Non-equilibrium Quasi-Chemical Nucleation Model

Science.gov (United States)

Gorbachev, Yuriy E.

2018-04-01

Quasi-chemical model, which is widely used for nucleation description, is revised on the basis of recent results in studying of non-equilibrium effects in reacting gas mixtures (Kolesnichenko and Gorbachev in Appl Math Model 34:3778-3790, 2010; Shock Waves 23:635-648, 2013; Shock Waves 27:333-374, 2017). Non-equilibrium effects in chemical reactions are caused by the chemical reactions themselves and therefore these contributions should be taken into account in the corresponding expressions for reaction rates. Corrections to quasi-equilibrium reaction rates are of two types: (a) spatially homogeneous (caused by physical-chemical processes) and (b) spatially inhomogeneous (caused by gas expansion/compression processes and proportional to the velocity divergency). Both of these processes play an important role during the nucleation and are included into the proposed model. The method developed for solving the generalized Boltzmann equation for chemically reactive gases is applied for solving the set of equations of the revised quasi-chemical model. It is shown that non-equilibrium processes lead to essential deviation of the quasi-stationary distribution and therefore the nucleation rate from its traditional form.

Computer program for calculation of complex chemical equilibrium compositions and applications. Part 1: Analysis

Science.gov (United States)

Gordon, Sanford; Mcbride, Bonnie J.

1994-01-01

This report presents the latest in a number of versions of chemical equilibrium and applications programs developed at the NASA Lewis Research Center over more than 40 years. These programs have changed over the years to include additional features and improved calculation techniques and to take advantage of constantly improving computer capabilities. The minimization-of-free-energy approach to chemical equilibrium calculations has been used in all versions of the program since 1967. The two principal purposes of this report are presented in two parts. The first purpose, which is accomplished here in part 1, is to present in detail a number of topics of general interest in complex equilibrium calculations. These topics include mathematical analyses and techniques for obtaining chemical equilibrium; formulas for obtaining thermodynamic and transport mixture properties and thermodynamic derivatives; criteria for inclusion of condensed phases; calculations at a triple point; inclusion of ionized species; and various applications, such as constant-pressure or constant-volume combustion, rocket performance based on either a finite- or infinite-chamber-area model, shock wave calculations, and Chapman-Jouguet detonations. The second purpose of this report, to facilitate the use of the computer code, is accomplished in part 2, entitled 'Users Manual and Program Description'. Various aspects of the computer code are discussed, and a number of examples are given to illustrate its versatility.

Incorporation of a Chemical Equilibrium Equation of State into LOCI-Chem

Science.gov (United States)

Cox, Carey F.

2005-01-01

Renewed interest in development of advanced high-speed transport, reentry vehicles and propulsion systems has led to a resurgence of research into high speed aerodynamics. As this flow regime is typically dominated by hot reacting gaseous flow, efficient models for the characteristic chemical activity are necessary for accurate and cost effective analysis and design of aerodynamic vehicles that transit this regime. The LOCI-Chem code recently developed by Ed Luke at Mississippi State University for NASA/MSFC and used by NASA/MSFC and SSC represents an important step in providing an accurate, efficient computational tool for the simulation of reacting flows through the use of finite-rate kinetics [3]. Finite rate chemistry however, requires the solution of an additional N-1 species mass conservation equations with source terms involving reaction kinetics that are not fully understood. In the equilibrium limit, where the reaction rates approach infinity, these equations become very stiff. Through the use of the assumption of local chemical equilibrium the set of governing equations is reduced back to the usual gas dynamic equations, and thus requires less computation, while still allowing for the inclusion of reacting flow phenomenology. The incorporation of a chemical equilibrium equation of state module into the LOCI-Chem code was the primary objective of the current research. The major goals of the project were: (1) the development of a chemical equilibrium composition solver, and (2) the incorporation of chemical equilibrium solver into LOCI-Chem. Due to time and resource constraints, code optimization was not considered unless it was important to the proper functioning of the code.

Chemical equilibrium of glycerol carbonate synthesis from glycerol

International Nuclear Information System (INIS)

Li Jiabo; Wang Tao

2011-01-01

Research highlights: → Transesterification of glycerol with cyclic carbonates or alkyl carbonates is thermodynamically favourable for the preparation of glycerol carbonate from glycerol. → The reaction of glycerol and carbon dioxide is thermodynamically limited. → High temperature and low pressure is favourable to the reaction of glycerol and urea. → Increasing temperature can increase the chemical equilibrium constant for the reaction of glycerol and dimethyl carbonate. → For the reaction of glycerol and ethylene carbonate, increasing temperature can decrease the chemical equilibrium constant. - Abstract: In this paper, the chemical equilibrium for the glycerol carbonate preparation from glycerol was investigated. The chemical equilibrium constants were calculated for the reactions to produce glycerol carbonate from glycerol. The theoretical calculation was compared with the experimental results for the transesterification of glycerol with dimethyl carbonate. Transesterification of glycerol with cyclic carbonates or alkyl carbonates is thermodynamically favourable for producing glycerol carbonate from glycerol according to the equilibrium constant. Increasing temperature can increase the chemical equilibrium constant for the reaction of glycerol with dimethyl carbonate. For the reaction of glycerol with ethylene carbonate, increasing temperature can decrease the chemical equilibrium constant. The reaction of glycerol with carbon dioxide is thermodynamically limited. High temperature and low pressure are favourable to the reaction of glycerol and urea.

Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels

DEFF Research Database (Denmark)

Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita

2011-01-01

, and pK+ are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy–Chapman–Stern triple-layer model...... of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary...

Exploring Chemical and Thermal Non-equilibrium in Nitrogen Arcs

International Nuclear Information System (INIS)

Ghorui, S; Das, A K

2012-01-01

Plasma torches operating with nitrogen are of special importance as they can operate with usual tungsten based refractory electrodes and offer radical rich non-oxidizing high temperature environment for plasma chemistry. Strong gradients in temperature as well as species densities and huge convective fluxes lead to varying degrees of chemical non-equilibrium in associated regions. An axi-symmetric two-temperature chemical non-equilibrium model of a nitrogen plasma torch has been developed to understand the effects of thermal and chemical non-equilibrium in arcs. A 2-D finite volume CFD code in association with a non-equilibrium property routine enabled extraction of steady state self-consistent distributions of various plasma quantities inside the torch under various thermal and chemical non-equilibrium conditions. Chemical non-equilibrium has been incorporated through computation of diffusive and convective fluxes in each finite volume cell in every iteration and associating corresponding thermodynamic and transport properties through the scheme of 'chemical non-equilibrium parameter' introduced by Ghorui et. al. Recombination coefficient data from Nahar et. al. and radiation data from Krey and Morris have been used in the simulation. Results are presented for distributions of temperature, pressure, velocity, current density, electric potential, species densities and chemical non-equilibrium effects. Obtained results are compared with similar results under LTE.

Investigating High School Students' Understanding of Chemical Equilibrium Concepts

Science.gov (United States)

Karpudewan, Mageswary; Treagust, David F.; Mocerino, Mauro; Won, Mihye; Chandrasegaran, A. L.

2015-01-01

This study investigated the year 12 students' (N = 56) understanding of chemical equilibrium concepts after instruction using two conceptual tests, the "Chemical Equilibrium Conceptual Test 1" ("CECT-1") consisting of nine two-tier multiple-choice items and the "Chemical Equilibrium Conceptual Test 2"…

Partial chemical equilibrium in fluid dynamics

International Nuclear Information System (INIS)

Ramshaw, J.D.

1980-01-01

An analysis is given for the flow of a multicomponent fluid in which an arbitrary number of chemical reactions may occur, some of which are in equilibrium while the others proceed kinetically. The primitive equations describing this situation are inconvenient to use because the progress rates omega-dot/sub s/ for the equilibrium reactions are determined implicitly by the associated equilibrium constraint conditions. Two alternative equivalent equation systems that are more pleasant to deal with are derived. In the first system, the omega-dot/sub s/ are eliminated by replacing the transport equations for the chemical species involved in the equilibrium reactions with transport equations for the basic components of which these species are composed. The second system retains the usual species transport equations, but eliminates the nonlinear algebraic equilibrium constraint conditions by deriving an explicit expression for the omega-dot/sub s/. Both systems are specialized to the case of an ideal gas mixture. Considerations involved in solving these equation systems numerically are discussed briefly

Simulations of NMR pulse sequences during equilibrium and non-equilibrium chemical exchange

International Nuclear Information System (INIS)

Helgstrand, Magnus; Haerd, Torleif; Allard, Peter

2000-01-01

The McConnell equations combine the differential equations for a simple two-state chemical exchange process with the Bloch differential equations for a classical description of the behavior of nuclear spins in a magnetic field. This equation system provides a useful starting point for the analysis of slow, intermediate and fast chemical exchange studied using a variety of NMR experiments. The McConnell equations are in the mathematical form of an inhomogeneous system of first-order differential equations. Here we rewrite the McConnell equations in a homogeneous form in order to facilitate fast and simple numerical calculation of the solution to the equation system. The McConnell equations can only treat equilibrium chemical exchange. We therefore also present a homogeneous equation system that can handle both equilibrium and non-equilibrium chemical processes correctly, as long as the kinetics is of first-order. Finally, the same method of rewriting the inhomogeneous form of the McConnell equations into a homogeneous form is applied to a quantum mechanical treatment of a spin system in chemical exchange. In order to illustrate the homogeneous McConnell equations, we have simulated pulse sequences useful for measuring exchange rates in slow, intermediate and fast chemical exchange processes. A stopped-flow NMR experiment was simulated using the equations for non-equilibrium chemical exchange. The quantum mechanical treatment was tested by the simulation of a sensitivity enhanced 15 N-HSQC with pulsed field gradients during slow chemical exchange and by the simulation of the transfer efficiency of a two-dimensional heteronuclear cross-polarization based experiment as a function of both chemical shift difference and exchange rate constants

Evaluation of activities of carbons in chemical equilibrium with uranium carbonitride

International Nuclear Information System (INIS)

Katsura, Masahiro; Hirota, Masayuki; Miyake, Masanobu; Hamada, Kazuo.

1992-01-01

A mixture of uranium sesquinitride and carbon was prepared by the reaction of UC of UC 2 with N 2 in the temperature range from 700 to 1400degC. When the mixture of uranium sesquinitride and carbon is kept at temperatures above 1200degC in the atmosphere of N 2 at low pressure, the state where uranium carbonitride (UC 1-x N x ) and carbon are present together in chemical equilibrium will be established. A thermodynamic analysis suggests that, in the equilibrium state, the composition of UC 1-x N x is determined by the chemical activity of carbon, a c , which is related to the chemical potential of the carbon, μ c , by the equation, μ c = μ c deg + RT 1n a c . Here μ c deg refers to graphite, which is usually taken as the standard state of carbon (a c = 1). Mixtures of U 2 N 3 and carbon with several degrees of graphitization were heat-treated at 1400degC, and the composition of UC 1-x N x in the reaction product was determined. From these experimental results and the thermodynamic analysis, values of the activity of the carbon coexisting with UC 1-x N x were estimated. (author)

The Conceptual Change Approach to Teaching Chemical Equilibrium

Science.gov (United States)

Canpolat, Nurtac; Pinarbasi, Tacettin; Bayrakceken, Samih; Geban, Omer

2006-01-01

This study investigates the effect of a conceptual change approach over traditional instruction on students' understanding of chemical equilibrium concepts (e.g. dynamic nature of equilibrium, definition of equilibrium constant, heterogeneous equilibrium, qualitative interpreting of equilibrium constant, changing the reaction conditions). This…

An implicit flux-split algorithm to calculate hypersonic flowfields in chemical equilibrium

Science.gov (United States)

Palmer, Grant

1987-01-01

An implicit, finite-difference, shock-capturing algorithm that calculates inviscid, hypersonic flows in chemical equilibrium is presented. The flux vectors and flux Jacobians are differenced using a first-order, flux-split technique. The equilibrium composition of the gas is determined by minimizing the Gibbs free energy at every node point. The code is validated by comparing results over an axisymmetric hemisphere against previously published results. The algorithm is also applied to more practical configurations. The accuracy, stability, and versatility of the algorithm have been promising.

Surface-dependent chemical equilibrium constants and capacitances for bare and 3-cyanopropyldimethylchlorosilane coated silica nanochannels.

Science.gov (United States)

Andersen, Mathias Bækbo; Frey, Jared; Pennathur, Sumita; Bruus, Henrik

2011-01-01

We present a combined theoretical and experimental analysis of the solid-liquid interface of fused-silica nanofabricated channels with and without a hydrophilic 3-cyanopropyldimethylchlorosilane (cyanosilane) coating. We develop a model that relaxes the assumption that the surface parameters C(1), C(2), and pK(+) are constant and independent of surface composition. Our theoretical model consists of three parts: (i) a chemical equilibrium model of the bare or coated wall, (ii) a chemical equilibrium model of the buffered bulk electrolyte, and (iii) a self-consistent Gouy-Chapman-Stern triple-layer model of the electrochemical double layer coupling these two equilibrium models. To validate our model, we used both pH-sensitive dye-based capillary filling experiments as well as electro-osmotic current-monitoring measurements. Using our model we predict the dependence of ζ potential, surface charge density, and capillary filling length ratio on ionic strength for different surface compositions, which can be difficult to achieve otherwise. Copyright © 2010 Elsevier Inc. All rights reserved.

An approximate method for calculating composition of the non-equilibrium explosion products of hydrocarbons and oxygen

International Nuclear Information System (INIS)

Shargatov, V A; Gubin, S A; Okunev, D Yu

2016-01-01

We develop a method for calculating the changes in composition of the explosion products in the case where the complete chemical equilibrium is absent but the bimolecular reactions are in quasi-equilibrium with the exception bimolecular reactions with one of the components of the mixture. We investigate the possibility of using the method of 'quasiequilibrium' for mixtures of hydrocarbons and oxygen. The method is based on the assumption of the existence of the partial chemical equilibrium in the explosion products. Without significant loss of accuracy to the solution of stiff differential equations detailed kinetic mechanism can be replaced by one or two differential equation and a system of algebraic equations. This method is always consistent with the detailed mechanism and can be used separately or in conjunction with the solution of a stiff system for chemically non-equilibrium mixtures replacing it when bimolecular reactions are near to equilibrium. (paper)

From Chemical Forces to Chemical Rates: A Historical/Philosophical Foundation for the Teaching of Chemical Equilibrium

Science.gov (United States)

Quilez, Juan

2009-01-01

With this paper, our main aim is to contribute to the realisation of the chemical reactivity concept, tracing the historical evolution of the concept of chemical affinity that eventually supported the concept of chemical equilibrium. We will concentrate on searching for the theoretical grounds of three key chemical equilibrium ideas: "incomplete…

Chemical Equilibrium as Balance of the Thermodynamic Forces

OpenAIRE

Zilbergleyt, B.

2004-01-01

The article sets forth comprehensive basics of thermodynamics of chemical equilibrium as balance of the thermodynamic forces. Based on the linear equations of irreversible thermodynamics, De Donder definition of the thermodynamic force, and Le Chatelier's principle, new thermodynamics of chemical equilibrium offers an explicit account for multiple chemical interactions within the system. Basic relations between energetic characteristics of chemical transformations and reaction extents are bas...

Teaching Chemical Equilibrium with the Jigsaw Technique

Science.gov (United States)

Doymus, Kemal

2008-03-01

This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students’ understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes was randomly assigned as the non-jigsaw group (control) and other as the jigsaw group (cooperative). Students participating in the jigsaw group were divided into four “home groups” since the topic chemical equilibrium is divided into four subtopics (Modules A, B, C and D). Each of these home groups contained four students. The groups were as follows: (1) Home Group A (HGA), representin g the equilibrium state and quantitative aspects of equilibrium (Module A), (2) Home Group B (HGB), representing the equilibrium constant and relationships involving equilibrium constants (Module B), (3) Home Group C (HGC), representing Altering Equilibrium Conditions: Le Chatelier’s principle (Module C), and (4) Home Group D (HGD), representing calculations with equilibrium constants (Module D). The home groups then broke apart, like pieces of a jigsaw puzzle, and the students moved into jigsaw groups consisting of members from the other home groups who were assigned the same portion of the material. The jigsaw groups were then in charge of teaching their specific subtopic to the rest of the students in their learning group. The main data collection tool was a Chemical Equilibrium Achievement Test (CEAT), which was applied to both the jigsaw and non-jigsaw groups The results indicated that the jigsaw group was more successful than the non-jigsaw group (individual learning method).

A kinetic and equilibrium analysis of silicon carbide chemical vapor deposition on monofilaments

Science.gov (United States)

Gokoglu, S. A.; Kuczmarski, M. A.

1993-01-01

Chemical kinetics of atmospheric pressure silicon carbide (SiC) chemical vapor deposition (CVD) from dilute silane and propane source gases in hydrogen is numerically analyzed in a cylindrical upflow reactor designed for CVD on monofilaments. The chemical composition of the SiC deposit is assessed both from the calculated total fluxes of carbon and silicon and from chemical equilibrium considerations for the prevailing temperatures and species concentrations at and along the filament surface. The effects of gas and surface chemistry on the evolution of major gas phase species are considered in the analysis.

Computer Program for Calculation of Complex Chemical Equilibrium Compositions and Applications II. Users Manual and Program Description. 2; Users Manual and Program Description

Science.gov (United States)

McBride, Bonnie J.; Gordon, Sanford

1996-01-01

This users manual is the second part of a two-part report describing the NASA Lewis CEA (Chemical Equilibrium with Applications) program. The program obtains chemical equilibrium compositions of complex mixtures with applications to several types of problems. The topics presented in this manual are: (1) details for preparing input data sets; (2) a description of output tables for various types of problems; (3) the overall modular organization of the program with information on how to make modifications; (4) a description of the function of each subroutine; (5) error messages and their significance; and (6) a number of examples that illustrate various types of problems handled by CEA and that cover many of the options available in both input and output. Seven appendixes give information on the thermodynamic and thermal transport data used in CEA; some information on common variables used in or generated by the equilibrium module; and output tables for 14 example problems. The CEA program was written in ANSI standard FORTRAN 77. CEA should work on any system with sufficient storage. There are about 6300 lines in the source code, which uses about 225 kilobytes of memory. The compiled program takes about 975 kilobytes.

Using Analogies to Prevent Misconceptions about Chemical Equilibrium

Science.gov (United States)

Sahin Pekmez, Esin

2010-01-01

The main purpose of this study was to find the effectiveness of using analogies to prevent misconceptions about chemical equilibrium. Nineteen analogies, which were based on dynamic aspects of chemical equilibrium and application of Le Chatelier's principle, were developed. The participations of this study consisted of 11th grade students (n: 151)…

Wave propagation in a quasi-chemical equilibrium plasma

Science.gov (United States)

Fang, T.-M.; Baum, H. R.

1975-01-01

Wave propagation in a quasi-chemical equilibrium plasma is studied. The plasma is infinite and without external fields. The chemical reactions are assumed to result from the ionization and recombination processes. When the gas is near equilibrium, the dominant role describing the evolution of a reacting plasma is played by the global conservation equations. These equations are first derived and then used to study the small amplitude wave motion for a near-equilibrium situation. Nontrivial damping effects have been obtained by including the conduction current terms.

Implementing an Equilibrium Law Teaching Sequence for Secondary School Students to Learn Chemical Equilibrium

Science.gov (United States)

Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

2015-01-01

A didactic sequence is proposed for the teaching of chemical equilibrium law. In this approach, we have avoided the kinetic derivation and the thermodynamic justification of the equilibrium constant. The equilibrium constant expression is established empirically by a trial-and-error approach. Additionally, students learn to use the criterion of…

Exploring Chemical Equilibrium with Poker Chips: A General Chemistry Laboratory Exercise

Science.gov (United States)

Bindel, Thomas H.

2012-01-01

A hands-on laboratory exercise at the general chemistry level introduces students to chemical equilibrium through a simulation that uses poker chips and rate equations. More specifically, the exercise allows students to explore reaction tables, dynamic chemical equilibrium, equilibrium constant expressions, and the equilibrium constant based on…

On the Concept "Chemical Equilibrium": The Associative Framework.

Science.gov (United States)

Gussarsky, Esther; Gorodetsky, Malka

1990-01-01

Word associations were used to map high school students' concepts of "chemical equilibrium" and "equilibrium." It was found that the preconception of the two concepts was differentiated on noncritical dimensions. (Author/CW)

Calculation of Multiphase Chemical Equilibrium by the Modified RAND Method

DEFF Research Database (Denmark)

Tsanas, Christos; Stenby, Erling Halfdan; Yan, Wei

2017-01-01

method. The modified RAND extends the classical RAND method from single-phase chemical reaction equilibrium of ideal systems to multiphase chemical equilibrium of nonideal systems. All components in all phases are treated in the same manner and the system Gibbs energy can be used to monitor convergence....... This is the first time that modified RAND was applied to multiphase chemical equilibrium systems. The combined algorithm was tested using nine examples covering vapor–liquid (VLE) and vapor–liquid–liquid equilibria (VLLE) of ideal and nonideal reaction systems. Successive substitution provided good initial......A robust and efficient algorithm for simultaneous chemical and phase equilibrium calculations is proposed. It combines two individual nonstoichiometric solving procedures: a nested-loop method with successive substitution for the first steps and final convergence with the second-order modified RAND...

Algorithm For Hypersonic Flow In Chemical Equilibrium

Science.gov (United States)

Palmer, Grant

1989-01-01

Implicit, finite-difference, shock-capturing algorithm calculates inviscid, hypersonic flows in chemical equilibrium. Implicit formulation chosen because overcomes limitation on mathematical stability encountered in explicit formulations. For dynamical portion of problem, Euler equations written in conservation-law form in Cartesian coordinate system for two-dimensional or axisymmetric flow. For chemical portion of problem, equilibrium state of gas at each point in computational grid determined by minimizing local Gibbs free energy, subject to local conservation of molecules, atoms, ions, and total enthalpy. Major advantage: resulting algorithm naturally stable and captures strong shocks without help of artificial-dissipation terms to damp out spurious numerical oscillations.

SOLGASMIX-PV, Chemical System Equilibrium of Gaseous and Condensed Phase Mixtures

International Nuclear Information System (INIS)

Besmann, T.M.

