS stress coefficient test apparatus. - Highlights: • This paper performs mathematic deduction to the physical model of Hold Down Spring (HDS), establishes a mathematic model of axial load P and stress, stress coefficient and friction coefficient and designs a set of test apparatuses for simulating the pretightening process of the HDS for the first time according to a model similarity criterion. • The mathematical relation between the load and the strain is obtained about the HDS, and the mathematical model of the stress coefficient and the friction coefficient is established. So, a set of test apparatuses for obtaining the stress coefficient is designed according to the model scaling criterion and the friction coefficient of the K1000 HDS is calculated to be 0.336 through the obtained stress coefficient. • The relation curve between the theoretical load and the friction coefficient is obtained through analysis and indicates that the change of the friction coefficient f would influence the pretightening load under the condition of designed stress. The necessary pretightening load in the design process is calculated to be 5469 kN according to the obtained friction coefficient. Therefore, the friction coefficient and the pretightening load under the design conditions can provide accurate pretightening data for the analysis and design of the reactor HDS according to the operations. - Abstract: This paper performs mathematic deduction to the physical model of Hold Down Spring (HDS), establishes a mathematic model of axial load P and stress, stress coefficient and friction coefficient and designs a set of test apparatuses for simulating the pretightening process of the HDS for the first time according to a model similarity criterion. By carrying out tests and researches through a stress testing technique, P–σ curves in loading and unloading processes of the HDS are obtained and the stress coefficient k f of the HDS is obtained. So, the

Research on friction coefficient of nuclear Reactor Vessel Internals Hold Down Spring: Stress coefficient test analysis method

Energy Technology Data Exchange (ETDEWEB)

Linjun, Xie, E-mail: linjunx@zjut.edu.cn [College of Mechanical Engineering, Zhejiang University of Technology, Hangzhou 310014 (China); Guohong, Xue; Ming, Zhang [Shanghai Nuclear Engineering Research & Design Institute, Shanghai 200233 (China)

2016-08-01

Graphical abstract: HDS stress coefficient test apparatus. - Highlights: • This paper performs mathematic deduction to the physical model of Hold Down Spring (HDS), establishes a mathematic model of axial load P and stress, stress coefficient and friction coefficient and designs a set of test apparatuses for simulating the pretightening process of the HDS for the first time according to a model similarity criterion. • The mathematical relation between the load and the strain is obtained about the HDS, and the mathematical model of the stress coefficient and the friction coefficient is established. So, a set of test apparatuses for obtaining the stress coefficient is designed according to the model scaling criterion and the friction coefficient of the K1000 HDS is calculated to be 0.336 through the obtained stress coefficient. • The relation curve between the theoretical load and the friction coefficient is obtained through analysis and indicates that the change of the friction coefficient f would influence the pretightening load under the condition of designed stress. The necessary pretightening load in the design process is calculated to be 5469 kN according to the obtained friction coefficient. Therefore, the friction coefficient and the pretightening load under the design conditions can provide accurate pretightening data for the analysis and design of the reactor HDS according to the operations. - Abstract: This paper performs mathematic deduction to the physical model of Hold Down Spring (HDS), establishes a mathematic model of axial load P and stress, stress coefficient and friction coefficient and designs a set of test apparatuses for simulating the pretightening process of the HDS for the first time according to a model similarity criterion. By carrying out tests and researches through a stress testing technique, P–σ curves in loading and unloading processes of the HDS are obtained and the stress coefficient k{sub f} of the HDS is obtained. So, the

Experimental and theoretical studies of the reaction of the OH radical with alkyl sulfides: 3. Kinetics and mechanism of the OH initiated oxidation of dimethyl, dipropyl, and dibutyl sulfides: reactivity trends in the alkyl sulfides and development of a predictive expression for the reaction of OH with DMS.