1986-01-01

1 - Description of program or function: SOLGASMIX-PV, which is based on the earlier SOLGAS and SOLGASMIX codes, calculates equilibrium relationships in complex chemical systems. Chemical equilibrium calculations involve finding the system composition, within certain constraints, which contains the minimum free energy. The constraints are the preservation of the masses of each element present and either constant pressure or volume. SOLGASMIX-PV can calculate equilibria in systems containing a gaseous phase, condensed phase solutions, and condensed phases of invariant and variable stoichiometry. Either a constant total gas volume or a constant total pressure can be assumed. Unit activities for condensed phases and ideality for solutions are assumed, although nonideal systems can be handled provided activity coefficient relationships are available. 2 - Restrictions on the complexity of the problem: The program is designed to handle a maximum of 20 elements, 99 substances, and 10 mixtures, where the gas phase is considered a mixture. Each substance is either a gas or condensed phase species, or a member of a condensed phase mixture

A multidimensional framework of conceptual change for developing chemical equilibrium learning

Science.gov (United States)

Chanyoo, Wassana; Suwannoi, Paisan; Treagust, David F.

2018-01-01

The purposes of this research is to investigate the existing chemical equilibrium lessons in Thailand based on the multidimensional framework of conceptual change, to determine how the existing lessons could enhance students' conceptual change. This research was conducted based on qualitative perspective. Document, observations and interviews were used to collect data. To comprehend all students conceptions, diagnostic tests were applied comprised of The Chemical Equilibrium Diagnostic Test (the CEDT) and The Chemical Equilibrium Test for Reveal Conceptual Change (the CETforRCC). In addition, to study students' motivations, the Motivated Strategies for Learning Questionnaire (the MSLQ) and students' task engagement were applied. Following each perspective of conceptual change - ontological, epistemological, and social/affective - the result showed that the existing chemical equilibrium unit did not enhance students' conceptual change, and some issues were found. The problems obstructed students conceptual change should be remedy under the multidimensional framework of conceptual change. Finally, some suggestions were provided to enhance students' conceptual change in chemical equilibrium effectively

Self-organization of grafted polyelectrolyte layers via the coupling of chemical equilibrium and physical interactions.

Science.gov (United States)

Tagliazucchi, Mario; de la Cruz, Mónica Olvera; Szleifer, Igal

2010-03-23

The competition between chemical equilibrium, for example protonation, and physical interactions determines the molecular organization and functionality of biological and synthetic systems. Charge regulation by displacement of acid-base equilibrium induced by changes in the local environment provides a feedback mechanism that controls the balance between electrostatic, van der Waals, steric interactions and molecular organization. Which strategies do responsive systems follow to globally optimize chemical equilibrium and physical interactions? We address this question by theoretically studying model layers of end-grafted polyacids. These layers spontaneously form self-assembled aggregates, presenting domains of controlled local pH and whose morphologies can be manipulated by the composition of the solution in contact with the film. Charge regulation stabilizes micellar domains over a wide range of pH by reducing the local charge in the aggregate at the cost of chemical free energy and gaining in hydrophobic interactions. This balance determines the boundaries between different aggregate morphologies. We show that a qualitatively new form of organization arises from the coupling between physical interactions and protonation equilibrium. This optimization strategy presents itself with polyelectrolytes coexisting in two different and well-defined protonation states. Our results underline the need of considering the coupling between chemical equilibrium and physical interactions due to their highly nonadditive behavior. The predictions provide guidelines for the creation of responsive polymer layers presenting self-organized patterns with functional properties and they give insights for the understanding of competing interactions in highly inhomogeneous and constrained environments such as those relevant in nanotechnology and those responsible for biological cells function.

Non-equilibrium vibrational and chemical kinetics in shock heated carbon dioxide

Science.gov (United States)

Kosareva, A. A.

2018-05-01

The flows of CO2/CO/O2/O/C and CO2/CO/O mixtures behind shock waves are studied in the three-temperature, two-temperature and one-temperature approximations. The influence of the vibrational relaxation and chemical reactions on the flow composition, temperature and velocity is investigated. It is shown that the vibrational non-equilibrium has a significant effect on the macroscopic parameters of the flow near the front of the shock wave. It was found that the composition of the mixture has the greatest effect on the numerical density of CO molecules and O atoms. Also, significant differences between the values of the vibrational temperature of the asymmetric regime have been revealed.

Non-Equilibrium Heavy Flavored Hadron Yields from Chemical Equilibrium Strangeness-Rich QGP

OpenAIRE

Kuznetsova, Inga; Rafelski, Johann

2008-01-01

The yields of heavy flavored hadrons emitted from strangeness-rich QGP are evaluated within chemical non-equilibrium statistical hadronization model, conserving strangeness, charm, and entropy yields at hadronization.

Approach to chemical equilibrium in thermal models

International Nuclear Information System (INIS)

Boal, D.H.

1984-01-01

The experimentally measured (μ - , charged particle)/(μ - ,n) and (p,n/p,p') ratios for the emission of energetic nucleons are used to estimate the time evolution of a system of secondary nucleons produced in a direct interaction of a projectile or captured muon. The values of these ratios indicate that chemical equilibrium is not achieved among the secondary nucleons in noncomposite induced reactions, and this restricts the time scale for the emission of energetic nucleons to be about 0.7 x 10 -23 sec. It is shown that the reason why thermal equilibrium can be reached so rapidly for a particular nucleon species is that the sum of the particle spectra produced in multiple direct reactions looks surprisingly thermal. The rate equations used to estimate the reaction times for muon and nucleon induced reactions are then applied to heavy ion collisions, and it is shown that chemical equilibrium can be reached more rapidly, as one would expect

Determination of equilibrium composition of thermally ionized monoatomic gas under different physical conditions

Science.gov (United States)

Romanova, M. S.; Rydalevskaya, M. A.

2017-05-01

Perfect gas mixtures that result from thermal ionization of spatially and chemically homogeneous monoatomic gases are considered. Equilibrium concentrations of the components of such mixtures are determined using integration over the momentum space and summation with respect to energy levels of the distribution functions that maximize the entropy of system under condition for constancy of the total number of nuclei and electrons. It is demonstrated that such a method allows significant simplification of the calculation of the equilibrium composition for ionized mixtures at different temperatures and makes it possible to study the degree of ionization of gas versus gas density and number in the periodic table of elements.

The effect of chemically adjusting cement compositions on leachabilities of waste ions

International Nuclear Information System (INIS)

Barnes, M.W.; Scheetz, B.E.; Roy, D.M.

1986-01-01

The chemical composition of both portland and aluminate cements was adjusted by adding amorphous silica. In the case of portland cement, the object was to react with excess portlandite and obtain an overall composition compatible with C-S-H gel or C-S-H gel + silica at low temperatures, and to obtain the tobermorite composition in order to be in equilibrium with this phase at temperatures above normal ambient. In the case of aluminate cement, the object was to be in equilibrium with more silica-rich phases. These silica-adjusted cements were used to make composites with nuclear waste forms. Leach tests showed that the silica-adjusted composites were chemically more stable than those made with as-received cement. Leach rates were lower in the case of the adjusted cements for Rb, Cs, Ca, Sr, Ba, La, Ce, Nd, Gd, Al, and Si. Only Na in the case of both portland and aluminate cements, and Mg and U in the case of aluminate cements, had greater leach rates in adjusted cements. Adjusting the composition of cements with silica is concluded to be beneficial when making composites to encapsulate nuclear waste forms

Theory of chemical equilibrium in a lattice

International Nuclear Information System (INIS)

Dietrich, K.; Dufour, M.; Balazs, N.L.

1989-01-01

The chemical equilibrium is studied for the reaction A+B↔C, assuming that, initially, the particles B form a lattice and the particles A are statistically distributed on interstices. A mass action law is derived which defines the numbers n A , n B , n C of particles A, B, C in the chemical equilibrium assuming the initial distribution to be known. It predicts a considerably larger number n C of fused particles C compared to the mass action law for the gaseous phase. The result holds for an ordinary as well as for a nuclear lattice. Its possible relevance for the production of proton-rich isotopes in the universe is discussed. (orig.)

Minimizing the Free Energy: A Computer Method for Teaching Chemical Equilibrium Concepts.

Science.gov (United States)

Heald, Emerson F.

1978-01-01

Presents a computer method for teaching chemical equilibrium concepts using material balance conditions and the minimization of the free energy. Method for the calculation of chemical equilibrium, the computer program used to solve equilibrium problems and applications of the method are also included. (HM)

Conceptual Integration of Chemical Equilibrium by Prospective Physical Sciences Teachers

Science.gov (United States)

Ganaras, Kostas; Dumon, Alain; Larcher, Claudine

2008-01-01

This article describes an empirical study concerning the mastering of the chemical equilibrium concept by prospective physical sciences teachers. The main objective was to check whether the concept of chemical equilibrium had become an integrating and unifying concept for them, that is to say an operational and functional knowledge to explain and…

Chemical Principles Revisited: Chemical Equilibrium.

Science.gov (United States)

Mickey, Charles D.

1980-01-01

Describes: (1) Law of Mass Action; (2) equilibrium constant and ideal behavior; (3) general form of the equilibrium constant; (4) forward and reverse reactions; (5) factors influencing equilibrium; (6) Le Chatelier's principle; (7) effects of temperature, changing concentration, and pressure on equilibrium; and (8) catalysts and equilibrium. (JN)

The η/s of hadrons out of chemical equilibrium

International Nuclear Information System (INIS)

Wiranata, A; Wang, X N; Prakash, M; Huovinen, P; Koch, V

2014-01-01

We study how the shear viscosity, η, entropy density, s, and η/s depend on growing hadron chemical potentials resulting from the loss of chemical equilibrium during the evolution of a relativistic heavy-ion collision. Our calculations here are for an interacting pion gas in a system of net baryon number zero. Time evolution of the temperature and pion chemical potential are taken from ideal fluid hydrodynamic calculations of RHIC and LHC collisions. We find that the shear viscosity decreases whereas the entropy density increases with increasing pion chemical potential resulting in values of η/s that are slightly reduced from the case of chemical potentials being zero when chemical equilibrium prevails. Our results indicate that the inclusion of additional mesons and baryons will likely lead to further reduction in the value of η/s.

Phase Equilibrium, Chemical Equilibrium, and a Test of the Third Law: Experiments for Physical Chemistry.

Science.gov (United States)

Dannhauser, Walter

1980-01-01

Described is an experiment designed to provide an experimental basis for a unifying point of view (utilizing theoretical framework and chemistry laboratory experiments) for physical chemistry students. Three experiments are described: phase equilibrium, chemical equilibrium, and a test of the third law of thermodynamics. (Author/DS)

Evidence-Based Approaches to Improving Chemical Equilibrium Instruction

Science.gov (United States)

Davenport, Jodi L.; Leinhardt, Gaea; Greeno, James; Koedinger, Kenneth; Klahr, David; Karabinos, Michael; Yaron, David J.

2014-01-01

Two suggestions for instruction in chemical equilibrium are presented, along with the evidence that supports these suggestions. The first is to use diagrams to connect chemical reactions to the effects of reactions on concentrations. The second is the use of the majority and minority species (M&M) strategy to analyze chemical equilibrium…

Two-temperature chemically non-equilibrium modelling of an air supersonic ICP

Energy Technology Data Exchange (ETDEWEB)

El Morsli, Mbark; Proulx, Pierre [Laboratoire de Modelisation de Procedes Chimiques par Ordinateur Oppus, Departement de Genie Chimique, Universite de Sherbrooke (Ciheam) J1K 2R1 (Canada)

2007-08-21

In this work, a non-equilibrium mathematical model for an air inductively coupled plasma torch with a supersonic nozzle is developed without making thermal and chemical equilibrium assumptions. Reaction rate equations are written, and two coupled energy equations are used, one for the calculation of the translational-rotational temperature T{sub hr} and one for the calculation of the electro-vibrational temperature T{sub ev}. The viscous dissipation is taken into account in the translational-rotational energy equation. The electro-vibrational energy equation also includes the pressure work of the electrons, the Ohmic heating power and the exchange due to elastic collision. Higher order approximations of the Chapman-Enskog method are used to obtain better accuracy for transport properties, taking advantage of the most recent sets of collisions integrals available in the literature. The results obtained are compared with those obtained using a chemical equilibrium model and a one-temperature chemical non-equilibrium model. The influence of the power and the pressure chamber on the chemical and thermal non-equilibrium is investigated.

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.

Development of a Chemical Equilibrium Model for a Molten Core-Concrete Interaction Analysis Module

Energy Technology Data Exchange (ETDEWEB)

Seo, Jae Uk; Lee, Dae Young; Park, Chang Hwan [FNC Technology Co., Yongin (Korea, Republic of)

2016-10-15

This molten core could interact with the reactor cavity region which consists of concrete. In this process, components of molten core react with components of concrete through a lot of chemical reactions. As a result, many kinds of gas species are generated and those move up forming rising bubbles into the reactor containment atmosphere. These rising bubbles are the carrier of the many kinds of the aerosols coming from the MCCI (Molten Core Concrete Interaction) layers. To evaluate the amount of the aerosols released from the MCCI layers, the amount of the gas species generated from those layers should be calculated. The chemical equilibrium state originally implies the final state of the multiple chemical reactions; therefore, investigating the equilibrium composition of molten core can be applicable to predict the gas generation status. The most common way for finding the chemical equilibrium state is a minimization of total Gibbs free energy of the system. In this paper, the method to make good guess of initial state is suggested and chemical reaction results are compared with results of CSSI report No 164. Total mass of system and the number of atoms of each element are conserved. The tendency of calculation results is similar with results presented in CSNI Report except a few species. These differences may be caused by absence of Gibbs energy data of the species such as Fe{sub 2}SiO{sub 4}, CaFe{sub 2}O{sub 4}, U(OH){sub 3}, UO(OH), UO{sub 2}(OH), U{sub 3}O{sub 7}, La, Ce.

BGK-type models in strong reaction and kinetic chemical equilibrium regimes

International Nuclear Information System (INIS)

Monaco, R; Bianchi, M Pandolfi; Soares, A J

2005-01-01

A BGK-type procedure is applied to multi-component gases undergoing chemical reactions of bimolecular type. The relaxation process towards local Maxwellians, depending on mass and numerical densities of each species as well as common velocity and temperature, is investigated in two different cases with respect to chemical regimes. These cases are related to the strong reaction regime characterized by slow reactions, and to the kinetic chemical equilibrium regime where fast reactions take place. The consistency properties of both models are stated in detail. The trend to equilibrium is numerically tested and comparisons for the two regimes are performed within the hydrogen-air and carbon-oxygen reaction mechanism. In the spatial homogeneous case, it is also shown that the thermodynamical equilibrium of the models recovers satisfactorily the asymptotic equilibrium solutions to the reactive Euler equations

Chemical equilibrium. [maximizing entropy of gas system to derive relations between thermodynamic variables

Science.gov (United States)

1976-01-01

The entropy of a gas system with the number of particles subject to external control is maximized to derive relations between the thermodynamic variables that obtain at equilibrium. These relations are described in terms of the chemical potential, defined as equivalent partial derivatives of entropy, energy, enthalpy, free energy, or free enthalpy. At equilibrium, the change in total chemical potential must vanish. This fact is used to derive the equilibrium constants for chemical reactions in terms of the partition functions of the species involved in the reaction. Thus the equilibrium constants can be determined accurately, just as other thermodynamic properties, from a knowledge of the energy levels and degeneracies for the gas species involved. These equilibrium constants permit one to calculate the equilibrium concentrations or partial pressures of chemically reacting species that occur in gas mixtures at any given condition of pressure and temperature or volume and temperature.

Identification and Analysis of Student Conceptions Used To Solve Chemical Equilibrium Problems.

Science.gov (United States)

Voska, Kirk W.; Heikkinen, Henry W.

2000-01-01

Identifies and quantifies the chemistry conceptions used by students when solving chemical equilibrium problems requiring application of LeChatelier's Principle, and explores the feasibility of designing a paper and pencil test to accomplish these purposes. Eleven prevalent incorrect student conceptions about chemical equilibrium were identified…

Adaptive Chemical Networks under Non-Equilibrium Conditions: The Evaporating Droplet.

Science.gov (United States)

Armao, Joseph J; Lehn, Jean-Marie

2016-10-17

Non-volatile solutes in an evaporating drop experience an out-of-equilibrium state due to non-linear concentration effects and complex flow patterns. Here, we demonstrate a small molecule chemical reaction network that undergoes a rapid adaptation response to the out-of-equilibrium conditions inside the droplet leading to control over the molecular constitution and spatial arrangement of the deposition pattern. Adaptation results in a pronounced coffee stain effect and coupling to chemical concentration gradients within the drop is demonstrated. Amplification and suppression of network species are readily identifiable with confocal fluorescence microscopy. We anticipate that these observations will contribute to the design and exploration of out-of-equilibrium chemical systems, as well as be useful towards the development of point-of-care medical diagnostics and controlled deposition of small molecules through inkjet printing. © 2016 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Dynamic Processes of Conceptual Change: Analysis of Constructing Mental Models of Chemical Equilibrium.

Science.gov (United States)

Chiu, Mei-Hung; Chou, Chin-Cheng; Liu, Chia-Ju

2002-01-01

Investigates students' mental models of chemical equilibrium using dynamic science assessments. Reports that students at various levels have misconceptions about chemical equilibrium. Involves 10th grade students (n=30) in the study doing a series of hands-on chemical experiments. Focuses on the process of constructing mental models, dynamic…

Diffusion approximations to the chemical master equation only have a consistent stochastic thermodynamics at chemical equilibrium.

Science.gov (United States)

Horowitz, Jordan M

2015-07-28

The stochastic thermodynamics of a dilute, well-stirred mixture of chemically reacting species is built on the stochastic trajectories of reaction events obtained from the chemical master equation. However, when the molecular populations are large, the discrete chemical master equation can be approximated with a continuous diffusion process, like the chemical Langevin equation or low noise approximation. In this paper, we investigate to what extent these diffusion approximations inherit the stochastic thermodynamics of the chemical master equation. We find that a stochastic-thermodynamic description is only valid at a detailed-balanced, equilibrium steady state. Away from equilibrium, where there is no consistent stochastic thermodynamics, we show that one can still use the diffusive solutions to approximate the underlying thermodynamics of the chemical master equation.

CLOUDS IN SUPER-EARTH ATMOSPHERES: CHEMICAL EQUILIBRIUM CALCULATIONS

Energy Technology Data Exchange (ETDEWEB)

Mbarek, Rostom; Kempton, Eliza M.-R., E-mail: mbarekro@grinnell.edu, E-mail: kemptone@grinnell.edu [Department of Physics, Grinnell College, Grinnell, IA 50112 (United States)

2016-08-20

Recent studies have unequivocally proven the existence of clouds in super-Earth atmospheres. Here we provide a theoretical context for the formation of super-Earth clouds by determining which condensates are likely to form under the assumption of chemical equilibrium. We study super-Earth atmospheres of diverse bulk composition, which are assumed to form by outgassing from a solid core of chondritic material, following Schaefer and Fegley. The super-Earth atmospheres that we study arise from planetary cores made up of individual types of chondritic meteorites. They range from highly reducing to oxidizing and have carbon to oxygen (C:O) ratios that are both sub-solar and super-solar, thereby spanning a range of atmospheric composition that is appropriate for low-mass exoplanets. Given the atomic makeup of these atmospheres, we minimize the global Gibbs free energy of formation for over 550 gases and condensates to obtain the molecular composition of the atmospheres over a temperature range of 350–3000 K. Clouds should form along the temperature–pressure boundaries where the condensed species appear in our calculation. We find that the composition of condensate clouds depends strongly on both the H:O and C:O ratios. For the super-Earth archetype GJ 1214b, KCl and ZnS are the primary cloud-forming condensates at solar composition, in agreement with previous work. However, for oxidizing atmospheres, K{sub 2}SO{sub 4} and ZnO condensates are favored instead, and for carbon-rich atmospheres with super-solar C:O ratios, graphite clouds appear. For even hotter planets, clouds form from a wide variety of rock-forming and metallic species.

QUIL: a chemical equilibrium code

International Nuclear Information System (INIS)

Lunsford, J.L.

1977-02-01

A chemical equilibrium code QUIL is described, along with two support codes FENG and SURF. QUIL is designed to allow calculations on a wide range of chemical environments, which may include surface phases. QUIL was written specifically to calculate distributions associated with complex equilibria involving fission products in the primary coolant loop of the high-temperature gas-cooled reactor. QUIL depends upon an energy-data library called ELIB. This library is maintained by FENG and SURF. FENG enters into the library all reactions having standard free energies of reaction that are independent of concentration. SURF enters all surface reactions into ELIB. All three codes are interactive codes written to be used from a remote terminal, with paging control provided. Plotted output is also available

Students' and Teachers' Misapplication of Le Chatelier's Principle: Implications for the Teaching of Chemical Equilibrium.

Science.gov (United States)

Quilez-Pardo, Juan; Solaz-Portoles, Joan Josep

1995-01-01

Study of strategies and procedures of 170 students and 40 teachers when solving chemical equilibrium problems found misconceptions emerging through: misapplication of Le Chatelier's Principle, use of rote-learning recall, incorrect control of variables, limited use of chemical equilibrium law, lack of mastery of chemical equilibrium principles,…

Dynamics of chemical equilibrium of hadronic matter close to Tc

International Nuclear Information System (INIS)

Noronha-Hostler, J.; Beitel, M.; Greiner, C.; Shovkovy, I.

2010-01-01

Quick chemical equilibration times of hadrons (specifically, pp-bar, KK-bar, ΛΛ-bar, and ΩΩ-bar pairs) within a hadron gas are explained dynamically using Hagedorn states, which drive particles into equilibrium close to the critical temperature. Within this scheme, we use master equations and derive various analytical estimates for the chemical equilibration times. We compare our model to recent lattice results and find that for both T c =176 MeV and T c =196 MeV, the hadrons can reach chemical equilibrium almost immediately, well before the chemical freeze-out temperatures found in thermal fits for a hadron gas without Hagedorn states. Furthermore, the ratios p/π, K/π, Λ/π, and Ω/π match experimental values well in our dynamical scenario.

Using a Spreadsheet Scroll Bar to Solve Equilibrium Concentrations

Science.gov (United States)

Raviolo, Andres

2012-01-01

A simple, conceptual method is described for using the spreadsheet scroll bar to find the composition of a system at chemical equilibrium. Simulation of any kind of chemical equilibrium can be carried out using this method, and the effects of different disturbances can be predicted. This simulation, which can be used in general chemistry…

Transesterification of canola, palm, peanut, soybean and sunflower oil with methanol, ethanol, isopropanol, butanol and tert-butanol to biodiesel: Modelling of chemical equilibrium, reaction kinetics and mass transfer based on fatty acid composition

International Nuclear Information System (INIS)

Likozar, Blaž; Levec, Janez

2014-01-01

Graphical abstract: Modelling of chemical equilibrium, reaction kinetics and mass transfer for triglyceride transesterification with different alcohols based on fatty acid composition. - Highlights: • Catalysed transesterification to biodiesel with various oils, alcohols and catalysts. • Analysis of components and reactivity based on fatty acid composition of all species. • Simultaneous modelling of mass transfer, reaction kinetics and chemical equilibrium. • Diffusivities, distribution and mass transfer coefficients for individual components. • Correlation of kinetic parameters with molecular structure of reactants and products. - Abstract: Mechanism of alcoholysis (e.g. methanolysis) using different oils, alcohols and homogeneous base catalysts was utilized to devise chemical kinetics and thermodynamics based on fatty acid composition, differentiating among triglycerides, diglycerides, monoglycerides and fatty acid alkyl esters (e.g. fatty acid alkyl esters, FAME) with bonded gadoleic, linoleic, linolenic, oleic, palmitic and stearic acid-originating substituents. Their concentrations were measured using an optimized high-performance liquid chromatography (HPLC) method. Hydrodynamics and diffusion limitations in emulsion were considered in overall model by determining diffusivities, distribution coefficients, molar volumes, boiling points and viscosities of individual components. Pre-exponential factors and activation energies were related with structure of reactants, intermediates and products acknowledging number of carbons, double bonds and alkyl branches by linear and mixed response surface methodology. Developed model may be used with batch and continuous flow reactors, e.g. for novel micro-structured or industrial-scale process intensification, different vegetable or non-edible oils (waste cooking Jatropha or microalgae lipids)

A Computational Method for Determining the Equilibrium Composition and Product Temperature in a LH2/LOX Combustor

Science.gov (United States)

Sozen, Mehmet

2003-01-01

In what follows, the model used for combustion of liquid hydrogen (LH2) with liquid oxygen (LOX) using chemical equilibrium assumption, and the novel computational method developed for determining the equilibrium composition and temperature of the combustion products by application of the first and second laws of thermodynamics will be described. The modular FORTRAN code developed as a subroutine that can be incorporated into any flow network code with little effort has been successfully implemented in GFSSP as the preliminary runs indicate. The code provides capability of modeling the heat transfer rate to the coolants for parametric analysis in system design.

Non-equilibrium assembly of microtubules: from molecules to autonomous chemical robots.

Science.gov (United States)

Hess, H; Ross, Jennifer L

2017-09-18

Biological systems have evolved to harness non-equilibrium processes from the molecular to the macro scale. It is currently a grand challenge of chemistry, materials science, and engineering to understand and mimic biological systems that have the ability to autonomously sense stimuli, process these inputs, and respond by performing mechanical work. New chemical systems are responding to the challenge and form the basis for future responsive, adaptive, and active materials. In this article, we describe a particular biochemical-biomechanical network based on the microtubule cytoskeletal filament - itself a non-equilibrium chemical system. We trace the non-equilibrium aspects of the system from molecules to networks and describe how the cell uses this system to perform active work in essential processes. Finally, we discuss how microtubule-based engineered systems can serve as testbeds for autonomous chemical robots composed of biological and synthetic components.

Understanding Chemical Reaction Kinetics and Equilibrium with Interlocking Building Blocks

Science.gov (United States)

Cloonan, Carrie A.; Nichol, Carolyn A.; Hutchinson, John S.

2011-01-01

Chemical reaction kinetics and equilibrium are essential core concepts of chemistry but are challenging topics for many students, both at the high school and undergraduate university level. Visualization at the molecular level is valuable to aid understanding of reaction kinetics and equilibrium. This activity provides a discovery-based method to…

Calculating Shocks In Flows At Chemical Equilibrium

Science.gov (United States)

Eberhardt, Scott; Palmer, Grant

1988-01-01

Boundary conditions prove critical. Conference paper describes algorithm for calculation of shocks in hypersonic flows of gases at chemical equilibrium. Although algorithm represents intermediate stage in development of reliable, accurate computer code for two-dimensional flow, research leading up to it contributes to understanding of what is needed to complete task.

Influence of arc current and pressure on non-chemical equilibrium air arc behavior

Science.gov (United States)

Yi, WU; Yufei, CUI; Jiawei, DUAN; Hao, SUN; Chunlin, WANG; Chunping, NIU

2018-01-01

The influence of arc current and pressure on the non-chemical equilibrium (non-CE) air arc behavior of a nozzle structure was investigated based on the self-consistent non-chemical equilibrium model. The arc behavior during both the arc burning and arc decay phases were discussed at different currents and different pressures. We also devised the concept of a non-equilibrium parameter for a better understanding of non-CE effects. During the arc burning phase, the increasing current leads to a decrease of the non-equilibrium parameter of the particles in the arc core, while the increasing pressure leads to an increase of the non-equilibrium parameter of the particles in the arc core. During the arc decay phase, the non-CE effect will decrease by increasing the arc burning current and the nozzle pressure. Three factors together—convection, diffusion and chemical reactions—influence non-CE behavior.

Numerical simulation of hypersonic inlet flows with equilibrium or finite rate chemistry

Science.gov (United States)

Yu, Sheng-Tao; Hsieh, Kwang-Chung; Shuen, Jian-Shun; Mcbride, Bonnie J.

1988-01-01

An efficient numerical program incorporated with comprehensive high temperature gas property models has been developed to simulate hypersonic inlet flows. The computer program employs an implicit lower-upper time marching scheme to solve the two-dimensional Navier-Stokes equations with variable thermodynamic and transport properties. Both finite-rate and local-equilibrium approaches are adopted in the chemical reaction model for dissociation and ionization of the inlet air. In the finite rate approach, eleven species equations coupled with fluid dynamic equations are solved simultaneously. In the local-equilibrium approach, instead of solving species equations, an efficient chemical equilibrium package has been developed and incorporated into the flow code to obtain chemical compositions directly. Gas properties for the reaction products species are calculated by methods of statistical mechanics and fit to a polynomial form for C(p). In the present study, since the chemical reaction time is comparable to the flow residence time, the local-equilibrium model underpredicts the temperature in the shock layer. Significant differences of predicted chemical compositions in shock layer between finite rate and local-equilibrium approaches have been observed.

Speeding up compositional reservoir simulation through an efficient implementation of phase equilibrium calculation

DEFF Research Database (Denmark)

Belkadi, Abdelkrim; Yan, Wei; Moggia, Elsa

2013-01-01

Compositional reservoir simulations are widely used to simulate reservoir processes with strong compositional effects, such as gas injection. The equations of state (EoS) based phase equilibrium calculation is a time consuming part in this type of simulations. The phase equilibrium problem can....... Application of the shadow region method to skip stability analysis can further cut the phase equilibrium calculation time. Copyright 2013, Society of Petroleum Engineers....

Development of chemical equilibrium analysis code 'CHEEQ'

International Nuclear Information System (INIS)

Nagai, Shuichiro

2006-08-01

'CHEEQ' code which calculates the partial pressure and the mass of the system consisting of ideal gas and pure condensed phase compounds, was developed. Characteristics of 'CHEEQ' code are as follows. All the chemical equilibrium equations were described by the formation reactions from the mono-atomic gases in order to simplify the code structure and input preparation. Chemical equilibrium conditions, Σν i μ i =0 for the gaseous compounds and precipitated condensed phase compounds and Σν i μ i > 0 for the non-precipitated condensed phase compounds, were applied. Where, ν i and μ i are stoichiometric coefficient and chemical potential of component i. Virtual solid model was introduced to perform the calculation of constant partial pressure condition. 'CHEEQ' was consisted of following 3 parts, (1) analysis code, zc132. f. (2) thermodynamic data base, zmdb01 and (3) input data file, zindb. 'CHEEQ' code can calculate the system which consisted of elements (max.20), condensed phase compounds (max.100) and gaseous compounds. (max.200). Thermodynamic data base, zmdb01 contains about 1000 elements and compounds, and 200 of them were Actinide elements and their compounds. This report describes the basic equations, the outline of the solution procedure and instructions to prepare the input data and to evaluate the calculation results. (author)

Teaching Chemical Equilibrium with the Jigsaw Technique

Science.gov (United States)

Doymus, Kemal

2008-01-01

This study investigates the effect of cooperative learning (jigsaw) versus individual learning methods on students' understanding of chemical equilibrium in a first-year general chemistry course. This study was carried out in two different classes in the department of primary science education during the 2005-2006 academic year. One of the classes…

Phase rule calculations and the thermodynamics of reactive systems under chemical equilibrium

Directory of Open Access Journals (Sweden)

PLATT G. M.

1999-01-01

Full Text Available In this paper, we examine the resolution of some phase rule problems within the context of multiple chemical equilibrium reactions, using cubic equations of state and an activity coefficient model. Bubble and dew reactive surfaces, reactive azeotropic loci and reactive critical loci are generated and presented in graphical form. Also isobaric bubble and dew reactive enthalpy loci, which may be useful in the modeling of reactive distillation operations, are depicted. All the formalism here employed is developed within the coordinate transformation of Ung and Doherty, which is appropriate for equilibrium reactive or multireactive systems. The major contribution of this work is the determination of critical loci for reactive or multireactive equilibrium systems. Since it is known that for some class of chemical reactions the kinetics and product distribution exhibit high sensitivity to pressure near criticality, the present study may be useful as a predicting tool in these cases if the chemical equilibrium condition is not too far from the real phenomenon.

The local temperature and chemical potential inside a mesoscopic device driven out of equilibrium

International Nuclear Information System (INIS)

Wang, Pei

2011-01-01

In this paper we introduce a method for calculating the local temperature and chemical potential inside a mesoscopic device out of equilibrium. We show how to check the conditions of local thermal equilibrium when the whole system is out of equilibrium. In particular, we study the on-site chemical potentials inside a chain coupled to two reservoirs at a finite voltage bias. We observe in the presence of disorder a large fluctuation in on-site chemical potentials, which can be suppressed by the electron–electron interaction. By taking the average with respect to the configurations of the disorder, we recover the classical picture where the voltage drops monotonically through the resistance wire. We prove the existence of local intensive variables in a mesoscopic device which is in equilibrium or not far from equilibrium

Spectral Quasi-Equilibrium Manifold for Chemical Kinetics.

Science.gov (United States)

Kooshkbaghi, Mahdi; Frouzakis, Christos E; Boulouchos, Konstantinos; Karlin, Iliya V

2016-05-26

The Spectral Quasi-Equilibrium Manifold (SQEM) method is a model reduction technique for chemical kinetics based on entropy maximization under constraints built by the slowest eigenvectors at equilibrium. The method is revisited here and discussed and validated through the Michaelis-Menten kinetic scheme, and the quality of the reduction is related to the temporal evolution and the gap between eigenvalues. SQEM is then applied to detailed reaction mechanisms for the homogeneous combustion of hydrogen, syngas, and methane mixtures with air in adiabatic constant pressure reactors. The system states computed using SQEM are compared with those obtained by direct integration of the detailed mechanism, and good agreement between the reduced and the detailed descriptions is demonstrated. The SQEM reduced model of hydrogen/air combustion is also compared with another similar technique, the Rate-Controlled Constrained-Equilibrium (RCCE). For the same number of representative variables, SQEM is found to provide a more accurate description.

Effectiveness of Instruction Based on the Constructivist Approach on Understanding Chemical Equilibrium Concepts

Science.gov (United States)

Akkus, Huseyin; Kadayifci, Hakki; Atasoy, Basri; Geban, Omer

2003-01-01

The purpose of this study was to identify misconceptions concerning chemical equilibrium concepts and to investigate the effectiveness of instruction based on the constructivist approach over traditional instruction on 10th grade students' understanding of chemical equilibrium concepts. The subjects of this study consisted of 71 10th grade…

QUIC: a chemical kinetics code for use with the chemical equilibrium code QUIL

International Nuclear Information System (INIS)

Lunsford, J.L.

1977-10-01

A chemical rate kinetics code QUIC is described, along with a support code RATE. QUIC is designed to allow chemical kinetics calculations on a wide variety of chemical environments while operating in the overlay environment of the chemical equilibrium code QUIL. QUIC depends upon a rate-data library called LIBR. This library is maintained by RATE. RATE enters into the library all reactions in a standardized format. The code QUIC, operating in conjunction with QUIL, is interactive and written to be used from a remote terminal, with paging control provided. Plotted output is also available

A Colorful Demonstration to Visualize and Inquire into Essential Elements of Chemical Equilibrium

Science.gov (United States)

Eilks, Ingo; Gulacar, Ozcan

2016-01-01

One of the topics that chemistry teachers have a great challenge introducing is chemical equilibrium. When being introduced to chemical equilibrium, many students have difficulties in understanding that some reactions do not go to completion, as this contrasts most of their supposed prior experiences in chemistry lessons. Students may also…

The Adverse Effects of Le Chatelier's Principle on Teacher Understanding of Chemical Equilibrium

Science.gov (United States)

Cheung, Derek

2009-01-01

Although the scientific inadequacy of Le Chatelier's principle has long been documented in the literature, the principle is still treated as a central concept of chemical equilibrium by textbook writers and teachers in many countries. In the past, researchers' interest has focused on student misconceptions about chemical equilibrium and has…

A Study of Interactions between Mixing and Chemical Reaction Using the Rate-Controlled Constrained-Equilibrium Method

Science.gov (United States)

Hadi, Fatemeh; Janbozorgi, Mohammad; Sheikhi, M. Reza H.; Metghalchi, Hameed

2016-10-01

The rate-controlled constrained-equilibrium (RCCE) method is employed to study the interactions between mixing and chemical reaction. Considering that mixing can influence the RCCE state, the key objective is to assess the accuracy and numerical performance of the method in simulations involving both reaction and mixing. The RCCE formulation includes rate equations for constraint potentials, density and temperature, which allows taking account of mixing alongside chemical reaction without splitting. The RCCE is a dimension reduction method for chemical kinetics based on thermodynamics laws. It describes the time evolution of reacting systems using a series of constrained-equilibrium states determined by RCCE constraints. The full chemical composition at each state is obtained by maximizing the entropy subject to the instantaneous values of the constraints. The RCCE is applied to a spatially homogeneous constant pressure partially stirred reactor (PaSR) involving methane combustion in oxygen. Simulations are carried out over a wide range of initial temperatures and equivalence ratios. The chemical kinetics, comprised of 29 species and 133 reaction steps, is represented by 12 RCCE constraints. The RCCE predictions are compared with those obtained by direct integration of the same kinetics, termed detailed kinetics model (DKM). The RCCE shows accurate prediction of combustion in PaSR with different mixing intensities. The method also demonstrates reduced numerical stiffness and overall computational cost compared to DKM.

Analysing chemical equilibrium conditions when studying butyl acetate synthesis

OpenAIRE

Álvaro Orjuela Londoño; Fernando Leiva Lenis; Luis Alejandro Boyacá Mendivelso; Gerardo Rodríguez Niño; Luis María Carballo Suárez

2010-01-01

This work studied the liquid phase of acetic acid and butyl alcohol esterification reaction (P atm = 560 mmHg),using an ion exchange resin (Lewatit K-2431) as catalyst. A set of assays were carried out for determining the effect of catalyst load, temperature and molar ratio (acid/alcohol) on chemical equilibrium constant. Components’ selective sorption on the resin matrix was noticed; its effect on equilibrium conditions was verified, by using different acid/alcohol starting ratios. A non-ide...

Thermodynamic and transport properties of gaseous tetrafluoromethane in chemical equilibrium

Science.gov (United States)

Hunt, J. L.; Boney, L. R.

1973-01-01

Equations and in computer code are presented for the thermodynamic and transport properties of gaseous, undissociated tetrafluoromethane (CF4) in chemical equilibrium. The computer code calculates the thermodynamic and transport properties of CF4 when given any two of five thermodynamic variables (entropy, temperature, volume, pressure, and enthalpy). Equilibrium thermodynamic and transport property data are tabulated and pressure-enthalpy diagrams are presented.

Iteration scheme for implicit calculations of kinetic and equilibrium chemical reactions in fluid dynamics

International Nuclear Information System (INIS)

Ramshaw, J.D.; Chang, C.H.

1995-01-01

An iteration scheme for the implicit treatment of equilibrium chemical reactions in partial equilibrium flow has previously been described. Here we generalize this scheme to kinetic reactions as well as equilibrium reactions. This extends the applicability of the scheme to problems with kinetic reactions that are fast in regions of the flow field but slow in others. The resulting scheme thereby provides a single unified framework for the implicit treatment of an arbitrary number of coupled equilibrium and kinetic reactions in chemically reacting fluid flow. 10 refs., 2 figs

Investigation of Chemical Equilibrium Kinetics by the Electromigration Method

CERN Document Server

Bozhikov, G A; Bontchev, G D; Maslov, O D; Milanov, M V; Dmitriev, S N

2002-01-01

Measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the complex formation of Hf(IV) and DTPA is determined.

Chemical Equilibrium and Polynomial Equations: Beware of Roots.

Science.gov (United States)

Smith, William R.; Missen, Ronald W.

1989-01-01

Describes two easily applied mathematical theorems, Budan's rule and Rolle's theorem, that in addition to Descartes's rule of signs and intermediate-value theorem, are useful in chemical equilibrium. Provides examples that illustrate the use of all four theorems. Discusses limitations of the polynomial equation representation of chemical…

Students' and teachers' misapplication of le chatelier's principle: Implications for the teaching of chemical equilibrium

Science.gov (United States)

Quílez-Pardo, Juan; Solaz-Portolés, Joan Josep

The aim of this article was to study the reasons, strategies, and procedures that both students and teachers use to solve some chemical equilibrium questions and problems. Inappropriate conceptions on teaching and a lack of knowledge regarding the limited usefulness of Le Chatelier's principle, with its vague and ambiguous formulation and textbook presentation, may be some of the sources of misconceptions about the prediction of the effect of changing conditions on chemical equilibrium. To diagnose misconceptions and their possible sources, a written test was developed and administered to 170 1st-year university chemistry students. A chemical equilibrium problem, relating to the students' test, was solved by 40 chemistry teachers. First, we ascertained that teacher's conceptions might influence the problem-solving strategies of the learner. Based on this first aspect, our discussion also concerns students' and teachers' misconceptions related to the Le Chatelier's principle. Misconceptions emerged through: (a) misapplication and misunderstanding of Le Chatelier's principle; (b) use of rote-learning recall and algorithmic procedures; (c) incorrect control of the variables involved; (d) limited use of the chemical equilibrium law; (e) a lack of mastery of chemical equilibrium principles and difficulty in transferring such principles to new situations. To avoid chemical equilibrium misconceptions, a specific pattern of conceptual and methodological change may be considered.Received: 16 November 1993; Revised: 21 September 1994;

Coupling microscopic and mesoscopic scales to simulate chemical equilibrium between a nanometric carbon cluster and detonation products fluid.

Science.gov (United States)

Bourasseau, Emeric; Maillet, Jean-Bernard

2011-04-21

This paper presents a new method to obtain chemical equilibrium properties of detonation products mixtures including a solid carbon phase. In this work, the solid phase is modelled through a mesoparticle immersed in the fluid, such that the heterogeneous character of the mixture is explicitly taken into account. Inner properties of the clusters are taken from an equation of state obtained in a previous work, and interaction potential between the nanocluster and the fluid particles is derived from all-atoms simulations using the LCBOPII potential (Long range Carbon Bond Order Potential II). It appears that differences in chemical equilibrium results obtained with this method and the "composite ensemble method" (A. Hervouet et al., J. Phys. Chem. B, 2008, 112.), where fluid and solid phases are considered as non-interacting, are not significant, underlining the fact that considering the inhomogeneity of such system is crucial.

A two-temperature chemical non-equilibrium modeling of DC arc plasma

International Nuclear Information System (INIS)

Qian Haiyang; Wu Bin

2011-01-01

To a better understanding of non-equilibrium characteristics of DC arc plasma,a two-dimensional axisymmetric two-temperature chemical non-equilibrium (2T-NCE) model is applied for direct current arc argon plasma generator with water-cooled constrictor at atmospheric pressure. The results show that the electron temperature and heavy particle temperature has a relationship under different working parameters, indicating that DC arc plasma has a strong non-equilibrium characteristic, and the variation is obvious. (authors)

Learning of Chemical Equilibrium through Modelling-Based Teaching

Science.gov (United States)

Maia, Poliana Flavia; Justi, Rosaria

2009-01-01

This paper presents and discusses students' learning process of chemical equilibrium from a modelling-based approach developed from the use of the "Model of Modelling" diagram. The investigation was conducted in a regular classroom (students 14-15 years old) and aimed at discussing how modelling-based teaching can contribute to students…

Promoting Pre-Service Elementary Students' Understanding of Chemical Equilibrium through Discussions in Small Groups

Science.gov (United States)

Bilgin, Ibrahim

2006-01-01

The purpose of this study was to investigate the effectiveness of small group discussion on students' conceptual understanding of chemical equilibrium. Students' understanding of chemical equilibrium concepts was measured using the Misconception Identification Test. The test consisted of 30 items and administered as pre-posttests to a total of 81…

Teaching Chemical Equilibrium and Thermodynamics in Undergraduate General Chemistry Classes.

Science.gov (United States)

Banerjee, Anil C.

1995-01-01

Discusses some of the conceptual difficulties encountered by undergraduate students in learning certain aspects of chemical equilibrium and thermodynamics. Discusses teaching strategies for dealing with these difficulties. (JRH)

CHMTRNS, Non-Equilibrium Chemical Transport Code

International Nuclear Information System (INIS)

Noorishad, J.; Carnahan, C.L.; Benson, L.V.

1998-01-01

1 - Description of program or function: CHMTRNS simulates solute transport for steady one-dimensional fluid flow by convection and diffusion or dispersion in a saturated porous medium based on the assumption of local chemical equilibrium. The chemical interactions included in the model are aqueous-phase complexation, solid-phase ion exchange of bare ions and complexes using the surface complexation model, and precipitation or dissolution of solids. The program can simulate the kinetic dissolution or precipitation for calcite and silica as well as irreversible dissolution of glass. Thermodynamic parameters are temperature dependent and are coupled to a companion heat transport simulator; thus, the effects of transient temperature conditions can be considered. Options for oxidation-reduction (redox) and C-13 fractionation as well as non-isothermal conditions are included. 2 - Method of solution: The governing equations for both reactive chemical and heat transport are discretized in time and space. For heat transport, the Crank-Nicolson approximation is used in conjunction with a LU decomposition and backward substitution solution procedure. To deal with the strong nonlinearity of the chemical transport equations, a generalized Newton-Raphson method is used

Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system.