Science.gov (United States)

Williams, M B; Campuzano-Jost, P; Hynes, A J; Pounds, A J

2009-06-18

A pulsed laser photolysis-pulsed laser-induced fluorescence technique has been employed to measure rate coefficients for the OH-initiated oxidation of dimethyl sulfide (DMS), its deuterated analog (DMS-d(6)), dipropyl sulfide (DPS), and dibutyl sulfide (DBS). Effective rate coefficients have been measured as a function of the partial pressure of O(2) over the temperature range of 240-295 K and at 200 and 600 Torr total pressure. We report the first observations of an O(2) enhancement in the effective rate coefficients for the reactions of OH with DPS and DBS. All observations are consistent with oxidation proceeding via a two-channel oxidation mechanism involving abstraction and addition channels. Structures and thermochemistry of the DPSOH and DBSOH adducts were calculated. Calculated bond strengths of adducts increase with alkyl substitution but are comparable to that of the DMSOH adduct and are consistent with experimental observations. Reactivity trends across the series of alkyl sulfide (C(2)-C(8)) reactions are analyzed. All reactions proceed via a two-channel mechanism involving either an H-atom abstraction or the formation of an OH adduct that can then react with O(2). Measurements presented in this work, in conjunction with previous measurements, have been used to develop a predictive expression for the OH-initiated oxidation of DMS. This expression is based on the elementary rate coefficients in the two-channel mechanism. The expression can calculate the effective rate coefficient for the reaction of OH with DMS over the range of 200-300 K, 0-760 Torr, and 0-100% partial pressure of O(2). This expression expands on previously published work but is applicable to DMS oxidation throughout the troposphere.

A Shock Tube Study of the CO + OH Reaction Near the Low-Pressure Limit

KAUST Repository

Nasir, Ehson Fawad; Farooq, Aamir

2016-01-01

Rate coefficients for the reaction between carbon monoxide and hydroxyl radical were measured behind reflected shock waves over 700 – 1230 K and 1.2 – 9.8 bar. The temperature/pressure conditions correspond to the predicted low-pressure limit of this reaction, where the channel leading to carbon dioxide formation is dominant. The reaction rate coefficients were inferred by measuring the formation of carbon dioxide using quantum cascade laser absorption near 4.2 µm. Experiments were performed under pseudo-first order conditions with tert-butyl hydroperoxide (TBHP) as the OH precursor. Using ultraviolet laser absorption by OH radicals, the TBHP decomposition rate was measured to quantify potential facility effects under extremely dilute conditions used here. The measured CO + OH rate coefficients are provided in Arrhenius form for three different pressure ranges: kCO+OH (1.2 – 1.6 bar) = 9.14 x 10-13 exp(-1265/T) cm3 molecule-1 s-1 kCO+OH (4.3 – 5.1 bar) = 8.70 x 10-13 exp(-1156/T) cm3 molecule-1 s-1 kCO+OH (9.6 – 9.8 bar) = 7.48 x 10-13 exp(-929/T) cm3 molecule-1 s-1 The measured rate coefficients are found to be lower than the master equation modeling results by Weston et al. [J. Phys. Chem. A, 117 (2013) 821] at 819 K and in closer agreement with the expression provided by Joshi and Wang [Int. J. Chem. Kinet., 38 (2006) 57].

A Shock Tube Study of the CO + OH Reaction Near the Low-Pressure Limit

KAUST Repository

Nasir, Ehson Fawad

2016-05-16

Rate coefficients for the reaction between carbon monoxide and hydroxyl radical were measured behind reflected shock waves over 700 – 1230 K and 1.2 – 9.8 bar. The temperature/pressure conditions correspond to the predicted low-pressure limit of this reaction, where the channel leading to carbon dioxide formation is dominant. The reaction rate coefficients were inferred by measuring the formation of carbon dioxide using quantum cascade laser absorption near 4.2 µm. Experiments were performed under pseudo-first order conditions with tert-butyl hydroperoxide (TBHP) as the OH precursor. Using ultraviolet laser absorption by OH radicals, the TBHP decomposition rate was measured to quantify potential facility effects under extremely dilute conditions used here. The measured CO + OH rate coefficients are provided in Arrhenius form for three different pressure ranges: kCO+OH (1.2 – 1.6 bar) = 9.14 x 10-13 exp(-1265/T) cm3 molecule-1 s-1 kCO+OH (4.3 – 5.1 bar) = 8.70 x 10-13 exp(-1156/T) cm3 molecule-1 s-1 kCO+OH (9.6 – 9.8 bar) = 7.48 x 10-13 exp(-929/T) cm3 molecule-1 s-1 The measured rate coefficients are found to be lower than the master equation modeling results by Weston et al. [J. Phys. Chem. A, 117 (2013) 821] at 819 K and in closer agreement with the expression provided by Joshi and Wang [Int. J. Chem. Kinet., 38 (2006) 57].