Science.gov (United States)

Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

2016-01-20

The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for chemical reactions far from equilibrium. We mathematically reveal that the control mechanism is formulated as pulse-density modulation control of the fusion-fission timing. We produce the droplet open-reactor system using microfluidic technologies and then perform external control and autonomous feedback control over autocatalytic chemical oscillation reactions far from equilibrium. We believe that this system will be valuable for the dynamical control over self-organized phenomena far from equilibrium in chemical and biomedical studies.

Investigation on non-equilibrium performance of composite adsorbent for resorption refrigeration

International Nuclear Information System (INIS)

Jiang, L.; Wang, L.W.; Zhou, Z.S.; Zhu, F.Q.; Wang, R.Z.

2016-01-01

Highlights: • Performance of resorption refrigeration is analyzed based on non-equilibrium reaction process. • The porous matrix improves the heat and mass performance of composite adsorbent. • The actual desorption process has the significant hysteresis phenomenon. • The highest energy efficiency of Manganese and Calcium chloride working pair is 0.272. - Abstract: The aims of this paper is to indicate that the non-equilibrium adsorption testing results is more suitable for prediction of real refrigeration performance than equilibrium data. Therefore, a test unit is constructed to test the non-equilibrium performance of different composite adsorbents. The adsorption and desorption quantity are measured and calculated by smart differential pressure transmitter. The non-equilibrium adsorption performances of working pair of Manganese chloride–ammonia, Calcium chloride–ammonia and Ammonium chloride–ammonia are investigated respectively. Results show that hysteresis phenomena happens obviously in non-equilibrium desorption process, which is related with dual variables rather than single variable. Based on the testing results, resorption refrigeration performance is analyzed, in which Manganese chloride is used as high temperature salt (HTS), and Calcium chloride, Ammonium chloride are selected as low temperature salt (LTS) for comparison. Results show that the highest COP and SCP for resorption refrigeration are about 0.272 and 45.6 W/kg, respectively. Performance of Manganese chloride–Calcium chloride and Manganese chloride–Ammonium chloride working pairs are much lower when compared with theoretical data.

Analysis of the trend to equilibrium of a chemically reacting system

International Nuclear Information System (INIS)

Kremer, Gilberto M; Bianchi, Miriam Pandolfi; Soares, Ana Jacinta

2007-01-01

In this present paper, a quaternary gaseous reactive mixture, for which the chemical reaction is close to its final stage and the elastic and reactive frequencies are comparable, is modelled within the Boltzmann equation extended to reacting gases. The main objective is a detailed analysis of the non-equilibrium effects arising in the reactive system A 1 + A 2 ↔ A 3 + A 4 , in a flow regime which is considered not far away from thermal, mechanical and chemical equilibrium. A first-order perturbation solution technique is applied to the macroscopic field equations for the spatially homogeneous gas system, and the trend to equilibrium is studied in detail. Adopting elastic hard-spheres and reactive line-of-centres cross sections and an appropriate choice of the input distribution functions-which allows us to distinguish the two cases where the constituents are either at same or different temperatures-explicit computations of the linearized production terms for mass, momentum and total energy are performed for each gas species. The departures from the equilibrium states of densities, temperatures and diffusion fluxes are characterized by small perturbations of their corresponding equilibrium values. For the hydrogen-chlorine system, the perturbations are plotted as functions of time for both cases where the species are either at the same or different temperatures. Moreover, the trend to equilibrium of the reaction rates is represented for the forward and backward reaction H 2 + Cl ↔ HCl + H

Chemical vapour deposition of silicon under reduced pressure in a hot-wall reactor: Equilibrium and kinetics

International Nuclear Information System (INIS)

Langlais, F.; Hottier, F.; Cadoret, R.

1982-01-01

Silicon chemical vapour deposition (SiH 2 Cl 2 /H 2 system), under reduced pressure conditions, in a hot-wall reactor, is presented. The vapour phase composition is assessed by evaluating two distinct equilibria. The homogeneous equilibrium , which assumes that the vapour phase is not in equilibrium with solid silicon, is thought to give an adequate description of the vapour phase in the case of low pressure, high gas velocities, good temperature homogeneity conditions. A comparison with heterogeneous equilibrium enables us to calculate the supersaturation so evidencing a highly irreversible growth system. The experimental determination of the growth rates reveals two distinct temperature ranges: below 1000 0 C, polycrystalline films are usually obtained with a thermally activated growth rate (+40 kcal mole -1 ) and a reaction order, with respect to the predominant species SiCl 2 , close to one; above 1000 0 C, the films are always monocrystalline and their growth rate exhibits a much lower or even negative activation energy, the reaction order in SiCl 2 remaining about one. (orig.)

Teachers' Misconceptions about the Effects of Addition of More Reactants or Products on Chemical Equilibrium

Science.gov (United States)

Cheung, Derek; Ma, Hong-jia; Yang, Jie

2009-01-01

The importance of research on misconceptions about chemical equilibrium is well recognized by educators, but in the past, researchers' interest has centered on student misconceptions and has neglected teacher misconceptions. Focusing on the effects of adding more reactants or products on chemical equilibrium, this article discusses the various…

Geometrical Description of Chemical Equilibrium and Le Cha^telier's Principle: Two-Component Systems

Science.gov (United States)

Novak, Igor

2018-01-01

Chemical equilibrium is one of the most important concepts in chemistry. The changes in properties of the chemical system at equilibrium induced by variations in pressure, volume, temperature, and concentration are always included in classroom teaching and discussions. This work introduces a novel, geometrical approach to understanding the…

Time-dependent two-temperature chemically non-equilibrium modelling of high-power Ar-N2 pulse-modulated inductively coupled plasmas at atmospheric pressure

International Nuclear Information System (INIS)

Tanaka, Yasunori

2006-01-01

A time-dependent, two-dimensional, two-temperature and chemical non-equilibrium model was developed for high-power Ar-N 2 pulse-modulated inductively coupled plasmas (PMICPs) at atmospheric pressure. The high-power PMICP is a new technique for sustaining high-power induction plasmas. It can control the plasma temperature and radical densities in the time domain. The PMICP promotes non-equilibrium effects by a sudden application of electric field, even in the high-power density plasmas. The developed model accounts separately for the time-dependent energy conservation equations of electrons and heavy particles. This model also considers reaction heat effects and energy transfer between electrons and heavy particles as well as enthalpy flow resulting from diffusion caused by the particle density gradient. Chemical non-equilibrium effects are also taken into account by solving time-dependent mass conservation equations for each particle, considering diffusion, convection and net production terms resulting from 30 chemical reactions. Transport and thermodynamic properties of Ar-N 2 plasmas are calculated self-consistently using the first order approximation of the Chapman-Enskog method at each position and iteration using the local particle composition, heavy particle temperature and electron temperature. This model is useful to discuss time evolution in temperature, gas flow fields and distribution of chemical species

Response to Contradiction: Conflict Resolution Strategies Used by Students in Solving Problems of Chemical Equilibrium.

Science.gov (United States)

Niaz, Mansoor

2001-01-01

Illustrates how a novel problem of chemical equilibrium based on a closely related sequence of items can facilitate students' conceptual understanding. Students were presented with a chemical reaction in equilibrium to which a reactant was added as an external effect. Three studies were conducted to assess alternative conceptions. (Author/SAH)

The technique for calculation of equilibrium in heterogeneous systems of the InP-GaP-HCl type

International Nuclear Information System (INIS)

Voronin, V.A.; Prokhorov, V.A.; Goliusov, V.A.; Chuchmarev, S.K.

1983-01-01

Technique for calculation of equilibrium in heterogeneous systems based on A 1 3 B 5 -A 2 3 B 5 solid solutions implying the use of structural-topological models of chemical equilibrium in the investigated systems, is developed. Chemical equilibrium in the InP-GaP-HCl systems is analyzed by means of the suggested technique and the equilibrium composition of the gas phase is calculated

The efficiency of driving chemical reactions by a physical non-equilibrium is kinetically controlled.

Science.gov (United States)

Göppel, Tobias; Palyulin, Vladimir V; Gerland, Ulrich

2016-07-27

An out-of-equilibrium physical environment can drive chemical reactions into thermodynamically unfavorable regimes. Under prebiotic conditions such a coupling between physical and chemical non-equilibria may have enabled the spontaneous emergence of primitive evolutionary processes. Here, we study the coupling efficiency within a theoretical model that is inspired by recent laboratory experiments, but focuses on generic effects arising whenever reactant and product molecules have different transport coefficients in a flow-through system. In our model, the physical non-equilibrium is represented by a drift-diffusion process, which is a valid coarse-grained description for the interplay between thermophoresis and convection, as well as for many other molecular transport processes. As a simple chemical reaction, we consider a reversible dimerization process, which is coupled to the transport process by different drift velocities for monomers and dimers. Within this minimal model, the coupling efficiency between the non-equilibrium transport process and the chemical reaction can be analyzed in all parameter regimes. The analysis shows that the efficiency depends strongly on the Damköhler number, a parameter that measures the relative timescales associated with the transport and reaction kinetics. Our model and results will be useful for a better understanding of the conditions for which non-equilibrium environments can provide a significant driving force for chemical reactions in a prebiotic setting.

Stability fields of smectites and illites as a function of temperature and chemical composition

International Nuclear Information System (INIS)

Tardy, Y.; Duplay, J.; Fritz, B.; Strasbourg-1 Univ., 67

1987-04-01

A thermodynamic ideal solid solution analogue is proposed which accounts the correlations which clearly reflect the temperatures at which the nonmineralic population are supposed to have been formed. The solid solution is considered, at a particle scale, as an ideal mixture of individual layers, weakly bent each to the next. Each layer presents the chemical composition of a given end member, so that the proportions of the different end members change from one particle to another. Considering one particle of a given chemical composition, the multipole solid solution theory allows to calculate the wheighted contributions of each end member into the ideal clay solid solution along with the chemical composition of the aqueous solutions in equilibrium with the considered particle in its independent microenvironment. This model is able to predict the nature of the chemical correlations which are expected, at a given temperature, within a given population. This model is also applied to the prediction of the temperature required for the conversion of smectite into illite during the burial diagenesis. (orig./HP)

FastChem: An ultra-fast equilibrium chemistry

Science.gov (United States)

Kitzmann, Daniel; Stock, Joachim

2018-04-01

FastChem is an equilibrium chemistry code that calculates the chemical composition of the gas phase for given temperatures and pressures. Written in C++, it is based on a semi-analytic approach, and is optimized for extremely fast and accurate calculations.

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.

Modified NASA-Lewis chemical equilibrium code for MHD applications

Science.gov (United States)

Sacks, R. A.; Geyer, H. K.; Grammel, S. J.; Doss, E. D.

1979-01-01

A substantially modified version of the NASA-Lewis Chemical Equilibrium Code was recently developed. The modifications were designed to extend the power and convenience of the Code as a tool for performing combustor analysis for MHD systems studies. The effect of the programming details is described from a user point of view.

Non-equilibrium effects in high temperature chemical reactions

Science.gov (United States)

Johnson, Richard E.

1987-01-01

Reaction rate data were collected for chemical reactions occurring at high temperatures during reentry of space vehicles. The principle of detailed balancing is used in modeling kinetics of chemical reactions at high temperatures. Although this principle does not hold for certain transient or incubation times in the initial phase of the reaction, it does seem to be valid for the rates of internal energy transitions that occur within molecules and atoms. That is, for every rate of transition within the internal energy states of atoms or molecules, there is an inverse rate that is related through an equilibrium expression involving the energy difference of the transition.

Cross-coupling effects in chemically non-equilibrium viscous compressible flows

International Nuclear Information System (INIS)

Kustova, E.V.; Giordano, D.

2011-01-01

Graphical abstract: Self-cosistent kinetic-theory description of chemical-reaction rates and mean normal stress in one-temperature viscous compressible gas flows. Reaearch highlights: → In chemically non-equilibrium viscous compressible flows, the rate of each reaction depends on the velocity divergence and rates of all other reactions. → Cross effects between the rates of chemical reactions and normal mean stress can be found in the symmetric form and expressed in terms of the reaction affinities. → In the case of small affinities, the entropy production is unconditionally non-negative; in the case of finite affinities, the entropy production related to the scalar forces has no definite sign. - Abstract: A closed self-consistent description of a one-temperature non-equilibrium reacting flow is presented on the basis of the kinetic theory methods. A general case including internal degrees of freedom, dissociation-recombination and exchange reactions, and arbitrary values of affinities of chemical reactions is considered. Chemical-reaction rates and mean normal stress in viscous compressible flows are studied and a symmetric cross coupling between these terms is found. It is shown that the rate of each chemical reaction and the mean normal stress depend on velocity divergence and affinities of all chemical reactions; the law of mass action is violated in viscous flows. The results obtained in the frame of linear irreversible thermodynamics can be deduced from the proposed model for the particular case of small affinities. The reciprocal Onsager-Casimir relations are verified, the symmetry of kinetic coefficients is demonstrated, and the entropy production in a viscous flow is studied.

Determination of solute organic concentration in contaminated soils using a chemical-equilibrium soil column system

DEFF Research Database (Denmark)

Gamst, Jesper; Kjeldsen, Peter; Christensen, Thomas Højlund

2007-01-01

using two soils with different content of organic carbon (f(oc) of 1.5 and 6.5%, respectively). A quadruple blind test of the ER-V system using glass beads in stead of soil showed an acceptable recovery (65-85%) of all of the 11 VOCs tested. Only for the most volatile compound (heptane, K-H similar...... to 80) an unacceptable recovery was found (9%). The contact time needed for obtaining chemical equilibrium was tested in the ER-H system by performing five test with different duration (1, 2, 4, 7 and 19 days) using the low organic carbon soil. Seven days of contact time appeared sufficient...... for determination of solute concentration in a contaminated soil were developed; (1) a chemical Equilibrium and Recirculation column test for Volatile organic chemicals (ER-V) and (2) a chemical Equilibrium and Recirculation column test for Hydrophobic organic chemicals (ER-H). The two test systems were evaluated...

KEMOD: A mixed chemical kinetic and equilibrium model of aqueous and solid phase geochemical reactions

International Nuclear Information System (INIS)

Yeh, G.T.; Iskra, G.A.

1995-01-01

This report presents the development of a mixed chemical Kinetic and Equilibrium MODel in which every chemical species can be treated either as a equilibrium-controlled or as a kinetically controlled reaction. The reaction processes include aqueous complexation, adsorption/desorption, ion exchange, precipitation/dissolution, oxidation/reduction, and acid/base reactions. Further development and modification of KEMOD can be made in: (1) inclusion of species switching solution algorithms, (2) incorporation of the effect of temperature and pressure on equilibrium and rate constants, and (3) extension to high ionic strength

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation.

Science.gov (United States)

de Oliveira, Luciana Renata; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C

2014-08-14

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their "far from equilibrium behavior," hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative "external vector field" whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the "plasticity property" of biological systems and to their

The role of non-equilibrium fluxes in the relaxation processes of the linear chemical master equation

International Nuclear Information System (INIS)

Oliveira, Luciana Renata de; Bazzani, Armando; Giampieri, Enrico; Castellani, Gastone C.

2014-01-01

We propose a non-equilibrium thermodynamical description in terms of the Chemical Master Equation (CME) to characterize the dynamics of a chemical cycle chain reaction among m different species. These systems can be closed or open for energy and molecules exchange with the environment, which determines how they relax to the stationary state. Closed systems reach an equilibrium state (characterized by the detailed balance condition (D.B.)), while open systems will reach a non-equilibrium steady state (NESS). The principal difference between D.B. and NESS is due to the presence of chemical fluxes. In the D.B. condition the fluxes are absent while for the NESS case, the chemical fluxes are necessary for the state maintaining. All the biological systems are characterized by their “far from equilibrium behavior,” hence the NESS is a good candidate for a realistic description of the dynamical and thermodynamical properties of living organisms. In this work we consider a CME written in terms of a discrete Kolmogorov forward equation, which lead us to write explicitly the non-equilibrium chemical fluxes. For systems in NESS, we show that there is a non-conservative “external vector field” whose is linearly proportional to the chemical fluxes. We also demonstrate that the modulation of these external fields does not change their stationary distributions, which ensure us to study the same system and outline the differences in the system's behavior when it switches from the D.B. regime to NESS. We were interested to see how the non-equilibrium fluxes influence the relaxation process during the reaching of the stationary distribution. By performing analytical and numerical analysis, our central result is that the presence of the non-equilibrium chemical fluxes reduces the characteristic relaxation time with respect to the D.B. condition. Within a biochemical and biological perspective, this result can be related to the “plasticity property” of biological

Evaluating role of interactive visualization tool in improving students' conceptual understanding of chemical equilibrium

Science.gov (United States)

Sampath Kumar, Bharath

The purpose of this study is to examine the role of partnering visualization tool such as simulation towards development of student's concrete conceptual understanding of chemical equilibrium. Students find chemistry concepts abstract, especially at the microscopic level. Chemical equilibrium is one such topic. While research studies have explored effectiveness of low tech instructional strategies such as analogies, jigsaw, cooperative learning, and using modeling blocks, fewer studies have explored the use of visualization tool such as simulations in the context of dynamic chemical equilibrium. Research studies have identified key reasons behind misconceptions such as lack of systematic understanding of foundational chemistry concepts, failure to recognize the system is dynamic, solving numerical problems on chemical equilibrium in an algorithmic fashion, erroneous application Le Chatelier's principle (LCP) etc. Kress et al. (2001) suggested that external representation in the form of visualization is more than a tool for learning, because it enables learners to make meanings or express their ideas which cannot be readily done so through a verbal representation alone. Mixed method study design was used towards data collection. The qualitative portion of the study is aimed towards understanding the change in student's mental model before and after the intervention. A quantitative instrument was developed based on common areas of misconceptions identified by research studies. A pilot study was conducted prior to the actual study to obtain feedback from students on the quantitative instrument and the simulation. Participants for the pilot study were sampled from a single general chemistry class. Following the pilot study, the research study was conducted with a total of 27 students (N=15 in experimental group and N=12 in control group). Prior to participating in the study, students have completed their midterm test on the topic of chemical equilibrium. Qualitative

Theoretical Adiabatic Temperature and Chemical Composition of Sodium Combustion Flame

International Nuclear Information System (INIS)

Okano, Yasushi; Yamaguchi, Akira

2003-01-01

Sodium fire safety analysis requires fundamental combustion properties, e.g., heat of combustion, flame temperature, and composition. We developed the GENESYS code for a theoretical investigation of sodium combustion flame.Our principle conclusions on sodium combustion under atmospheric air conditions are (a) the maximum theoretical flame temperature is 1950 K, and it is not affected by the presence of moisture; the uppermost limiting factor is the chemical instability of the condensed sodium-oxide products under high temperature; (b) the main combustion product is liquid Na 2 O in dry air condition and liquid Na 2 O with gaseous NaOH in moist air; and (c) the chemical equilibrium prediction of the residual gaseous reactants in the flame is indispensable for sodium combustion modeling

Status of chemical equilibrium in relativistic heavy-ion collisions

Indian Academy of Sciences (India)

Chemical equilibrium; particle multiplicities. PACS Nos 24.10.Pa; 25.75.Dw; 25.75.-q. 1. Introduction. In hydrodynamic models [1] the freeze-out surface is very sensitive on the initial condi- tions and is therefore ... not agree with a recent similar analysis of Pb–Pb data [12] imposing full strangeness equi- librium. The main ...

Chemistry and Chemical Equilibrium Dynamics of BMAA and Its Carbamate Adducts.

Science.gov (United States)

Diaz-Parga, Pedro; Goto, Joy J; Krishnan, V V

2018-01-01

Beta-N-methylamino-L-alanine (BMAA) has been demonstrated to contribute to the onset of the ALS/Parkinsonism-dementia complex (ALS/PDC) and is implicated in the progression of other neurodegenerative diseases. While the role of BMAA in these diseases is still debated, one of the suggested mechanisms involves the activation of excitatory glutamate receptors. In particular, the excitatory effects of BMAA are shown to be dependent on the presence of bicarbonate ions, which in turn forms carbamate adducts in physiological conditions. The formation of carbamate adducts from BMAA and bicarbonate is similar to the formation of carbamate adducts from non-proteinogenic amino acids. Structural, chemical, and biological information related to non-proteinogenic amino acids provide insight into the formation of and possible neurological action of BMAA. This article reviews the carbamate formation of BMAA in the presence of bicarbonate ions, with a particular focus on how the chemical equilibrium of BMAA carbamate adducts may affect the molecular mechanism of its function. Highlights of nuclear magnetic resonance (NMR)-based studies on the equilibrium process between free BMAA and its adducts are presented. The role of divalent metals on the equilibrium process is also explored. The formation and the equilibrium process of carbamate adducts of BMAA may answer questions on their neuroactive potency and provide strong motivation for further investigations into other toxic mechanisms.

Numerical Verification Of Equilibrium Chemistry

International Nuclear Information System (INIS)

Piro, Markus; Lewis, Brent; Thompson, William T.; Simunovic, Srdjan; Besmann, Theodore M.

2010-01-01

A numerical tool is in an advanced state of development to compute the equilibrium compositions of phases and their proportions in multi-component systems of importance to the nuclear industry. The resulting software is being conceived for direct integration into large multi-physics fuel performance codes, particularly for providing boundary conditions in heat and mass transport modules. However, any numerical errors produced in equilibrium chemistry computations will be propagated in subsequent heat and mass transport calculations, thus falsely predicting nuclear fuel behaviour. The necessity for a reliable method to numerically verify chemical equilibrium computations is emphasized by the requirement to handle the very large number of elements necessary to capture the entire fission product inventory. A simple, reliable and comprehensive numerical verification method is presented which can be invoked by any equilibrium chemistry solver for quality assurance purposes.

Computing multi-species chemical equilibrium with an algorithm based on the reaction extents

DEFF Research Database (Denmark)

Paz-Garcia, Juan Manuel; Johannesson, Björn; Ottosen, Lisbeth M.

2013-01-01

-negative constrains. The residual function, representing the distance to the equilibrium, is defined from the chemical potential (or Gibbs energy) of the chemical system. Local minimums are potentially avoided by the prioritization of the aqueous reactions with respect to the heterogeneous reactions. The formation......A mathematical model for the solution of a set of chemical equilibrium equations in a multi-species and multiphase chemical system is described. The computer-aid solution of model is achieved by means of a Newton-Raphson method enhanced with a line-search scheme, which deals with the non...... and release of gas bubbles is taken into account in the model, limiting the concentration of volatile aqueous species to a maximum value, given by the gas solubility constant.The reaction extents are used as state variables for the numerical method. As a result, the accepted solution satisfies the charge...

The temporal evolution of magnesium isotope fractionation during hydromagnesite dissolution, precipitation, and at equilibrium

Science.gov (United States)

Oelkers, Eric H.; Berninger, Ulf-Niklas; Pérez-Fernàndez, Andrea; Chmeleff, Jérôme; Mavromatis, Vasileios

2018-04-01

This study provides experimental evidence of the resetting of the magnesium (Mg) isotope signatures of hydromagnesite in the presence of an aqueous fluid during its congruent dissolution, precipitation, and at equilibrium at ambient temperatures over month-long timescales. All experiments were performed in batch reactors in aqueous sodium carbonate buffer solutions having a pH from 7.8 to 9.2. The fluid phase in all experiments attained bulk chemical equilibrium within analytical uncertainty with hydromagnesite within several days, but the experiments were allowed to continue for up to 575 days. During congruent hydromagnesite dissolution, the fluid first became enriched in isotopically light Mg compared to the dissolving hydromagnesite, but this Mg isotope composition became heavier after the fluid attained chemical equilibrium with the mineral. The δ26Mg composition of the fluid was up to ∼0.35‰ heavier than the initial dissolving hydromagnesite at the end of the dissolution experiments. Hydromagnesite precipitation was provoked during one experiment by increasing the reaction temperature from 4 to 50 °C. The δ26Mg composition of the fluid increased as hydromagnesite precipitated and continued to increase after the fluid attained bulk equilibrium with this phase. These observations are consistent with the hypothesis that mineral-fluid equilibrium is dynamic (i.e. dissolution and precipitation occur at equal, non-zero rates at equilibrium). Moreover the results presented in this study confirm (1) that the transfer of material from the solid to the fluid phase may not be conservative during stoichiometric dissolution, and (2) that the isotopic compositions of carbonate minerals can evolve even when the mineral is in bulk chemical equilibrium with its coexisting fluid. This latter observation suggests that the preservation of isotopic signatures of carbonate minerals in the geological record may require a combination of the isolation of fluid-mineral system

Effect of a Perturbation on the Chemical Equilibrium: Comparison with Le Chatelier's Principle

Science.gov (United States)

Torres, Emilio Martinez

2007-01-01

This article develops a general thermodynamic treatment to predict the direction of shift in a chemical equilibrium when it is subjected to a stress. This treatment gives an inequality that relates the change in the perturbed variable and the change that the equilibrium shift produces in the conjugated variable. To illustrate the generality of…

Use of the nonsteady monotonic heating method for complex determination of thermophysical properties of chemically reacting mixture in the case of non-equilibrium proceeding of the chemical reaction

International Nuclear Information System (INIS)

Serebryanyj, G.Z.

1984-01-01

Theoretical analysis is made for the monotonic heating method as applied for complex determination of thermophysical properties of chemically reacting gases. The possibility is shown of simultaneous determination of frozen and equilibrium heat capacity, frozen and equilibrium heat conduction provided non-equilibrium occuring of the reaction in the wide range of temperatures and pressures. The monotonic heating method can be used for complex determination of thermophysical properties of chemically reacting systems in case of non-equilibrium proceeding of the chemical reaction

Equilibrium chemical vapor deposition growth of Bernal-stacked bilayer graphene.

Science.gov (United States)

Zhao, Pei; Kim, Sungjin; Chen, Xiao; Einarsson, Erik; Wang, Miao; Song, Yenan; Wang, Hongtao; Chiashi, Shohei; Xiang, Rong; Maruyama, Shigeo

2014-11-25

Using ethanol as the carbon source, self-limiting growth of AB-stacked bilayer graphene (BLG) has been achieved on Cu via an equilibrium chemical vapor deposition (CVD) process. We found that during this alcohol catalytic CVD (ACCVD) a source-gas pressure range exists to break the self-limitation of monolayer graphene on Cu, and at a certain equilibrium state it prefers to form uniform BLG with a high surface coverage of ∼94% and AB-stacking ratio of nearly 100%. More importantly, once the BLG is completed, this growth shows a self-limiting manner, and an extended ethanol flow time does not result in additional layers. We investigate the mechanism of this equilibrium BLG growth using isotopically labeled (13)C-ethanol and selective surface aryl functionalization, and results reveal that during the equilibrium ACCVD process a continuous substitution of graphene flakes occurs to the as-formed graphene and the BLG growth follows a layer-by-layer epitaxy mechanism. These phenomena are significantly in contrast to those observed for previously reported BLG growth using methane as precursor.

The effect of natural weathering on the chemical and isotopic composition of biotites

International Nuclear Information System (INIS)

Clauer, N.; Bonnot-Courtois, C.

1982-01-01

The effect of progressive natural weathering on the isotopic (Rb-Sr, K-Ar, deltaD, delta 18 O) and chemical (REE, H 2 O + ) compositions of biotite has been studied on a suite of migmatitic biotites from the Chad Republic. During the early stages of weathering the Rb-Sr system is strongly affected, the hydrogen and oxygen isotope compositions change markedly, the minerals are depleted in light REE, the water content increases by a factor of two, and the K-Ar system is relatively little disturbed. During intensive weathering the K-Ar system is more strongly disturbed than the Rb-Sr system. Most of the isotopic and chemical modifications take place under nonequilibrium conditions and occur before newly formed kaolinite and/or smectite can be detected. These observations suggest that (a) 'protominerals' may form within the biotite structure during the initial period of weathering, and (b) only when chemical equilibrium is approached in the weathering profile are new minerals able to form. (author)

The Navy/NASA Engine Program (NNEP89): Interfacing the program for the calculation of complex Chemical Equilibrium Compositions (CEC)

Science.gov (United States)

Gordon, Sanford

1991-01-01

The NNEP is a general computer program for calculating aircraft engine performance. NNEP has been used extensively to calculate the design and off-design (matched) performance of a broad range of turbine engines, ranging from subsonic turboprops to variable cycle engines for supersonic transports. Recently, however, there has been increased interest in applications for which NNEP is not capable of simulating, such as the use of alternate fuels including cryogenic fuels and the inclusion of chemical dissociation effects at high temperatures. To overcome these limitations, NNEP was extended by including a general chemical equilibrium method. This permits consideration of any propellant system and the calculation of performance with dissociation effects. The new extended program is referred to as NNEP89.

Two-temperature chemically non-equilibrium modelling of transferred arcs

International Nuclear Information System (INIS)

Baeva, M; Kozakov, R; Gorchakov, S; Uhrlandt, D

2012-01-01

A two-temperature chemically non-equilibrium model describing in a self-consistent manner the heat transfer, the plasma chemistry, the electric and magnetic field in a high-current free-burning arc in argon has been developed. The model is aimed at unifying the description of a thermionic tungsten cathode, a flat copper anode, and the arc plasma including the electrode sheath regions. The heat transfer in the electrodes is coupled to the plasma heat transfer considering the energy fluxes onto the electrode boundaries with the plasma. The results of the non-equilibrium model for an arc current of 200 A and an argon flow rate of 12 slpm are presented along with results obtained from a model based on the assumption of local thermodynamic equilibrium (LTE) and from optical emission spectroscopy. The plasma shows a near-LTE behaviour along the arc axis and in a region surrounding the axis which becomes wider towards the anode. In the near-electrode regions, a large deviation from LTE is observed. The results are in good agreement with experimental findings from optical emission spectroscopy. (paper)

Atomistic-level non-equilibrium model for chemically reactive systems based on steepest-entropy-ascent quantum thermodynamics

International Nuclear Information System (INIS)

Li, Guanchen; Al-Abbasi, Omar; Von Spakovsky, Michael R

2014-01-01

This paper outlines an atomistic-level framework for modeling the non-equilibrium behavior of chemically reactive systems. The framework called steepest- entropy-ascent quantum thermodynamics (SEA-QT) is based on the paradigm of intrinsic quantum thermodynamic (IQT), which is a theory that unifies quantum mechanics and thermodynamics into a single discipline with wide applications to the study of non-equilibrium phenomena at the atomistic level. SEA-QT is a novel approach for describing the state of chemically reactive systems as well as the kinetic and dynamic features of the reaction process without any assumptions of near-equilibrium states or weak-interactions with a reservoir or bath. Entropy generation is the basis of the dissipation which takes place internal to the system and is, thus, the driving force of the chemical reaction(s). The SEA-QT non-equilibrium model is able to provide detailed information during the reaction process, providing a picture of the changes occurring in key thermodynamic properties (e.g., the instantaneous species concentrations, entropy and entropy generation, reaction coordinate, chemical affinities, reaction rate, etc). As an illustration, the SEA-QT framework is applied to an atomistic-level chemically reactive system governed by the reaction mechanism F + H 2 ↔ FH + H

Magnetic field effects on the chemical equilibrium in LaCo5-H system

International Nuclear Information System (INIS)

Yamamoto, Isao; Yamaguchi, Masuhiro; Deguchi, Noritaka; Miura, Shigeto.

1997-01-01

Magnetic field effects on the chemical equilibrium were investigated for a ferromagnetic metal hydride-hydrogen system. The equilibrium hydrogen pressure, measured in the β+γ region for LaCo 5 H x , changed significantly with the applied magnetic fields up to 15 T in the temperature range between 293 and 343 K. Namely, the measured hydrogen pressure increased with increasing magnetic fields. However, such a change in the equilibrium pressure became less remarkable with increasing temperature. These experimental results agreed with the thermodynamic calculation based on magnetic data. (author)

Molecular finite-size effects in stochastic models of equilibrium chemical systems.

Science.gov (United States)

Cianci, Claudia; Smith, Stephen; Grima, Ramon

2016-02-28

The reaction-diffusion master equation (RDME) is a standard modelling approach for understanding stochastic and spatial chemical kinetics. An inherent assumption is that molecules are point-like. Here, we introduce the excluded volume reaction-diffusion master equation (vRDME) which takes into account volume exclusion effects on stochastic kinetics due to a finite molecular radius. We obtain an exact closed form solution of the RDME and of the vRDME for a general chemical system in equilibrium conditions. The difference between the two solutions increases with the ratio of molecular diameter to the compartment length scale. We show that an increase in the fraction of excluded space can (i) lead to deviations from the classical inverse square root law for the noise-strength, (ii) flip the skewness of the probability distribution from right to left-skewed, (iii) shift the equilibrium of bimolecular reactions so that more product molecules are formed, and (iv) strongly modulate the Fano factors and coefficients of variation. These volume exclusion effects are found to be particularly pronounced for chemical species not involved in chemical conservation laws. Finally, we show that statistics obtained using the vRDME are in good agreement with those obtained from Brownian dynamics with excluded volume interactions.

Attainment of chemical equilibrium in effusive beam sources of the heterogeneous reaction type

International Nuclear Information System (INIS)

Hildenbrand, D.L.

1979-01-01

Effusive beam sources derived from gas-solid reactions provide a very important pathway for widening the scope of high temperature thermodynamic studies, but the attainment of chemical equilibrium within these sources is problematical. Some of the underlying kinetic factors associated with the use of these sources are discussed. As one might expect, it is important to maximize the ratio of reactive surface area to exit orifice area. Equilibrium seems to be achieved more readily among the products of gas-solid reactions than among reactant and products, as suggested by the quasi-equilibrium model. Some experiences with the use of heterogeneous reaction sources are described, and two definitive tests for the establishment of equilibrium are outlined

Development of a Thermo-chemical Non-equilibrium Solver for Hypervelocity Flows

Science.gov (United States)

Balasubramanian, R.; Anandhanarayanan, K.

2015-04-01

In the present study, a three dimensional flowsolver is indigenously developed to numerically simulate hypervelocity thermal and chemical non equilibrium reactive air flow past flight vehicles. The two-temperature, five species, seventeen reactions, thermo-chemical non equilibrium, non-ionizing, air-chemistry model of Park is implemented in a compressible viscous code CERANS and solved in the finite volume framework. The energy relaxation is addressed by a conservation equation for the vibrational energy of the gas mixture resulting in the evaluation of its vibrational temperature. The AUSM-PW+ numerical flux function has been used for modeling the convective fluxes and a central differencing approximation is used for modeling the diffusive fluxes. The flowsolver had been validated for specifically chosen test cases with inherent flow complexities of non-ionizing hypervelocity thermochemical nonequilibrium flows and results obtained are in good agreement with results available in open literature.

A New Multimedia Application for Teaching and Learning Chemical Equilibrium

Science.gov (United States)

Ollino, Mario; Aldoney, Jenny; Domínguez, Ana M.; Merino, Cristian

2018-01-01

This study presents a method for teaching the subject of chemical equilibrium in which students engage in self-learning mediated by the use of a new multimedia animation (SEQ-alfa©). This method is presented together with evidence supporting its advantages. At a microscopic level, the simulator shows the mutual transformation of A molecules into B…

Convergence to equilibrium of renormalised solutions to nonlinear chemical reaction–diffusion systems

Science.gov (United States)

Fellner, Klemens; Tang, Bao Quoc

2018-06-01

The convergence to equilibrium for renormalised solutions to nonlinear reaction-diffusion systems is studied. The considered reaction-diffusion systems arise from chemical reaction networks with mass action kinetics and satisfy the complex balanced condition. By applying the so-called entropy method, we show that if the system does not have boundary equilibria, i.e. equilibrium states lying on the boundary of R_+^N, then any renormalised solution converges exponentially to the complex balanced equilibrium with a rate, which can be computed explicitly up to a finite-dimensional inequality. This inequality is proven via a contradiction argument and thus not explicitly. An explicit method of proof, however, is provided for a specific application modelling a reversible enzyme reaction by exploiting the specific structure of the conservation laws. Our approach is also useful to study the trend to equilibrium for systems possessing boundary equilibria. More precisely, to show the convergence to equilibrium for systems with boundary equilibria, we establish a sufficient condition in terms of a modified finite-dimensional inequality along trajectories of the system. By assuming this condition, which roughly means that the system produces too much entropy to stay close to a boundary equilibrium for infinite time, the entropy method shows exponential convergence to equilibrium for renormalised solutions to complex balanced systems with boundary equilibria.

Activity Enhancement Based on the Chemical Equilibrium of Multiple-Subunit Nitrile Hydratase from Bordetella petrii.

Science.gov (United States)

Liu, Yi; Liu, Ping; Lin, Lu; Zhao, Yueqin; Zhong, Wenjuan; Wu, Lunjie; Zhou, Zhemin; Sun, Weifeng

2016-09-01

The maturation mechanism of nitrile hydratase (NHase) of Pseudomonas putida NRRL-18668 was discovered and named as "self-subunit swapping." Since the NHase of Bordetella petrii DSM 12804 is similar to that of P. putida, the NHase maturation of B. petrii is proposed to be the same as that of P. putida. However, there is no further information on the application of NHase according to these findings. We successfully rapidly purified NHase and its activator through affinity his tag, and found that the cell extracts of NHase possessed multiple types of protein ingredients including α, β, α2β2, and α(P14K)2 who were in a state of chemical equilibrium. Furthermore, the activity was significantly enhanced through adding extra α(P14K)2 to the cell extracts of NHase according to the chemical equilibrium. Our findings are useful for the activity enhancement of multiple-subunit enzyme and for the first time significantly increased the NHase activity according to the chemical equilibrium.

Investigation of chemical equilibrium kinetics by the electromigration method

International Nuclear Information System (INIS)

Bozhikov, G.A.; Ivanov, P.I.; Maslov, O.D.; Dmitriev, S.N.; Bontchev, G.D.; Milanov, M.V.

2003-01-01

The measurement of the chemical reaction rates for complex formation as well as hydrolysis type reactions by the method of horizontal zone electrophoresis is outlined. The correlation between chemical equilibrium kinetics and electrodiffusion processes in a constant d.c. electric field is described. In model electromigration experiments the reaction rate constant of the formation a complex by Hf(IV) and diethylenetriaminepentaacetic acid (DTPA) is determined. The electrophoretic mobility, diffusion coefficient and stability constant of the [HfDTPA] - complex are calculated, taking into account experimental electrophoretic data obtained at 298.15±0.05 K and constant ionic strength. No-carrier-added 175 Hf radionuclide was used in electromigration experiments at concentrations of 10 -10 -10 -11 M. (orig.)

Achieving Chemical Equilibrium: The Role of Imposed Conditions in the Ammonia Formation Reaction

Science.gov (United States)

Tellinghuisen, Joel

2006-01-01

Under conditions of constant temperature T and pressure P, chemical equilibrium occurs in a closed system (fixed mass) when the Gibbs free energy G of the reaction mixture is minimized. However, when chemical reactions occur under other conditions, other thermodynamic functions are minimized or maximized. For processes at constant T and volume V,…

Effects of Confinement on Chemical Reaction Equilibrium in Nanoporous Materials

Czech Academy of Sciences Publication Activity Database

Smith, W.R.; Lísal, Martin; Brennan, J.K.

2006-01-01

Roč. 3984, - (2006), s. 743-751 ISSN 0302-9743 R&D Projects: GA ČR(CZ) GA203/05/0725; GA AV ČR 1ET400720507 Grant - others:NRCC(CA) OGP 1041 Institutional research plan: CEZ:AV0Z40720504 Keywords : nanoporous materials * chemical reaction equilibrium Subject RIV: CF - Physical ; Theoretical Chemistry Impact factor: 0.402, year: 2005

A study of chemical equilibrium of tri-component mixtures of hydrogen isotopes

International Nuclear Information System (INIS)

Cristescu, Ioana; Cristescu, I.; Peculea, M.

1998-01-01

In this paper we present a model for computing the equilibrium constants for chemical reactions between hydrogen's isotopes as function of temperature. The equilibrium constants were expressed with the aid of Gibbs potential and the partition function of the mixture. We assessed the partition function for hydrogen's isotopes having in view that some nuclei are fermions and other bosons. As results we plotted the values of equilibrium constants as function of temperature. Knowing these values we determined the deuterium distribution on species (for mixture H 2 -HD-D 2 ) as function of total deuterium concentration and the tritium distribution on species (for mixtures D 2 -DT-T 2 and H 2 -HT-T 2 ) as function of total tritium concentration. (authors)

Radiation Fog in the US Mid-Atlantic Region: Chemical Composition, Trends, and Gas-Liquid Partitioning

Science.gov (United States)

Straub, D.

2016-12-01

The chemical composition of radiation fog has been studied at a rural site in central Pennsylvania over an eight year period extending through 2015. Bulk fog samples were collected with an automated Caltech Heated Rod Cloud Collector (CHRCC) and analyzed for pH, inorganic ions, organic acids, total organic carbon (TOC), and total nitrogen (TN). Over the duration of the project, 146 samples were collected and used to document chemical composition, evaluate changes over time, and to investigate partitioning between the gas and aqueous phases. Ammonium, sulfate, calcium, and nitrate were the most abundant inorganic ions while acetate and formate were the dominant organic acids. Organic acids contributed about 15% to TOC. Inorganic nitrogen accounted for the majority of TN, with only 18% of TN attributed to organic nitrogen. Overall, organic matter contributed 52% to the total mass loading of the fog samples, a value that is higher than reported for other radiation fog studies. Statistically significant decreasing trends were observed for sulfate, ammonium, chloride, nitrate, and pH. These trends coincide with reductions in emissions from fossil fuel combustion that have been documented over this time period. Seasonal trends were also detected for nitrate, ammonium, potassium, phosphate, acetate and formate which appear to be related to the agricultural growing season. Based on simultaneous measurements of gas phase ammonia and ammonium in the fog samples, significant deviations from equilibrium were found. In low pH samples, ammonium concentrations were much lower than equilibrium predicts, while the opposite occurred in high pH samples. Modeling suggested that mass transfer limitations contributed to the departure from equilibrium. Similarly, predictions of bicarbonate concentrations based on equilibrium with gas phase carbon dioxide appears to underestimate the actual amount of bicarbonate present in samples collected during this study.

Observation of non-chemical equilibrium effect on Ar-CO2-H2 thermal plasma model by changing pressure

International Nuclear Information System (INIS)

Al-Mamun, Sharif Abdullah; Tanaka, Yasunori; Uesugi, Yoshihiko

2009-01-01

The authors developed a two-dimensional one-temperature chemical non-equilibrium (1T-NCE) model of Ar-CO 2 -H 2 inductively coupled thermal plasmas (ICTP) to investigate the effect of pressure variation. The basic concept of one-temperature model is the assumption and treatment of the same energy conservation equation for electrons and heavy particles. The energy conservation equations consider reaction heat effects and energy transfer among the species produced as well as enthalpy flow resulting from diffusion. Assuming twenty two (22) different particles in this model and by solving mass conservation equations for each particle, considering diffusion, convection and net production terms resulting from hundred and ninety eight (198) chemical reactions, chemical non-equilibrium effects were taken into account. Transport and thermodynamic properties of Ar-CO 2 -H 2 thermal plasmas were self-consistently calculated using the first-order approximation of the Chapman-Enskog method. Finally results obtained at atmospheric pressure (760 Torr) and at reduced pressure (500, 300 Torr) were compared with results from one-temperature chemical equilibrium (1T-CE) model. And of course, this comparison supported discussion of chemical non-equilibrium effects in the inductively coupled thermal plasmas (ICTP).

Two-phase quasi-equilibrium in β-type Ti-based bulk metallic glass composites

Science.gov (United States)

Zhang, L.; Pauly, S.; Tang, M. Q.; Eckert, J.; Zhang, H. F.