Thermochemistry of ionic liquid-catalysed reactions. Isomerisation and transalkylation of tert-alkyl-benzenes. Are these systems ideal?

International Nuclear Information System (INIS)

Verevkin, Sergey P.; Emel'yanenko, Vladimir N.; Hopmann, Elisabeth; Arlt, Wolfgang

2010-01-01

The chemical equilibrium of mutual interconversions of tert-alkyl-benzenes was studied in the temperature range (286 to 423) K using chloroaluminate ionic liquids as a catalyst. The knowledge of the activity coefficients is required in order to obtain the thermodynamic equilibrium constants K a . A well established procedure, COSMO-RS, has been used to assess activity coefficients of the reaction participants in the liquid phase. Enthalpies of five reactions of isomerisation and transalkylation of tert-alkyl-benzenes were obtained from temperature dependences of the corresponding equilibrium constants in the liquid phase. For the sake of comparison, high-level ab initio calculations of the reaction participants have been performed using the Gaussian-03 program package. Absolute electronic energy values of the molecules have been obtained using B3LYP and G3MP2 level. Using these results enthalpies of reaction of isomerisation and transalkylation of tert-alkyl-benzenes in the liquid phase based on the first principles are found to be in good agreement with the data obtained from the thermochemical measurements.

Influence of vibrations and rotations of diatomic molecules on their physical properties: II. Refractive index, reactivity and diffusion coefficients

International Nuclear Information System (INIS)

Sharipov, Alexander S; Loukhovitski, Boris I; Starik, Alexander M

2016-01-01

The influence of the excitation of vibrational and rotational states of diatomic molecules (H 2 , N 2 , O 2 , NO, OH, CO, CH, HF and HCl) on refractive index, reactivity and transport coefficients was analyzed by using ab initio calculated data on the effective state-specific dipole moment and static polarizability obtained in the preceding paper of the present series. It has been revealed that, for non-polar molecules, the excitation both of vibrational and rotational degrees of freedom increases the averaged polarizability and, as a consequence, the refractive index. Meanwhile, for polar molecules, the effect of molecule excitation is more complex: it can either increase or decrease the refractive index. It was also shown that the excitation of molecules slightly influences the rate constants of barrierless chemical reactions between neutral particles; whereas, for ion–molecule reactions, this effect can be more pronounced. Analysis of the variation of diffusion coefficients, taking into account the effect of molecule excitation both on the collision diameter and on the well depth of intermolecular potential, exhibited that, for non-polar molecules, the effect associated with the change of collision diameter prevails. However, for polar molecules, the effect of the excitation of vibrational states on the well depth of intermolecular potential can compensate or even exceed the decrease of diffusion coefficient due to the averaged collision diameter rise. (paper)

Indirect techniques in nuclear astrophysics. Asymptotic normalization coefficient and trojan horse

International Nuclear Information System (INIS)

Mukhamedzhanov, A.M.; Gagliardi, C.A.; Pirlepesov, F.; Trache, L.; Tribble, R.E.; Blokhintsev, L.D.; Brown, B.A.; Nunes, F.M.; Burjan, V.; Kroha, V.; Cherubini, S.; Pizzone, R.G.; Romano, S.; Spitaleri, C.; Tumino, A.; Irgaziev, B.F.; Tang, X.D.