2016-01-01

The microstructural evolution of cast Ti/Zr-based bulk metallic glass composites (BMGCs) containing β-Ti still remains ambiguous. This is why to date the strategies and alloys suitable for producing such BMGCs with precisely controllable volume fractions and crystallite sizes are still rather limited. In this work, a Ti-based BMGC containing β-Ti was developed in the Ti-Zr-Cu-Co-Be system. The glassy matrix of this BMGC possesses an exceptional glass-forming ability and as a consequence, the volume fractions as well as the composition of the β-Ti dendrites remain constant over a wide range of cooling rates. This finding can be explained in terms of a two-phase quasi-equilibrium between the supercooled liquid and β-Ti, which the system attains on cooling. The two-phase quasi-equilibrium allows predicting the crystalline and glassy volume fractions by means of the lever rule and we succeeded in reproducing these values by slight variations in the alloy composition at a fixed cooling rate. The two-phase quasi-equilibrium could be of critical importance for understanding and designing the microstructures of BMGCs containing the β-phase. Its implications on the nucleation and growth of the crystalline phase are elaborated. PMID:26754315

Chemical compositions, methods of making the chemical compositions, and structures made from the chemical compositions

Science.gov (United States)

Yang, Lei; Cheng, Zhe; Liu, Ze; Liu, Meilin

2015-01-13

Embodiments of the present disclosure include chemical compositions, structures, anodes, cathodes, electrolytes for solid oxide fuel cells, solid oxide fuel cells, fuel cells, fuel cell membranes, separation membranes, catalytic membranes, sensors, coatings for electrolytes, electrodes, membranes, and catalysts, and the like, are disclosed.

Non-equilibrium mass transfer absorption model for the design of boron isotopes chemical exchange column

International Nuclear Information System (INIS)

Bai, Peng; Fan, Kaigong; Guo, Xianghai; Zhang, Haocui

2016-01-01

Highlights: • We propose a non-equilibrium mass transfer absorption model instead of a distillation equilibrium model to calculate boron isotopes separation. • We apply the model to calculate the needed column height to meet prescribed separation requirements. - Abstract: To interpret the phenomenon of chemical exchange in boron isotopes separation accurately, the process is specified as an absorption–reaction–desorption hybrid process instead of a distillation equilibrium model, the non-equilibrium mass transfer absorption model is put forward and a mass transfer enhancement factor E is introduced to find the packing height needed to meet the specified separation requirements with MATLAB.

Calculation of chemical equilibrium between aqueous solution and minerals: the EQ3/6 software package

International Nuclear Information System (INIS)

Wolery, T.J.

1979-01-01

The newly developed EQ/36 software package computes equilibrium models of aqueous geochemical systems. The package contains two principal programs: EQ3 performs distribution-of-species calculations for natural water compositions; EQ6 uses the results of EQ3 to predict the consequences of heating and cooling aqueous solutions and of irreversible reaction in rock--water systems. The programs are valuable for studying such phenomena as the formation of ore bodies, scaling and plugging in geothermal development, and the long-term disposal of nuclear waste. EQ3 and EQ6 are compared with such well-known geochemical codes as SOLMNEQ, WATEQ, REDEQL, MINEQL, and PATHI. The data base allows calculations in the temperature interval 0 to 350 0 C, at either 1 atm-steam saturation pressures or a constant 500 bars. The activity coefficient approximations for aqueous solutes limit modeling to solutions of ionic strength less than about one molal. The mathematical derivations and numerical techniques used in EQ6 are presented in detail. The program uses the Newton--Raphson method to solve the governing equations of chemical equilibrium for a system of specified elemental composition at fixed temperature and pressure. Convergence is aided by optimizing starting estimates and by under-relaxation techniques. The minerals present in the stable phase assemblage are found by several empirical methods. Reaction path models may be generated by using this approach in conjunction with finite differences. This method is analogous to applying high-order predictor--corrector methods to integrate a corresponding set of ordinary differential equations, but avoids propagation of error (drift). 8 figures, 9 tables

Mechanism of alkalinity lowering and chemical equilibrium model of high fly ash silica fume cement

International Nuclear Information System (INIS)

Hoshino, Seiichi; Honda, Akira; Negishi, Kumi

2014-01-01

The mechanism of alkalinity lowering of a High Fly ash Silica fume Cement (HFSC) under liquid/solid ratio conditions where the pH is largely controlled by the soluble alkali components (Region I) has been studied. This mechanism was incorporated in the chemical equilibrium model of HFSC. As a result, it is suggested that the dissolution and precipitation behavior of SO 4 2- partially contributes to alkalinity lowering of HFSC in Region I. A chemical equilibrium model of HFSC incorporating alkali (Na, K) adsorption, which was presumed as another contributing factor of the alkalinity lowering effect, was also developed, and an HFSC immersion experiment was analyzed using the model. The results of the developed model showed good agreement with the experiment results. From the above results, it was concluded that the alkalinity lowering of HFSC in Region I was attributed to both the dissolution and precipitation behavior of SO 4 2- and alkali adsorption, in addition to the absence of Ca(OH) 2 . A chemical equilibrium model of HFSC incorporating alkali and SO 4 2- adsorption was also proposed. (author)

Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

International Nuclear Information System (INIS)

Kustova, Elena V.; Kremer, Gilberto M.

2014-01-01

Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N 2 flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure

Chemical reaction rates and non-equilibrium pressure of reacting gas mixtures in the state-to-state approach

Energy Technology Data Exchange (ETDEWEB)

Kustova, Elena V., E-mail: e.kustova@spbu.ru [Department of Mathematics and Mechanics, Saint Petersburg State University, 198504 Universitetskiy pr. 28, Saint Petersburg (Russian Federation); Kremer, Gilberto M., E-mail: kremer@fisica.ufpr.br [Departamento de Física, Universidade Federal do Paraná, Caixa Postal 19044, 81531-980 Curitiba (Brazil)

2014-12-05

Highlights: • State-to-state approach for coupled vibrational relaxation and chemical reactions. • Self-consistent model for rates of non-equilibrium reactions and energy transitions. • In viscous flows mass action law is violated. • Cross coupling between reaction rates and non-equilibrium pressure in viscous flow. • Results allow implementing the state-to-state approach for viscous flow simulations. - Abstract: Viscous gas flows with vibrational relaxation and chemical reactions in the state-to-state approach are analyzed. A modified Chapman–Enskog method is used for the determination of chemical reaction and vibrational transition rates and non-equilibrium pressure. Constitutive equations depend on the thermodynamic forces: velocity divergence and chemical reaction/transition affinity. As an application, N{sub 2} flow with vibrational relaxation across a shock wave is investigated. Two distinct processes occur behind the shock: for small values of the distance the affinity is large and vibrational relaxation is in its initial stage; for large distances the affinity is small and the chemical reaction is in its final stage. The affinity contributes more to the transition rate than the velocity divergence and the effect of these two contributions are more important for small distances from the shock front. For the non-equilibrium pressure, the term associated with the bulk viscosity increases by a small amount the hydrostatic pressure.

Thermochemical equilibrium modelling of a gasifying process

International Nuclear Information System (INIS)

Melgar, Andres; Perez, Juan F.; Laget, Hannes; Horillo, Alfonso

2007-01-01

This article discusses a mathematical model for the thermochemical processes in a downdraft biomass gasifier. The model combines the chemical equilibrium and the thermodynamic equilibrium of the global reaction, predicting the final composition of the producer gas as well as its reaction temperature. Once the composition of the producer gas is obtained, a range of parameters can be derived, such as the cold gas efficiency of the gasifier, the amount of dissociated water in the process and the heating value and engine fuel quality of the gas. The model has been validated experimentally. This work includes a parametric study of the influence of the gasifying relative fuel/air ratio and the moisture content of the biomass on the characteristics of the process and the producer gas composition. The model helps to predict the behaviour of different biomass types and is a useful tool for optimizing the design and operation of downdraft biomass gasifiers

User's manual of BISHOP. A Bi-Phase, Sodium-Hydrogen-Oxygen system, chemical equilibrium calculation program

International Nuclear Information System (INIS)

Okano, Yasushi; Yamaguchi, Akira

2001-07-01

In an event of sodium leakage in liquid metal fast breeder reactors, liquid sodium flows out of piping, and droplet combustion might occur under a certain environmental condition. The combustion heat and reaction products should be evaluated in the sodium fire analysis codes for investigating the influence of the sodium leak age and fire incident. In order to analyze the reaction heat and products, the multi-phase chemical equilibrium calculation program for a sodium, oxygen and hydrogen system has been developed. The developed numerical program is named BISHOP, which denotes 'Bi-Phase, Sodium-Hydrogen-Oxygen, Chemical Equilibrium Calculation Program'. The Gibbs free energy minimization method is used because of the following advantages. Chemical species are easily added and changed. A variety of thermodynamic states, such as isothermal and isentropic changes, can be dealt with in addition to constant temperature and pressure processes. In applying the free energy minimization method to solve the multi-phase sodium reaction system, three new numerical calculation techniques are developed. One is theoretical simplification of phase description in equation system, the other is to extend the Gibbs free energy minimization method to a multi-phase system, and the last is to establish the efficient search for the minimum value. The reaction heat and products at the equilibrium state can be evaluated from the initial conditions, such as temperature, pressure and reactants, using BISHOP. This report describes the thermochemical basis of chemical equilibrium calculations, the system of equations, simplification models, and the procedure to prepare input data and usage of BISHOP. (author)

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions

International Nuclear Information System (INIS)

Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C.; Brooks, Scott C; Pace, Molly; Kim, Young Jin; Jardine, Philip M.; Watson, David B.

2007-01-01

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M. partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M. species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing NE equilibrium reactions and a set of reactive transport equations of M-NE kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions

A reaction-based paradigm to model reactive chemical transport in groundwater with general kinetic and equilibrium reactions.

Science.gov (United States)

Zhang, Fan; Yeh, Gour-Tsyh; Parker, Jack C; Brooks, Scott C; Pace, Molly N; Kim, Young-Jin; Jardine, Philip M; Watson, David B

2007-06-16

This paper presents a reaction-based water quality transport model in subsurface flow systems. Transport of chemical species with a variety of chemical and physical processes is mathematically described by M partial differential equations (PDEs). Decomposition via Gauss-Jordan column reduction of the reaction network transforms M species reactive transport equations into two sets of equations: a set of thermodynamic equilibrium equations representing N(E) equilibrium reactions and a set of reactive transport equations of M-N(E) kinetic-variables involving no equilibrium reactions (a kinetic-variable is a linear combination of species). The elimination of equilibrium reactions from reactive transport equations allows robust and efficient numerical integration. The model solves the PDEs of kinetic-variables rather than individual chemical species, which reduces the number of reactive transport equations and simplifies the reaction terms in the equations. A variety of numerical methods are investigated for solving the coupled transport and reaction equations. Simulation comparisons with exact solutions were performed to verify numerical accuracy and assess the effectiveness of various numerical strategies to deal with different application circumstances. Two validation examples involving simulations of uranium transport in soil columns are presented to evaluate the ability of the model to simulate reactive transport with complex reaction networks involving both kinetic and equilibrium reactions.

CFD analysis of laboratory scale phase equilibrium cell operation

Science.gov (United States)

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process.: Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

CFD analysis of laboratory scale phase equilibrium cell operation.

Science.gov (United States)

Jama, Mohamed Ali; Nikiforow, Kaj; Qureshi, Muhammad Saad; Alopaeus, Ville

2017-10-01

For the modeling of multiphase chemical reactors or separation processes, it is essential to predict accurately chemical equilibrium data, such as vapor-liquid or liquid-liquid equilibria [M. Šoóš et al., Chem. Eng. Process Intensif. 42(4), 273-284 (2003)]. The instruments used in these experiments are typically designed based on previous experiences, and their operation verified based on known equilibria of standard components. However, mass transfer limitations with different chemical systems may be very different, potentially falsifying the measured equilibrium compositions. In this work, computational fluid dynamics is utilized to design and analyze laboratory scale experimental gas-liquid equilibrium cell for the first time to augment the traditional analysis based on plug flow assumption. Two-phase dilutor cell, used for measuring limiting activity coefficients at infinite dilution, is used as a test case for the analysis. The Lagrangian discrete model is used to track each bubble and to study the residence time distribution of the carrier gas bubbles in the dilutor cell. This analysis is necessary to assess whether the gas leaving the cell is in equilibrium with the liquid, as required in traditional analysis of such apparatus. Mass transfer for six different bio-oil compounds is calculated to determine the approach equilibrium concentration. Also, residence times assuming plug flow and ideal mixing are used as reference cases to evaluate the influence of mixing on the approach to equilibrium in the dilutor. Results show that the model can be used to predict the dilutor operating conditions for which each of the studied gas-liquid systems reaches equilibrium.

Equilibrium simulations of proteins using molecular fragment replacement and NMR chemical shifts.

Science.gov (United States)

Boomsma, Wouter; Tian, Pengfei; Frellsen, Jes; Ferkinghoff-Borg, Jesper; Hamelryck, Thomas; Lindorff-Larsen, Kresten; Vendruscolo, Michele

2014-09-23

Methods of protein structure determination based on NMR chemical shifts are becoming increasingly common. The most widely used approaches adopt the molecular fragment replacement strategy, in which structural fragments are repeatedly reassembled into different complete conformations in molecular simulations. Although these approaches are effective in generating individual structures consistent with the chemical shift data, they do not enable the sampling of the conformational space of proteins with correct statistical weights. Here, we present a method of molecular fragment replacement that makes it possible to perform equilibrium simulations of proteins, and hence to determine their free energy landscapes. This strategy is based on the encoding of the chemical shift information in a probabilistic model in Markov chain Monte Carlo simulations. First, we demonstrate that with this approach it is possible to fold proteins to their native states starting from extended structures. Second, we show that the method satisfies the detailed balance condition and hence it can be used to carry out an equilibrium sampling from the Boltzmann distribution corresponding to the force field used in the simulations. Third, by comparing the results of simulations carried out with and without chemical shift restraints we describe quantitatively the effects that these restraints have on the free energy landscapes of proteins. Taken together, these results demonstrate that the molecular fragment replacement strategy can be used in combination with chemical shift information to characterize not only the native structures of proteins but also their conformational fluctuations.

Remarks on the chemical Fokker-Planck and Langevin equations: Nonphysical currents at equilibrium.

Science.gov (United States)

Ceccato, Alessandro; Frezzato, Diego

2018-02-14

The chemical Langevin equation and the associated chemical Fokker-Planck equation are well-known continuous approximations of the discrete stochastic evolution of reaction networks. In this work, we show that these approximations suffer from a physical inconsistency, namely, the presence of nonphysical probability currents at the thermal equilibrium even for closed and fully detailed-balanced kinetic schemes. An illustration is given for a model case.

A two-dimensional, TVD numerical scheme for inviscid, high Mach number flows in chemical equilibrium

Science.gov (United States)

Eberhardt, S.; Palmer, G.

1986-01-01

A new algorithm has been developed for hypervelocity flows in chemical equilibrium. Solutions have been achieved for Mach numbers up to 15 with no adverse effect on convergence. Two methods of coupling an equilibrium chemistry package have been tested, with the simpler method proving to be more robust. Improvements in boundary conditions are still required for a production-quality code.

A Study of the Polycondensation of (Tetrahydroxy(TetraarylCyclotetrasiloxanes under Equilibrium and Non-Equilibrium Conditions in the Presence and Absence of Montmorillonite

Directory of Open Access Journals (Sweden)

Nataliya N. Makarova

2018-04-01

Full Text Available Oligo- and polycyclosiloxanes were obtained by the polycondensation of (tetrahydroxy(tetraarylcyclotetrasiloxanes in equilibrium and non-equilibrium conditions in the presence and absence of montmorillonite (MMT. Their composition and the structures of their components were investigated by infrared (IR spectroscopy, 29Si nuclear magnetic resonance (NMR spectroscopy, atmospheric pressure chemical ionization (APCI mass spectrometry, powder X-ray diffraction (XRD, and gel-penetrating chromatography (GPC. Also, a comparison of polymers formed in the presence of MMT and via anionic polymerization was performed showing differences in their structures.

Student Misconceptions in Chemical Equilibrium as Related to Cognitive Level and Achievement.

Science.gov (United States)

Wheeler, Alan E.; Kass, Heidi

Reported is an investigation to determine the nature and extent of student misconceptions in chemical equilibrium and to ascertain the degree to which certain misconceptions are related to chemistry achievement and to performance on specific tasks involving cognitive transformations characteristic of the concrete and formal operational stages of…

Interstellar matrices: the chemical composition and evolution of interstellar ices as observed by ISO.

Science.gov (United States)

d'Hendecourt, L; Dartois, E

2001-03-15

Matrix isolation techniques have been developed in the early sixties as a tool for studying the spectroscopic properties of out of equilibrium species (atoms, radicals, ions, reactive molecules), embedded in rare gas inert matrices at low temperatures. Cold interstellar grains surfaces are able to condense out gas phase molecules, routinely observed by radioastronomy. These grain 'mantles' can be considered as 'interstellar matrices'. However, these matrices are not clean and unreactive. They are made principally of dirty ices whose composition must be determined carefully to assess the importance of the solid state chemistry that takes place in the Interstellar Medium. Infrared spectroscopy, both in astronomy and in the laboratory, is the unique tool to determine the chemical composition of these ices. Astronomical spectra can directly be compared with laboratory ones obtained using classical matrix isolation techniques. Furthermore, dedicated experiments may be undertaken to further improve the understanding of the basic physico-chemical processes that take place in cosmic ices.

Understanding Chemical Equilibrium Using Entropy Analysis: The Relationship between [delta]S[subscript tot](sys[superscript o]) and the Equilibrium Constant

Science.gov (United States)

Bindel, Thomas H.

2010-01-01

Entropy analyses as a function of the extent of reaction are presented for a number of physicochemical processes, including vaporization of a liquid, dimerization of nitrogen dioxide, and the autoionization of water. Graphs of the total entropy change versus the extent of reaction give a visual representation of chemical equilibrium and the second…

Calculation of liquid-liquid equilibrium of aqueous two-phase systems using a chemical-theory-based excess Gibbs energy model

Directory of Open Access Journals (Sweden)

Pessôa Filho P. A.

2004-01-01

Full Text Available Mixtures containing compounds that undergo hydrogen bonding show large deviations from ideal behavior. These deviations can be accounted for through chemical theory, according to which the formation of a hydrogen bond can be treated as a chemical reaction. This chemical equilibrium needs to be taken into account when applying stability criteria and carrying out phase equilibrium calculations. In this work, we illustrate the application of the stability criteria to establish the conditions under which a liquid-phase split may occur and the subsequent calculation of liquid-liquid equilibrium using a chemical-theory-modified Flory-Huggins equation to describe the non ideality of aqueous two-phase systems composed of poly(ethylene glycol and dextran. The model was found to be able to correlate ternary liquid-liquid diagrams reasonably well by simple adjustment of the polymer-polymer binary interaction parameter.

A tightly coupled non-equilibrium model for inductively coupled radio-frequency plasmas

International Nuclear Information System (INIS)

Munafò, A.; Alfuhaid, S. A.; Panesi, M.; Cambier, J.-L.

2015-01-01

The objective of the present work is the development of a tightly coupled magneto-hydrodynamic model for inductively coupled radio-frequency plasmas. Non Local Thermodynamic Equilibrium (NLTE) effects are described based on a hybrid State-to-State approach. A multi-temperature formulation is used to account for thermal non-equilibrium between translation of heavy-particles and vibration of molecules. Excited electronic states of atoms are instead treated as separate pseudo-species, allowing for non-Boltzmann distributions of their populations. Free-electrons are assumed Maxwellian at their own temperature. The governing equations for the electro-magnetic field and the gas properties (e.g., chemical composition and temperatures) are written as a coupled system of time-dependent conservation laws. Steady-state solutions are obtained by means of an implicit Finite Volume method. The results obtained in both LTE and NLTE conditions over a broad spectrum of operating conditions demonstrate the robustness of the proposed coupled numerical method. The analysis of chemical composition and temperature distributions along the torch radius shows that: (i) the use of the LTE assumption may lead to an inaccurate prediction of the thermo-chemical state of the gas, and (ii) non-equilibrium phenomena play a significant role close the walls, due to the combined effects of Ohmic heating and macroscopic gradients

Chemical composition of Chinese palm fruit and chemical properties ...

African Journals Online (AJOL)

... chemical properties and could be used as edible oils and for industrial applications. ... on it, which can provide useful information for Chinese oil palm industry. Key words: Chemical composition, palm fruit, palm oil, palm kernel oil, chemical ...

Self-organized crystallization mechanism of non-equilibrium 2:1 type phyllosilicate systems

Institute of Scientific and Technical Information of China (English)

无

2002-01-01

The crystallization mechanism of 2:1 type regular interstratified minerals is investigated in views of non-equilibrium thermodynamics. The structural chemistry of relative layers and their interstratified combinations is analyzed and six kinds of non-equilibrium chemical systems have been induced. The universal laws of chemical reactions which happened in the interface region of these non-equilibrium systems have been summarized. From these laws, two reaction systems crystallizing out Tosudite and Rectorite respectively have been recovered. The kinetic model of chemical reactions has been developed by means of the mass conservation law. The oscillatory solution showing regular interstratified features has also been obtained numerically. These results indicate that the difference in original chemical composition among systems can affect the chemical connotation of reactants, intermediate products and resultants, and the flow chart of chemical reaction, but cannot change their crystallization behavior of network-forming cations, bigger and smaller network-modifying cations during crystallization. Hence, their kinetic model reflecting the universal crystallization law of these cations is just the same. These systems will crystallize out regular interstratified minerals at suitable parameters, which always exist as domain with nanometer-sized in thickness and can be called the self-organized ordering structure.

Approximate method of calculation of non-equilibrium flow parameters of chemically reacting nitrogen tetroxide in the variable cross-section channels with energy exchange

International Nuclear Information System (INIS)

Bazhin, M.A.; Fedosenko, G.Eh.; Shiryaeva, N.M.; Mal'ko, M.V.

1986-01-01

It is shown that adiabatic non-equilibrium chemically reacting gas flow with energy exchange in a variable cross-section channel may be subdivided into five possible types: 1) quasi-equilibrium flow; 2) flow in the linear region of deviation from equilibrium state; 3) quasi-frozen flow; 4) flow in the linear region of deviation from frozen state; 5) non-equilibrium flow. Criteria of quasi-equilibrium and quazi-frozen flows, including factors of external action of chemically reacting gas on flow, allow to obtain simple but sufficiently reliable approximate method of calculation of flow parameters. The considered method for solving the problem of chemically reacting nitrogen tetroxide in the variable cross-section channel with energy exchange can be used for evaluation of chemical reaction kinetics on the flow parameter in the stages of axial-flow and radial-flow turbines and in another practical problems

Argumentation Practices in Classroom: Pre-Service Teachers' Conceptual Understanding of Chemical Equilibrium

Science.gov (United States)

Kaya, Ebru

2013-01-01

This study examines the impact of argumentation practices on pre-service teachers' understanding of chemical equilibrium. The sample consisted of 100 pre-service teachers in two classes of a public university. One of these classes was assigned as experimental and the other as control group, randomly. In the experimental group, the subject of…

Chemical equilibrium calculations for the high pressure and temperature dissociation of liquid nitrogen

Energy Technology Data Exchange (ETDEWEB)

Hamilton, D.C.; Ree, F.H.

1987-07-01

Calculations are reported for the equation-of-state properties of shock-compressed liquid nitrogen. The statistical mechanical, chemical equilibrium calculations, which allow for the simultaneous presence of both the diatomic and monatomic forms of nitrogen, show good agreement with recent dynamic experiments.

Chemical equilibrium calculations for the high pressure and temperature dissociation of liquid nitrogen

International Nuclear Information System (INIS)

Hamilton, D.C.; Ree, F.H.

1987-07-01

Calculations are reported for the equation-of-state properties of shock-compressed liquid nitrogen. The statistical mechanical, chemical equilibrium calculations, which allow for the simultaneous presence of both the diatomic and monatomic forms of nitrogen, show good agreement with recent dynamic experiments

Strategies Reported Used by Instructors to Address Student Alternate Conceptions in Chemical Equilibrium

Science.gov (United States)

Piquette, Jeff S.; Heikkinen, Henry W.

2005-01-01

This study explores general-chemistry instructors' awareness of and ability to identify and address common student learning obstacles in chemical equilibrium. Reported instructor strategies directed at remediating student alternate conceptions were investigated and compared with successful, literature-based conceptual change methods. Fifty-two…

Contribution to the knowledge of the Cu-Sn-Zn system for compositions close to brass alloys

International Nuclear Information System (INIS)

Vilarinho, C.; Soares, D.; Castro, F.

2004-01-01

The effect of tin content in the equilibrium phases of the Cu-Zn-based alloys, within the range of chemical compositions with interest to brass producers is described. For this purpose, ternary alloys with copper contents between 55.4 and 67.5 wt.% and tin contents up to 5.30 wt.% have been studied. The chemical composition of each alloy has been determined by X-ray fluorescence spectrometry (XRF). Isothermal homogenization, followed by rapid cooling, has been employed to determine the equilibrium phases at different temperatures. The homogenized alloys have been observed by scanning electron microscopy and the respective chemical analysis of the phases determined by electron probe microanalysis (EPMA). The statistical analysis of the obtained results enable to correlate the chemical composition of equilibrium phases with temperature. The chemical composition of the three-phase field, for the studied temperatures, has also been determined

Para-equilibrium phase diagrams

International Nuclear Information System (INIS)

Pelton, Arthur D.; Koukkari, Pertti; Pajarre, Risto; Eriksson, Gunnar

2014-01-01

Highlights: • A rapidly cooled system may attain a state of para-equilibrium. • In this state rapidly diffusing elements reach equilibrium but others are immobile. • Application of the Phase Rule to para-equilibrium phase diagrams is discussed. • A general algorithm to calculate para-equilibrium phase diagrams is described. - Abstract: If an initially homogeneous system at high temperature is rapidly cooled, a temporary para-equilibrium state may result in which rapidly diffusing elements have reached equilibrium but more slowly diffusing elements have remained essentially immobile. The best known example occurs when homogeneous austenite is quenched. A para-equilibrium phase assemblage may be calculated thermodynamically by Gibbs free energy minimization under the constraint that the ratios of the slowly diffusing elements are the same in all phases. Several examples of calculated para-equilibrium phase diagram sections are presented and the application of the Phase Rule is discussed. Although the rules governing the geometry of these diagrams may appear at first to be somewhat different from those for full equilibrium phase diagrams, it is shown that in fact they obey exactly the same rules with the following provision. Since the molar ratios of non-diffusing elements are the same in all phases at para-equilibrium, these ratios act, as far as the geometry of the diagram is concerned, like “potential” variables (such as T, pressure or chemical potentials) rather than like “normal” composition variables which need not be the same in all phases. A general algorithm to calculate para-equilibrium phase diagrams is presented. In the limit, if a para-equilibrium calculation is performed under the constraint that no elements diffuse, then the resultant phase diagram shows the single phase with the minimum Gibbs free energy at any point on the diagram; such calculations are of interest in physical vapor deposition when deposition is so rapid that phase

Chemical equilibrium model for high- Tc and heavy fermion superconductors: the density of states

International Nuclear Information System (INIS)

Kallio, A.; Hissa, J.; Hayrynen, T.; Braysy, V.; Sakkinen, T.

1998-01-01

The chemical equilibrium model is based on the idea of correlated electron pairs, which in singlet state can exist as quasimolecules in the superfluid and normal states of a superconductor. These preformed pairs are bosons which can undergo a Bose-Einstein condensation in analogy with the superfluidity of 4 He+ 3 He-mixture. The bosons (B ++ ) and the fermions (h + ) are in chemical equilibrium with respect to the reaction B ++ ↔ 2h + , at any temperature. The mean densities of bosons and fermions (quasiholes) n B (T) and n h (T) are determined from the thermodynamics of the equilibrium reaction in terms of a single function f(T). By thermodynamics the function f(T) is connected to equilibrium constant φ(T) by 1-f(T) = [1 + φ(T)] -1/2 . Using a simple power law, known to be valid near T = 0, for the chemical constant φ(T) α/t 2γ , t = T/T*, the mean density of quasiholes is given in closed form. This enables one to calculate the corresponding density of states (DOS) D(E) N s /N(0), by solving an integral equation. The NIS- tunneling conductivity near T = 0, given by D(E) compares well with the most recent experiments: D(E) ∼ E γ , for small E and a finite maximum of right size, corresponding to 'finite quasiparticle lifetime'. The corresponding SIS-tunneling conductivity is obtained from a simple convolution and is also in agreement with recent break junction experiments of Hancotte et al. The position of the maximum can be used to obtain the scaling temperature T*, which comes close to the one measured by Hall coefficient in the normal state. A simple explanation for the spingap effect in NMR is given. (Copyright (1998) World Scientific Publishing Co. Pte. Ltd)

Construction and repair of highly ordered 2D covalent networks by chemical equilibrium regulation.

Science.gov (United States)

Guan, Cui-Zhong; Wang, Dong; Wan, Li-Jun

2012-03-21

The construction of well-ordered 2D covalent networks via the dehydration of di-borate aromatic molecules was successfully realized through introducing a small amount of water into a closed reaction system to regulate the chemical equilibrium.

Non-Equilibrium Thermodynamic Chemistry and the Composition of the Atmosphere of Mars

Science.gov (United States)

Levine, J. S.; Summers, M. E.

2003-01-01

A high priority objective of the Mars Exploration Program is to Determine if life exists today (MEPAG Goal I, Objective A). The measurement of gases of biogenic origin may be an approach to detect the presence of microbial life on the surface or subsurface of Mars. Chemical thermodynamic calculations indicate that on both Earth and Mars, certain gases should exist in extremely low concentrations, if at all. Microbial metabolic activity is an important non-equilibrium chemistry process on Earth, and if microbial life exists on Mars, may be an important nonequilibrium chemistry process on Mars. The non-equilibrium chemistry of the atmosphere of Mars is discussed in this paper.

Computer program to solve two-dimensional shock-wave interference problems with an equilibrium chemically reacting air model

Science.gov (United States)

Glass, Christopher E.

1990-08-01

The computer program EASI, an acronym for Equilibrium Air Shock Interference, was developed to calculate the inviscid flowfield, the maximum surface pressure, and the maximum heat flux produced by six shock wave interference patterns on a 2-D, cylindrical configuration. Thermodynamic properties of the inviscid flowfield are determined using either an 11-specie, 7-reaction equilibrium chemically reacting air model or a calorically perfect air model. The inviscid flowfield is solved using the integral form of the conservation equations. Surface heating calculations at the impingement point for the equilibrium chemically reacting air model use variable transport properties and specific heat. However, for the calorically perfect air model, heating rate calculations use a constant Prandtl number. Sample calculations of the six shock wave interference patterns, a listing of the computer program, and flowcharts of the programming logic are included.

Systematic Approach to Calculate the Concentration of Chemical Species in Multi-Equilibrium Problems

Science.gov (United States)

Baeza-Baeza, Juan Jose; Garcia-Alvarez-Coque, Maria Celia

2011-01-01

A general systematic approach is proposed for the numerical calculation of multi-equilibrium problems. The approach involves several steps: (i) the establishment of balances involving the chemical species in solution (e.g., mass balances, charge balance, and stoichiometric balance for the reaction products), (ii) the selection of the unknowns (the…

Recurrence Relations for the Equilibrium Means of Distributions Arising in Chemical Reactions

Directory of Open Access Journals (Sweden)

E.K. Elsheikh

1997-12-01

Full Text Available In this paper we derive recurrence relations that describe how the equilibrium mean of the number molecules of a reactant varies with each of the parameters defining the initial state for four basic reversible chemical reactions. In essence, the relations provide a rationale for updating the equilibrium mean following the addition (or removal of a molecule of one of the types involved in the reaction, there being a relation for each type. With a new parameterization introduced for each reaction, the relations provide a convenient means of evaluating the means, variances and other important moments without any need to work out the underlying distributions. As an application, the relations are used to numerically assess-approximate expressions for the means and variances.

A study on the criticality search of transuranium recycling BWR core by adjusting supplied fuel composition in equilibrium state

International Nuclear Information System (INIS)

Seino, Takeshi; Sekimoto, Hiroshi

1997-01-01

There have been some difficulties in carrying out an extensive evaluation of the equilibrium state of Light Water Reactor (LWR) recycling operations keeping their fixed criticality condition using conventional design codes, because of the complexity of their calculational model for practical fuel and core design and because of a large amount of calculation time. This study presents an efficient approach to secure the criticality in an equilibrium cycle by adjusting a supplied fuel composition. The criticality search is performed by the use of fuel importance obtained from the equilibrium adjoint to a continuously fuel supplied core burnup equation. Using this method, some numerical analyses were carried out in order to evaluate the mixed oxide (MOX) fuel composition of equilibrium Boiling Water Reactor (BWR) cores satisfying the criticality requirement. The results showed the comprehensive and quantitative characteristics on the equilibrium cores confining transuranium for different MOX fuel loading fractions and irradiating conditions. (author)

Control of Chemical Equilibrium by Solvent: A Basis for Teaching Physical Chemistry of Solutions

Science.gov (United States)

Prezhdo, Oleg V.; Craig, Colleen F.; Fialkov, Yuriy; Prezhdo, Victor V.

2007-01-01

The study demonstrates that the solvent present in a system can highly alter and control the chemical equilibrium of a system. The results show that the dipole moment and polarizibility of a system can be highly altered by using different mixed solvents.

Exploring the Use of Multiple Analogical Models when Teaching and Learning Chemical Equilibrium

Science.gov (United States)

Harrison, Allan G.; De Jong, Onno

2005-01-01

This study describes the multiple analogical models used to introduce and teach Grade 12 chemical equilibrium. We examine the teacher's reasons for using models, explain each model's development during the lessons, and analyze the understandings students derived from the models. A case study approach was used and the data were drawn from the…

Efficient modeling of reactive transport phenomena by a multispecies random walk coupled to chemical equilibrium

International Nuclear Information System (INIS)

Pfingsten, W.

1996-01-01

Safety assessments for radioactive waste repositories require a detailed knowledge of physical, chemical, hydrological, and geological processes for long time spans. In the past, individual models for hydraulics, transport, or geochemical processes were developed more or less separately to great sophistication for the individual processes. Such processes are especially important in the near field of a waste repository. Attempts have been made to couple at least two individual processes to get a more adequate description of geochemical systems. These models are called coupled codes; they couple predominantly a multicomponent transport model with a chemical reaction model. Here reactive transport is modeled by the sequentially coupled code MCOTAC that couples one-dimensional advective, dispersive, and diffusive transport with chemical equilibrium complexation and precipitation/dissolution reactions in a porous medium. Transport, described by a random walk of multispecies particles, and chemical equilibrium calculations are solved separately, coupled only by an exchange term. The modular-structured code was applied to incongruent dissolution of hydrated silicate gels, to movement of multiple solid front systems, and to an artificial, numerically difficult heterogeneous redox problem. These applications show promising features with respect to applicability to relevant problems and possibilities of extensions

Development of a multi-species mass transport model for concrete with account to thermodynamic phase equilibriums

DEFF Research Database (Denmark)

Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn

2011-01-01

different types of cements. For example, the physicochemical evaluation of steel corrosion initiation can be studied by calculating the molar ratio of chloride ion to hydroxide ion in the pore solution. The model can, further, for example, calculate changes of solid-phase composition caused......) theory alone, not involving chemical processes, have no real practical interest since the chemical action is very dominant for cement based materials. Coupled mass transport and chemical equilibrium models can be used to calculate the variation in pore solution and solid-phase composition when using...

Analysis of non-equilibrium phenomena in inductively coupled plasma generators

Energy Technology Data Exchange (ETDEWEB)

Zhang, W.; Panesi, M., E-mail: mpanesi@illinois.edu [University of Illinois at Urbana-Champaign, Urbana, Illinois 61822 (United States); Lani, A. [Von Karman Institute for Fluid Dynamics, Rhode-Saint-Genèse (Belgium)

2016-07-15

This work addresses the modeling of non-equilibrium phenomena in inductively coupled plasma discharges. In the proposed computational model, the electromagnetic induction equation is solved together with the set of Navier-Stokes equations in order to compute the electromagnetic and flow fields, accounting for their mutual interaction. Semi-classical statistical thermodynamics is used to determine the plasma thermodynamic properties, while transport properties are obtained from kinetic principles, with the method of Chapman and Enskog. Particle ambipolar diffusive fluxes are found by solving the Stefan-Maxwell equations with a simple iterative method. Two physico-mathematical formulations are used to model the chemical reaction processes: (1) A Local Thermodynamics Equilibrium (LTE) formulation and (2) a thermo-chemical non-equilibrium (TCNEQ) formulation. In the TCNEQ model, thermal non-equilibrium between the translational energy mode of the gas and the vibrational energy mode of individual molecules is accounted for. The electronic states of the chemical species are assumed in equilibrium with the vibrational temperature, whereas the rotational energy mode is assumed to be equilibrated with translation. Three different physical models are used to account for the coupling of chemistry and energy transfer processes. Numerical simulations obtained with the LTE and TCNEQ formulations are used to characterize the extent of non-equilibrium of the flow inside the Plasmatron facility at the von Karman Institute. Each model was tested using different kinetic mechanisms to assess the sensitivity of the results to variations in the reaction parameters. A comparison of temperatures and composition profiles at the outlet of the torch demonstrates that the flow is in non-equilibrium for operating conditions characterized by pressures below 30 000 Pa, frequency 0.37 MHz, input power 80 kW, and mass flow 8 g/s.

Analogies in the Teaching of Chemical Equilibrium: A Synthesis/Analysis of the Literature

Science.gov (United States)

Raviolo, Andres; Garritz, Andoni

2009-01-01

This paper presents a thorough literature review of the analogies used to teach chemical equilibrium. The main objective is to compile all the analogies that have been found to be of service to the teacher and the student. Additionally, we categorize and analyze analogies in relation to the following aspects: representation of the dynamic nature…

Chemical vapor composites (CVC)

International Nuclear Information System (INIS)

Reagan, P.

1993-01-01

The Chemical Vapor Composite, CVC trademark , process fabricates composite material by simply mixing particles (powders and or fibers) with CVD reactants which are transported and co-deposited on a hot substrate. A key feature of the CVC process is the control provided by varing the density, geometry (aspect ratio) and composition of the entrained particles in the matrix material, during deposition. The process can fabricate composite components to net shape (± 0.013 mm) on a machined substrate in a single step. The microstructure of the deposit is described and several examples of different types of particles in the matrix are illustrated. Mechanical properties of SiC composite material fabricated with SiC powder and fiber will be presented. Several examples of low cost ceramic composite products will be shown. (orig.)

Chemical composition, secondary metabolites, in vitro gas ...

African Journals Online (AJOL)

Chemical composition, secondary metabolites, in vitro gas production characteristics and acceptability study of some forage for ruminant feeding in South-Western Nigeria. ... Chemical composition and qualitative analysis of saponins, phenol and steroids of the plants were determined. In vitro gas production (IVGP) was ...

Pulse-density modulation control of chemical oscillation far from equilibrium in a droplet open-reactor system

OpenAIRE

Sugiura, Haruka; Ito, Manami; Okuaki, Tomoya; Mori, Yoshihito; Kitahata, Hiroyuki; Takinoue, Masahiro

2016-01-01

The design, construction and control of artificial self-organized systems modelled on dynamical behaviours of living systems are important issues in biologically inspired engineering. Such systems are usually based on complex reaction dynamics far from equilibrium; therefore, the control of non-equilibrium conditions is required. Here we report a droplet open-reactor system, based on droplet fusion and fission, that achieves dynamical control over chemical fluxes into/out of the reactor for c...

Equilibrium flavor dynamics during the cosmic confinement transition

International Nuclear Information System (INIS)

Kaempfer, B.

1988-10-01

The dynamics of the flavor composition of strongly interacting matter during the cosmic confinement transition is followed up in a simplified thermodynamical model. Relying on thermal, mechanical and chemical equilibrium the strangeness fraction of strongly interacting matter is analyzed. Due to equilibrium with respect to ΔS=0 and ΔS=1 weak interactions the relations between different flavors depend strongly on the poorly known lepton excess. In a universe where the lepton (antilepton) excess is in the same order of magnitude as the baryon excess, the strange quark abundancies are suppressed (enhanced). In the hadron phase the strange baryons carry up to a half of the baryon excess. (author) 22 refs.; 9 figs

Adsorption Equilibrium and Kinetics of the Removal of Ammoniacal Nitrogen by Zeolite X/Activated Carbon Composite Synthesized from Elutrilithe

Directory of Open Access Journals (Sweden)

Yong Zhang

2017-01-01

Full Text Available Zeolite X/activated carbon composite material (X/AC was prepared from elutrilithe, by a process consisting of carbonization, activation, and subsequent hydrothermal transformation of aluminosilicate in alkaline solution, which was used for the removal of ammoniacal nitrogen from aqueous solutions. Adsorption kinetics, equilibrium, and thermodynamic were studied and fitted by various models. The adsorption kinetics is best depicted by pseudosecond-order model, and the adsorption isotherm fits the Freundlich and Redlich-Peterson model. This explains the ammoniacal nitrogen adsorption onto X/AC which was chemical adsorption in nature. Thermodynamic properties such as ΔG, ΔH, and ΔS were determined for the ammoniacal nitrogen adsorption, and the positive enthalpy confirmed that the adsorption process was endothermic. It can be inferred that ammoniacal nitrogen removal by X/AC composite is attributed to the ion exchange ability of zeolite X. Further, as a novel sorbent, this material has the potential application in removing ammoniacal nitrogen coexisting with other organic compounds from industrial wastewater.

Chemical composition and strength of dolomite geopolymer composites

Science.gov (United States)

Aizat, E. A.; Al Bakri, A. M. M.; Liew, Y. M.; Heah, C. Y.

2017-09-01

The chemical composition of dolomite and the compressive strength of dolomite geopolymer composites were studied. The both composites prepared with mechanical mixer manufactured by with rotor speed of 350 rpm and curing in the oven for 24 hours at 80˚C. XRF analysis showThe dolomite raw materials contain fewer amounts of Si and Al but high Ca in its composition. Dolomite geopolymer composites with 20M of NaOH shows greater and optimum compressive strength compared to dolomite geopolymer with other NaOH molarity. This indicated better interaction of dolomite raw material and alkaline activator need high molarity of NaOH in order to increase the reactivity of dolomite.

A development of multi-Species mass transport model considering thermodynamic phase equilibrium

DEFF Research Database (Denmark)

Hosokawa, Yoshifumi; Yamada, Kazuo; Johannesson, Björn

2008-01-01

) variation in solid-phase composition when using different types of cement, (ii) physicochemical evaluation of steel corrosion initiation behaviour by calculating the molar ratio of chloride ion to hydroxide ion [Cl]/[OH] in pore solution, (iii) complicated changes of solid-phase composition caused......In this paper, a multi-species mass transport model, which can predict time dependent variation of pore solution and solid-phase composition due to the mass transport into the hardened cement paste, has been developed. Since most of the multi-species models established previously, based...... on the Poisson-Nernst-Planck theory, did not involve the modeling of chemical process, it has been coupled to thermodynamic equilibrium model in this study. By the coupling of thermodynamic equilibrium model, the multi-species model could simulate many different behaviours in hardened cement paste such as: (i...

Phase diagram and structural evolution of tin/indium (Sn/In) nanosolder particles: from a non-equilibrium state to an equilibrium state.

Science.gov (United States)

Shu, Yang; Ando, Teiichi; Yin, Qiyue; Zhou, Guangwen; Gu, Zhiyong

2017-08-31

A binary system of tin/indium (Sn/In) in the form of nanoparticles was investigated for phase transitions and structural evolution at different temperatures and compositions. The Sn/In nanosolder particles in the composition range of 24-72 wt% In were synthesized by a surfactant-assisted chemical reduction method under ambient conditions. The morphology and microstructure of the as-synthesized nanoparticles were analyzed by scanning electron microscopy (SEM), high resolution transmission electron microscopy (HRTEM), selected area electron diffraction (SAED) and X-ray diffraction (XRD). HRTEM and SAED identified InSn 4 and In, with some Sn being detected by XRD, but no In 3 Sn was observed. The differential scanning calorimetry (DSC) thermographs of the as-synthesized nanoparticles exhibited an endothermic peak at around 116 °C, which is indicative of the metastable eutectic melting of InSn 4 and In. When the nanosolders were subjected to heat treatment at 50-225 °C, the equilibrium phase In 3 Sn appeared while Sn disappeared. The equilibrium state was effectively attained at 225 °C. A Tammann plot of the DSC data of the as-synthesized nanoparticles indicated that the metastable eutectic composition is about 62% In, while that of the DSC data of the 225 °C heat-treated nanoparticles yielded a eutectic composition of 54% In, which confirmed the attainment of the equilibrium state at 225 °C. The phase boundaries estimated from the DSC data of heat-treated Sn/In nanosolder particles matched well with those in the established Sn-In equilibrium phase diagram. The phase transition behavior of Sn/In nanosolders leads to a new understanding of binary alloy particles at the nanoscale, and provides important information for their low temperature soldering processing and applications.

Chemical equilibrium of hydrogen and aqueous solutions of 1:1 bicarbonate and formate salts with a common cation.