2006-01-01

Owing to the presence of the Coulomb barrier at astrophysically relevant kinetic energies it is very difficult, or sometimes impossible, to measure astrophysical reaction rates in the laboratory. That is why different indirect techniques are being used along with direct measurements. Here we address two important indirect techniques, the asymptotic normalization coefficient (ANC) and the Trojan Horse (TH) methods. We discuss the application of the ANC technique for calculation of the astrophysical processes in the presence of subthreshold bound states, in particular, two different mechanisms are discussed: direct capture to the subthreshold state and capture to the low-lying bound states through the subthreshold state, which plays the role of the subthreshold resonance. The ANC technique can also be used to determine the interference sign of the resonant and nonresonant (direct) terms of the reaction amplitude. The TH method is unique indirect technique allowing one to measure astrophysical rearrangement reactions down to astrophysically relevant energies. We explain why there is no Coulomb barrier in the sub-process amplitudes extracted from the TH reaction. The expressions for the TH amplitude for direct and resonant cases are presented. (orig.)

Study of transport coefficients of nanodiamond nanofluids

Science.gov (United States)

Pryazhnikov, M. I.; Minakov, A. V.; Guzei, D. V.

2017-09-01

Experimental data on the thermal conductivity coefficient and viscosity coefficient of nanodiamond nanofluids are presented. Distilled water and ethylene glycol were used as the base fluid. Dependences of transport coefficients on concentration are obtained. It was shown that the thermal conductivity coefficient increases with increasing nanodiamonds concentration. It was shown that base fluids properties and nanodiamonds concentration affect on the rheology of nanofluids.

Kinetics of the Reactions of IO Radicals with NO and NO2

Science.gov (United States)

Daykin, E. P.; Wine, P. H.

1997-01-01

A laser flash photolysis-long path absorption technique has been employed to study the kinetics of the reactions of IO radicals with NO and NO2 as a function of temperature and pressure. The IO and NO rate coefficient is independent of pressure over the range 40-200 Torr of N2, and its temperature dependence over the range 242-359 K is adequately described by the Arrhenius expression k(sub 1) = (6.9 +/- 1.7) x 10(exp -12) exp[(328 +/- 71)/T] cu cm/(molecule.s) (errors are 2 sigma, precision only). These Arrhenius parameters are similar to those determined previously for the ClO + NO and BrO + NO reactions. The IO and NO2 association reaction is found to be in the falloff regime over the temperature and pressure ranges investigated (254-354 K and 40-750 Torr of N2). Assuming F(sub c) = 0.4 independent of temperature, a physically reasonable set of falloff parameters which adequately describe the data are k(sub 0) = 7.7 x 10(exp -31)(T/300)(exp -5.0) cm(exp 6)/(molecule(exp 2).s) and k(sub infinity) = 1.55 x 10(exp -11)cu cm/(molecule.s) independent of temperature. The IO + NO2 rate coefficients determined in this study are about a factor of 2 faster than those reported in the only previous study of this reaction.

Determination of nuclear friction in strongly damped reactions from prescission neutron multiplicities

International Nuclear Information System (INIS)

Wilczynski, J.; Siwek-Wilczynska, K.; Wilschut, H.W.

1996-01-01

Nonfusion, fissionlike reactions in collisions of four heavy systems (well below the fusion extra-push energy threshold), for which Hinde and co-workers had measured the prescission neutron multiplicities, have been analyzed in terms of the deterministic dynamic model of Feldmeier coupled to a time-dependent statistical cascade calculation. In order to reproduce the measured prescission multiplicities and the observed (nearly symmetric) mass divisions, the energy dissipation must be dramatically changed with regard to the standard one-body dissipation: In the entrance channel, in the process of forming a composite system, the energy dissipation has to be reduced to at least half of the one-body dissipation strength (k s in ≤0.5), and in the exit channel (from a mononucleus shape to scission) it must be increased by a factor ranging for the studied reactions from k s out =4 to k s out =12. These results are compared with the temperature dependence of the friction coefficient, recently deduced by Hofman, Back, and Paul from data on the prescission giant dipole resonance emission in fusion-fission reactions. The combined picture of the temperature dependence of the friction coefficient, for both fusion-fission and nonfusion reactions, may indicate the onset of strong two-body dissipation already at a nuclear temperature of about 2 MeV. copyright 1996 The American Physical Society

Dynamics of the fusion reaction in the dtμ- system

International Nuclear Information System (INIS)

Belyaev, V.B.; Revai, J.; Zubarev, A.L.

1988-08-01

A dynamical scheme based on the (td,αn) two-channel model is derived for the description of the fusion reaction in the dtμ - system. Special attention is paid to the correct specification of the final states. Several possibilities are pointed out for the systematic improvement of the sudden approximation for the sticking coefficient. It seems to be useful to outline a general formulation of these processes which would allow a clear comparison of existing approaches. The lack of satisfactory agreement between experimental and theoretical values of the sticking coefficient is a further argument in favour of the programme. (R.P.) 10 refs

Investigation of the 9Be(a,n)12C reaction. Pt. 2

International Nuclear Information System (INIS)

Schmidt, D.; Boettger, R.; Klein, H.; Nolte, R.

1992-04-01

Differential cross sections of the 9 Be(α,n) 12 C reaction have been measured at 19 alpha energies between 7 MeV and 16 MeV. Besides the differential cross sections from the 9 Be(α,n) 12 C(g.s.) reaction, also those of the 9 Be(α,n) 12 C(E ex ) reactions were derived for excitation energies E ex = 4.439, 7.654, 9.641, 10.84, 11.83 and 12.71 MeV. Possible sources of uncertainties have been extensively investigated and the corresponding results have been published in part 1. All partial and integrated cross sections from the 9 Be(α,n) 12 C(g.s.) reaction were determined with uncertainties of less than 5%. The angular distributions were fitted to Legendre polynomial expansions by the least-squares method. A comparison of the measured cross sections with data from other authors and with an evaluation shows considerable deviations in some cases. Tests were also carried out to ascertain how well an interpolation of the Legendre coefficients reproduces the magnitude and shape of the experimentally determined angular distributions. All angular distributions are presented in figures, together with their Legendre polynomial expansions and data from the literature if available. The a l coefficients of the Legendre polynomial expansions are given in the Appendix. (orig.) [de

Dissociation coefficients of protein adsorption to nanoparticles as quantitative metrics for description of the protein corona: A comparison of experimental techniques and methodological relevance

KAUST Repository

Hü hn, Jonas; Fedeli, Chiara; Zhang, Qian; Masood, Atif; del Pino, Pablo; Khashab, Niveen M.; Papini, Emanuele; Parak, Wolfgang J.

2015-01-01

Protein adsorption to nanoparticles is described as a chemical reaction in which proteins attach to binding sites on the nanoparticle surface. This process can be described with a dissociation coefficient, which tells how many proteins are adsorbed per nanoparticle in dependence of the protein concentration. Different techniques to experimentally determine dissociation coefficients of protein adsorption to nanoparticles are reviewed. Results of more than 130 experiments in which dissociation coefficients have been determined are compared. Data show that different methods, nanoparticle systems, and proteins can lead to significantly different dissociation coefficients. However, we observed a clear tendency of smaller dissociation coefficients upon less negative towards more positive zeta potentials of the nanoparticles. The zeta potential thus is a key parameter influencing protein adsorption to the surface of nanoparticles. Our analysis highlights the importance of the characterization of the parameters governing protein-nanoparticle interaction for quantitative evaluation and objective literature comparison.

Dissociation coefficients of protein adsorption to nanoparticles as quantitative metrics for description of the protein corona: A comparison of experimental techniques and methodological relevance

KAUST Repository

Hühn, Jonas

2015-12-31

Protein adsorption to nanoparticles is described as a chemical reaction in which proteins attach to binding sites on the nanoparticle surface. This process can be described with a dissociation coefficient, which tells how many proteins are adsorbed per nanoparticle in dependence of the protein concentration. Different techniques to experimentally determine dissociation coefficients of protein adsorption to nanoparticles are reviewed. Results of more than 130 experiments in which dissociation coefficients have been determined are compared. Data show that different methods, nanoparticle systems, and proteins can lead to significantly different dissociation coefficients. However, we observed a clear tendency of smaller dissociation coefficients upon less negative towards more positive zeta potentials of the nanoparticles. The zeta potential thus is a key parameter influencing protein adsorption to the surface of nanoparticles. Our analysis highlights the importance of the characterization of the parameters governing protein-nanoparticle interaction for quantitative evaluation and objective literature comparison.

Coefficient Alpha: A Reliability Coefficient for the 21st Century?

Science.gov (United States)

Yang, Yanyun; Green, Samuel B.

2011-01-01

Coefficient alpha is almost universally applied to assess reliability of scales in psychology. We argue that researchers should consider alternatives to coefficient alpha. Our preference is for structural equation modeling (SEM) estimates of reliability because they are informative and allow for an empirical evaluation of the assumptions…

Probabilistic optimization of safety coefficients

International Nuclear Information System (INIS)

Marques, M.; Devictor, N.; Magistris, F. de

1999-01-01

This article describes a reliability-based method for the optimization of safety coefficients defined and used in design codes. The purpose of the optimization is to determine the partial safety coefficients which minimize an objective function for sets of components and loading situations covered by a design rule. This objective function is a sum of distances between the reliability of the components designed using the safety coefficients and a target reliability. The advantage of this method is shown on the examples of the reactor vessel, a vapour pipe and the safety injection circuit. (authors)

Converting Sabine absorption coefficients to random incidence absorption coefficients

DEFF Research Database (Denmark)

Jeong, Cheol-Ho

2013-01-01

are suggested: An optimization method for the surface impedances for locally reacting absorbers, the flow resistivity for extendedly reacting absorbers, and the flow resistance for fabrics. With four porous type absorbers, the conversion methods are validated. For absorbers backed by a rigid wall, the surface...... coefficients to random incidence absorption coefficients are proposed. The overestimations of the Sabine absorption coefficient are investigated theoretically based on Miki's model for porous absorbers backed by a rigid wall or an air cavity, resulting in conversion factors. Additionally, three optimizations...... impedance optimization produces the best results, while the flow resistivity optimization also yields reasonable results. The flow resistivity and flow resistance optimization for extendedly reacting absorbers are also found to be successful. However, the theoretical conversion factors based on Miki's model...

Shock tube study of the reactions of the hydroxyl radical with combustion species and pollutants. Final report

Energy Technology Data Exchange (ETDEWEB)

Cohen, N.; Koffend, J.B.

1998-02-01

Shock heating t-butyl hydroperoxide behind a reflected shock wave has proved to be as a convenient source of hydroxyl radicals at temperatures near 1000 K. We applied this technique to the measurement of reaction rate coefficients of OH with several species of interest in combustion chemistry, and developed a thermochemical kinetics/transition state theory (TK-TST) model for predicting the temperature dependence of OH rate coefficients.

Temperature dependence of He(2 3PJ) reactions: Collision-induced mixing and conversion to He2( 3Πg) molecules

International Nuclear Information System (INIS)

Zhao, X.; Soletsky, P.A.; Bryan, W.H.; Dunning, F.B.; Walters, G.K.

1993-01-01

The rate coefficients for mixing between He(2 3 P J, MJ) levels during collisions with ground-state helium atoms and for conversion of He(2 3 P J ) atoms to He 2 (b 3 Π g ) molecules via three-body reactions in helium gas have been investigated over the temperature range 1.6--300 K. The measured rate coefficients for collisionally induced P-state mixing decrease slowly with decreasing temperature, from (1.8±0.5)x10 -9 cm 3 s -1 at 300 K to (4.5±0.5)x10 -10 cm 3 s -1 at 4.2 K. The rate coefficients for the production of He 2 (b 3 Π g ) molecules via three-body reactions are observed to increase with decreasing temperature and are described by the relation k P congruent(2.5+267T -1 )x10 -32 cm 6 s -1 . This behavior, which is very different from that noted in earlier studies of the conversion of He(2 3 S 1 ) atoms to He 2 (a 3 Σ u + ) molecules through three-body reactions, suggests that the reaction is not thermally activated

Implications of NGA for NEHRP site coefficients

Science.gov (United States)

Borcherdt, Roger D.

2012-01-01

Three proposals are provided to update tables 11.4-1 and 11.4-2 of Minimum Design Loads for Buildings and Other Structures (7-10), by the American Society of Civil Engineers (2010) (ASCE/SEI 7-10), with site coefficients implied directly by NGA (Next Generation Attenuation) ground motion prediction equations (GMPEs). Proposals include a recommendation to use straight-line interpolation to infer site coefficients at intermediate values of ̅vs (average shear velocity). Site coefficients are recommended to ensure consistency with ASCE/SEI 7-10 MCER (Maximum Considered Earthquake) seismic-design maps and simplified site-specific design spectra procedures requiring site classes with associated tabulated site coefficients and a reference site class with unity site coefficients. Recommended site coefficients are confirmed by independent observations of average site amplification coefficients inferred with respect to an average ground condition consistent with that used for the MCER maps. The NGA coefficients recommended for consideration are implied directly by the NGA GMPEs and do not require introduction of additional models.

Estimation of the simple correlation coefficient.

Science.gov (United States)

Shieh, Gwowen

2010-11-01

This article investigates some unfamiliar properties of the Pearson product-moment correlation coefficient for the estimation of simple correlation coefficient. Although Pearson's r is biased, except for limited situations, and the minimum variance unbiased estimator has been proposed in the literature, researchers routinely employ the sample correlation coefficient in their practical applications, because of its simplicity and popularity. In order to support such practice, this study examines the mean squared errors of r and several prominent formulas. The results reveal specific situations in which the sample correlation coefficient performs better than the unbiased and nearly unbiased estimators, facilitating recommendation of r as an effect size index for the strength of linear association between two variables. In addition, related issues of estimating the squared simple correlation coefficient are also considered.

Importance of self-shielding for improving sensitivity coefficients in light water nuclear reactors

International Nuclear Information System (INIS)

Foad, Basma; Takeda, Toshikazu

2014-01-01

Highlights: • A new method has been developed for calculating sensitivity coefficients. • This method is based on the use of infinite dilution cross-sections instead of effective cross-sections. • The change of self-shielding factor due to cross-section perturbation has been considered. • SRAC and SAINT codes are used for calculating improved sensitivities, while MCNP code has been used for verification. - Abstract: In order to perform sensitivity analyzes in light water reactors where self-shielding effect becomes important, a new method has been developed for calculating sensitivity coefficient of core characteristics relative to the infinite dilution cross-sections instead of the effective cross-sections. This method considers the change of the self-shielding factor due to cross-section perturbation for different nuclides and reactions. SRAC and SAINT codes are used to calculate the improved sensitivity; while the accuracy of the present method has been verified by MCNP code and good agreement has been found

Determination of the surface drag coefficient

DEFF Research Database (Denmark)

Mahrt, L.; Vickers, D.; Sun, J.L.

2001-01-01

This study examines the dependence of the surface drag coefficient on stability, wind speed, mesoscale modulation of the turbulent flux and method of calculation of the drag coefficient. Data sets over grassland, sparse grass, heather and two forest sites are analyzed. For significantly unstable...... conditions, the drag coefficient does not depend systematically on z/L but decreases with wind speed for fixed intervals of z/L, where L is the Obukhov length. Even though the drag coefficient for weak wind conditions is sensitive to the exact method of calculation and choice of averaging time, the decrease...... of the drag coefficient with wind speed occurs for all of the calculation methods. A classification of flux calculation methods is constructed, which unifies the most common previous approaches. The roughness length corresponding to the usual Monin-Obukhov stability functions decreases with increasing wind...