NARCIS (Netherlands)

Engel, D.C.; Engel, D.C.; Versteeg, Geert; van Swaaij, Willibrordus Petrus Maria

1997-01-01

This was accomplished for the sodium (M = Na), potassium (M = K) and ammonium (M = NH4) systems by measuring the equilibrium composition. This reaction was allowed to proceed from both sides of the equilibrium in a suspension of Pd/C and Pd/γ-Al2O3 catalyst particles, and was carried out at 20, 40

A study on the criticality search of transuranium recycling BWR core by adjusting supplied fuel composition in equilibrium state

International Nuclear Information System (INIS)

Seino, Takeshi; Sekimoto, Hiroshi

1998-01-01

There have been some difficulties in carrying out an extensive evaluation of the equilibrium state of Light Water Reactor (LWR) recycling operations keeping their fixed criticality condition using conventional design codes because of the complexity of their calculation model for practical fuel and core design and because of a large amount of calculation time. This study presents an efficient approach to secure the criticality in an equilibrium cycle by adjusting a supplied fuel composition. The criticality search is performed by the use of fuel importance obtained from the equation adjoint to a continuously fuel supplied core burnup equation. Using this method, some numerical analyses were carried out in order to evaluate the mixed oxide (MOX) fuel composition of equilibrium Boiling Water Reactor (BWR) cores satisfying the criticality requirement. The results showed the comprehensive and quantitative characteristics on the equilibrium cores confining transuraniums for different MOX fuel loading fractions and irradiating conditions

Using Think-Aloud Protocols to Investigate Secondary School Chemistry Teachers' Misconceptions about Chemical Equilibrium

Science.gov (United States)

Cheung, Derek

2009-01-01

Secondary school chemistry teachers' understanding of chemical equilibrium was investigated through interviews using the think-aloud technique. The interviews were conducted with twelve volunteer chemistry teachers in Hong Kong. Their teaching experience ranged from 3 to 18 years. They were asked to predict what would happen to the equilibrium…

Understanding Chemical Equilibrium: The Role of Gas Phases and Mixing Contributions in the Minimum of Free Energy Plots

Science.gov (United States)

Tomba, J. Pablo

2017-01-01

The use of free energy plots to understand the concept of thermodynamic equilibrium has been shown to be of great pedagogical value in materials science. Although chemical equilibrium is also amenable to this kind of analysis, it is not part of the agenda of materials science textbooks. Something similar is found in chemistry branches, where free…

A Teaching Sequence for Learning the Concept of Chemical Equilibrium in Secondary School Education

Science.gov (United States)

Ghirardi, Marco; Marchetti, Fabio; Pettinari, Claudio; Regis, Alberto; Roletto, Ezio

2014-01-01

A novel didactic sequence is proposed for the teaching of chemical equilibrium. This teaching sequence takes into account the historical and epistemological evolution of the concept, the alternative conceptions and learning difficulties highlighted by teaching science and research in education, and the need to focus on both the students'…

Development of 19F-NMR chemical shift detection of DNA B-Z equilibrium using 19F-NMR.

Science.gov (United States)

Nakamura, S; Yang, H; Hirata, C; Kersaudy, F; Fujimoto, K

2017-06-28

Various DNA conformational changes are in correlation with biological events. In particular, DNA B-Z equilibrium showed a high correlation with translation and transcription. In this study, we developed a DNA probe containing 5-trifluoromethylcytidine or 5-trifluoromethylthymidine to detect DNA B-Z equilibrium using 19 F-NMR. Its probe enabled the quantitative detection of B-, Z-, and ss-DNA based on 19 F-NMR chemical shift change.

Methane on Mars: Thermodynamic Equilibrium and Photochemical Calculations

Science.gov (United States)

Levine, J. S.; Summers, M. E.; Ewell, M.

2010-01-01

The detection of methane (CH4) in the atmosphere of Mars by Mars Express and Earth-based spectroscopy is very surprising, very puzzling, and very intriguing. On Earth, about 90% of atmospheric ozone is produced by living systems. A major question concerning methane on Mars is its origin - biological or geological. Thermodynamic equilibrium calculations indicated that methane cannot be produced by atmospheric chemical/photochemical reactions. Thermodynamic equilibrium calculations for three gases, methane, ammonia (NH3) and nitrous oxide (N2O) in the Earth s atmosphere are summarized in Table 1. The calculations indicate that these three gases should not exist in the Earth s atmosphere. Yet they do, with methane, ammonia and nitrous oxide enhanced 139, 50 and 12 orders of magnitude above their calculated thermodynamic equilibrium concentration due to the impact of life! Thermodynamic equilibrium calculations have been performed for the same three gases in the atmosphere of Mars based on the assumed composition of the Mars atmosphere shown in Table 2. The calculated thermodynamic equilibrium concentrations of the same three gases in the atmosphere of Mars is shown in Table 3. Clearly, based on thermodynamic equilibrium calculations, methane should not be present in the atmosphere of Mars, but it is in concentrations approaching 30 ppbv from three distinct regions on Mars.

General method and thermodynamic tables for computation of equilibrium composition and temperature of chemical reactions

Science.gov (United States)

Huff, Vearl N; Gordon, Sanford; Morrell, Virginia E

1951-01-01

A rapidly convergent successive approximation process is described that simultaneously determines both composition and temperature resulting from a chemical reaction. This method is suitable for use with any set of reactants over the complete range of mixture ratios as long as the products of reaction are ideal gases. An approximate treatment of limited amounts of liquids and solids is also included. This method is particularly suited to problems having a large number of products of reaction and to problems that require determination of such properties as specific heat or velocity of sound of a dissociating mixture. The method presented is applicable to a wide variety of problems that include (1) combustion at constant pressure or volume; and (2) isentropic expansion to an assigned pressure, temperature, or Mach number. Tables of thermodynamic functions needed with this method are included for 42 substances for convenience in numerical computations.

The Rate-Controlled Constrained-Equilibrium Approach to Far-From-Local-Equilibrium Thermodynamics

Directory of Open Access Journals (Sweden)

Hameed Metghalchi

2012-01-01

Full Text Available The Rate-Controlled Constrained-Equilibrium (RCCE method for the description of the time-dependent behavior of dynamical systems in non-equilibrium states is a general, effective, physically based method for model order reduction that was originally developed in the framework of thermodynamics and chemical kinetics. A generalized mathematical formulation is presented here that allows including nonlinear constraints in non-local equilibrium systems characterized by the existence of a non-increasing Lyapunov functional under the system’s internal dynamics. The generalized formulation of RCCE enables to clarify the essentials of the method and the built-in general feature of thermodynamic consistency in the chemical kinetics context. In this paper, we work out the details of the method in a generalized mathematical-physics framework, but for definiteness we detail its well-known implementation in the traditional chemical kinetics framework. We detail proofs and spell out explicit functional dependences so as to bring out and clarify each underlying assumption of the method. In the standard context of chemical kinetics of ideal gas mixtures, we discuss the relations between the validity of the detailed balance condition off-equilibrium and the thermodynamic consistency of the method. We also discuss two examples of RCCE gas-phase combustion calculations to emphasize the constraint-dependent performance of the RCCE method.

The Effect of a Conceptual Change Approach on Understanding of Students' Chemical Equilibrium Concepts

Science.gov (United States)

Atasoy, Basri; Akkus, Huseyin; Kadayifci, Hakki

2009-01-01

The purpose of this study was to compare the effects of a conceptual change approach over traditional instruction on tenth-grade students' conceptual achievement in understanding chemical equilibrium. The study was conducted in two classes of the same teacher with participation of a total of 44 tenth-grade students. In this study, a…

Equilibrium sampling of environmental pollutants in fish: Comparison with lipid- normalized concentrations and homogenization effects on chemical activity

DEFF Research Database (Denmark)

Jahnke, Annika; Mayer, Philipp; Adolfsson-Erici, Margaretha

2011-01-01

of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher...... in the homogenates (statistically significant in 18 of 21 cases, phomogenization increased the chemical activity of the PCBs and decreased the fugacity capacity of the tissue. This observation has implications for equilibrium sampling and partition coefficients determined using tissue...... homogenates....

Numerical simulation of air hypersonic flows with equilibrium chemical reactions

Science.gov (United States)

Emelyanov, Vladislav; Karpenko, Anton; Volkov, Konstantin

2018-05-01

The finite volume method is applied to solve unsteady three-dimensional compressible Navier-Stokes equations on unstructured meshes. High-temperature gas effects altering the aerodynamics of vehicles are taken into account. Possibilities of the use of graphics processor units (GPUs) for the simulation of hypersonic flows are demonstrated. Solutions of some test cases on GPUs are reported, and a comparison between computational results of equilibrium chemically reacting and perfect air flowfields is performed. Speedup of solution on GPUs with respect to the solution on central processor units (CPUs) is compared. The results obtained provide promising perspective for designing a GPU-based software framework for practical applications.

Visualising the equilibrium distribution and mobility of organic contaminants in soil using the chemical partitioning space.

Science.gov (United States)

Wong, Fiona; Wania, Frank

2011-06-01

Assessing the behaviour of organic chemicals in soil is a complex task as it is governed by the physical chemical properties of the chemicals, the characteristics of the soil as well as the ambient conditions of the environment. The chemical partitioning space, defined by the air-water partition coefficient (K(AW)) and the soil organic carbon-water partition coefficient (K(OC)), was employed to visualize the equilibrium distribution of organic contaminants between the air-filled pores, the pore water and the solid phases of the bulk soil and the relative importance of the three transport processes removing contaminants from soil (evaporation, leaching and particle erosion). The partitioning properties of twenty neutral organic chemicals (i.e. herbicides, pharmaceuticals, polychlorinated biphenyls and volatile chemicals) were estimated using poly-parameter linear free energy relationships and superimposed onto these maps. This allows instantaneous estimation of the equilibrium phase distribution and mobility of neutral organic chemicals in soil. Although there is a link between the major phase and the dominant transport process, such that chemicals found in air-filled pore space are subject to evaporation, those in water-filled pore space undergo leaching and those in the sorbed phase are associated with particle erosion, the partitioning coefficient thresholds for distribution and mobility can often deviate by many orders of magnitude. In particular, even a small fraction of chemical in pore water or pore air allows for evaporation and leaching to dominate over solid phase transport. Multiple maps that represent soils that differ in the amount and type of soil organic matter, water saturation, temperature, depth of surface soil horizon, and mineral matters were evaluated.

Numerical verification of equilibrium chemistry software within nuclear fuel performance codes

International Nuclear Information System (INIS)

Piro, M.H.; Lewis, B.J.; Thompson, W.T.; Simunovic, S.; Besmann, T.M.

2010-01-01

A numerical tool is in an advanced state of development to compute the equilibrium compositions of phases and their proportions in multi-component systems of importance to the nuclear industry. The resulting software is being conceived for direct integration into large multi-physics fuel performance codes, particularly for providing transport source terms, material properties, and boundary conditions in heat and mass transport modules. Consequently, any numerical errors produced in equilibrium chemistry computations will be propagated in subsequent heat and mass transport calculations, thus falsely predicting nuclear fuel behaviour. The necessity for a reliable method to numerically verify chemical equilibrium computations is emphasized by the requirement to handle the very large number of elements necessary to capture the entire fission product inventory. A simple, reliable and comprehensive numerical verification method called the Gibbs Criteria is presented which can be invoked by any equilibrium chemistry solver for quality assurance purposes. (author)

Chemical behavior of lanthanides-tungsten composite materials used in thermo-emissive cathodes

International Nuclear Information System (INIS)

Cadoret, K.; Cachard, J. de; Martinez, L.; Millot, F.; Hennet, L.; Douy, A.; Licheron, M.

2001-01-01

This work presents the crystallography and chemistry of new lanthanides-tungsten composite materials developed to manufacture thermionic cathodes for power grid tubes, based on the same principle than thorium-free cathodes. By mean of x-Ray diffraction at high temperature and under vacuum with synchrotron radiation facilities, we followed in real time the different phases and phase transitions that can occur during the heating process and the carburization at 1550 o C of such tungstates deposits on thin tungsten ribbons. Melting points for composition between 9 La 2 O 3 - 1 WO 3 and 2 La 2 O 3 - 9 WO 3 were specified under the pressure of 1x10 -6 mbar. After interpretation of x-ray diffraction results, phase diagram of n La 2 O 3 - m WO 3 system under vacuum in equilibrium with metallic tungsten have been deduced. Moreover we underline by these works the fact that using a lanthanum-rich tungstate involves better stability and chemical homogeneity of the cathodes surfaces with temperature. (author)

Non-equilibrium Microwave Plasma for Efficient High Temperature Chemistry.

Science.gov (United States)

van den Bekerom, Dirk; den Harder, Niek; Minea, Teofil; Gatti, Nicola; Linares, Jose Palomares; Bongers, Waldo; van de Sanden, Richard; van Rooij, Gerard

2017-08-01

A flowing microwave plasma based methodology for converting electric energy into internal and/or translational modes of stable molecules with the purpose of efficiently driving non-equilibrium chemistry is discussed. The advantage of a flowing plasma reactor is that continuous chemical processes can be driven with the flexibility of startup times in the seconds timescale. The plasma approach is generically suitable for conversion/activation of stable molecules such as CO2, N2 and CH4. Here the reduction of CO2 to CO is used as a model system: the complementary diagnostics illustrate how a baseline thermodynamic equilibrium conversion can be exceeded by the intrinsic non-equilibrium from high vibrational excitation. Laser (Rayleigh) scattering is used to measure the reactor temperature and Fourier Transform Infrared Spectroscopy (FTIR) to characterize in situ internal (vibrational) excitation as well as the effluent composition to monitor conversion and selectivity.

Transport Coefficients for the NASA Lewis Chemical Equilibrium Program

Science.gov (United States)

Svehla, Roger A.

1995-01-01

The new transport property data that will be used in the NASA Lewis Research Center's Chemical Equilibrium and Applications Program (CEA) is presented. It complements a previous publication that documented the thermodynamic and transport property data then in use. Sources of the data and a brief description of the method by which the data were obtained are given. Coefficients to calculate the viscosity, thermal conductivity, and binary interactions are given for either one, or usually, two temperature intervals, typically 300 to 1000 K and 1000 to 5000 K. The form of the transport equation is the same as used previously. The number of species was reduced from the previous database. Many species for which the data were estimated were eliminated from the database. Some ionneutral interactions were added.

Chemical composition and antioxidant activity of essential oil ...

African Journals Online (AJOL)

In the present work, we studied the chemical composition of the essential oil of Cistus ladanifer and Cistus libanotis growing in Eastern Morocco. The essential oils were obtained by hydrodistillation and their chemical composition was analysed using gas chromatography- mass spectrometry (GC–MS). Camphene, borneol ...

Fatty acid and cholesterol content, chemical composition and ...

African Journals Online (AJOL)

This study aimed to determine the fatty acid and chemical composition and cholesterol concentration of horsemeat, and to evaluate its taste acceptability by the Brazilian population. Horsemeat samples (M. longissimus dorsi) were obtained from a Paraná State slaughterhouse. The chemical composition revealed a low lipid ...

Concentration effect on inter-mineral equilibrium isotope fractionation: insights from Mg and Ca isotopic systems

Science.gov (United States)

Huang, F.; Wang, W.; Zhou, C.; Kang, J.; Wu, Z.

2017-12-01

Many naturally occurring minerals, such as carbonate, garnet, pyroxene, and feldspar, are solid solutions with large variations in chemical compositions. Such variations may affect mineral structures and modify the chemical bonding environment around atoms, which further impacts the equilibrium isotope fractionation factors among minerals. Here we investigated the effects of Mg content on equilibrium Mg and Ca isotope fractionation among carbonates and Ca content on equilibrium Ca isotope fractionation between orthopyroxene (opx) and clinopyroxene (cpx) using first-principles calculations. Our results show that the average Mg-O bond length increases with decreasing Mg/(Mg+Ca) in calcite when it is greater than 1/48[1] and the average Ca-O bond length significantly decreases with decreasing Ca/(Ca+Mg+Fe) in opx when it ranges from 2/16 to 1/48[2]. Equilibrium isotope fractionation is mainly controlled by bond strengths, which could be measured by bond lengths. Thus, 103lnα26Mg/24Mg between dolomite and calcite dramatically increases with decreasing Mg/(Mg+Ca) in calcite [1] and it reaches a constant value when it is lower than 1/48. 103lnα44Ca/40Ca between opx and cpx significantly increases with decreasing Ca content in opx when Ca/(Ca+Mg+Fe) ranges from 2/16 to 1/48 [2]. If Ca/(Ca+Mg+Fe) is below 1/48, 103lnα44Ca/40Ca is not sensitive to Ca content. Based on our results, we conclude that the concentration effect on equilibrium isotope fractionation could be significant within a certain range of chemical composition of minerals, which should be a ubiquitous phenomenon in solid solution systems. [1] Wang, W., Qin, T., Zhou, C., Huang, S., Wu, Z., Huang, F., 2017. GCA 208, 185-197. [2] Feng, C., Qin, T., Huang, S., Wu, Z., Huang, F., 2014. GCA 143, 132-142.

Chemical Equilibrium Modeling of Hanford Waste Tank Processing: Applications of Fundamental Science

International Nuclear Information System (INIS)

Felmy, Andrew R.; Wang, Zheming; Dixon, David A.; Hess, Nancy J.

2004-01-01

The development of computational models based upon fundamental science is one means of quantitatively transferring the results of scientific investigations to practical application by engineers in laboratory and field situations. This manuscript describes one example of such efforts, specifically the development and application of chemical equilibrium models to different waste management issues at the U.S. Department of Energy (DOE) Hanford Site. The development of the chemical models is described with an emphasis on the fundamental science investigations that have been undertaken in model development followed by examples of different waste management applications. The waste management issues include the leaching of waste slurries to selective remove non-hazardous components and the separation of Sr90 and transuranics from the waste supernatants. The fundamental science contributions include: molecular simulations of the energetics of different molecular clusters to assist in determining the species present in solution, advanced synchrotron research to determine the chemical form of precipitates, and laser based spectroscopic studies of solutions and solids.

New fundamental equations of thermodynamics for systems in chemical equilibrium at a specified partial pressure of a reactant and the standard transformed formation properties of reactants

International Nuclear Information System (INIS)

Alberty, R.A.; Oppenheim, I.

1993-01-01

When temperature, pressure, and the partial pressure of a reactant are fixed, the criterion of chemical equilibrium can be expressed in terms of the transformed Gibbs energy G' that is obtained by using a Legendre transform involving the chemical potential of the reactant that is fixed. For reactions of ideal gases, the most natural variables to use in the fundamental equation are T, P', and P B , where P' is the partial pressure of the reactants other than the one that is fixed and P B is the partial pressure of the reactant that is fixed. The fundamental equation for G' yields the expression for the transformed entropy S', and a transformed enthalpy can be defined by the additional Legendre transform H'=G'+TS'. This leads to an additional form of the fundamental equation. The calculation of transformed thermodynamic properties and equilibrium compositions is discussed for a simple system and for a general multireaction system. The change, in a reaction, of the binding of the reactant that is at a specified pressure can be calculated using one of the six Maxwell equations of the fundamental equation in G'

Chemical composition of stars in Ruprecht 106 .

Science.gov (United States)

François, P.

High resolution spectra of 9 stars belonging to the globular cluster Rup 106 have been used to determine their chemical composition. The results reveal that Ruprecht 106 exhibits abundance anomalies when compared to galactic globular cluster of similar metallicity. The chemical composition of these stars is similar to what is found in Dwarf spheroidal galaxies favoring the hypothesis that Rup 106 has not been formed in our Galaxy.

Out-of-equilibrium catalysis of chemical reactions by electronic tunnel currents.

Science.gov (United States)

Dzhioev, Alan A; Kosov, Daniel S; von Oppen, Felix

2013-04-07

We present an escape rate theory for current-induced chemical reactions. We use Keldysh nonequilibrium Green's functions to derive a Langevin equation for the reaction coordinate. Due to the out of equilibrium electronic degrees of freedom, the friction, noise, and effective temperature in the Langevin equation depend locally on the reaction coordinate. As an example, we consider the dissociation of diatomic molecules induced by the electronic current from a scanning tunnelling microscope tip. In the resonant tunnelling regime, the molecular dissociation involves two processes which are intricately interconnected: a modification of the potential energy barrier and heating of the molecule. The decrease of the molecular barrier (i.e., the current induced catalytic reduction of the barrier) accompanied by the appearance of the effective, reaction-coordinate-dependent temperature is an alternative mechanism for current-induced chemical reactions, which is distinctly different from the usual paradigm of pumping vibrational degrees of freedom.

Chemical equilibrium between particles and complex particles in quantum many-body system at very low temperature

International Nuclear Information System (INIS)

Matsumoto, Atsushi

2004-01-01

The equilibrium state at very low temperature and phase state at 0 K between the particle 1 and particle 2 and the particle 12, which particle 1 bond with particle 2, of infinite uniform system was investigated. Boson and fermion are thought as particle and three kinds of reactions are considered. On the case of boson + boson ? boson, the system is all molecules or atoms when ΔE≠0 and T=0, and the density is not determined under Tc when ΔE=0. On the case of boson + fermion ? fermion, molecules and atoms are able to exist together at T=0. On fermion + fermion ? boson, molecule is formed and condensed. The chemical equilibrium between particles and complex particles and three cases of equilibrium are explained. (S.Y.)

Phase equilibrium engineering

CERN Document Server

Brignole, Esteban Alberto

2013-01-01

Traditionally, the teaching of phase equilibria emphasizes the relationships between the thermodynamic variables of each phase in equilibrium rather than its engineering applications. This book changes the focus from the use of thermodynamics relationships to compute phase equilibria to the design and control of the phase conditions that a process needs. Phase Equilibrium Engineering presents a systematic study and application of phase equilibrium tools to the development of chemical processes. The thermodynamic modeling of mixtures for process development, synthesis, simulation, design and

Addition to the Lewis Chemical Equilibrium Program to allow computation from coal composition data

Science.gov (United States)

Sevigny, R.

1980-01-01

Changes made to the Coal Gasification Project are reported. The program was developed by equilibrium combustion in rocket engines. It can be applied directly to the entrained flow coal gasification process. The particular problem addressed is the reduction of the coal data into a form suitable to the program, since the manual process is involved and error prone. A similar problem in relating the normal output of the program to parameters meaningful to the coal gasification process is also addressed.

The Chemical Composition of Mercury

OpenAIRE

Nittler, Larry R.; Chabot, Nancy L.; Grove, Timothy L.; Peplowski, Patrick N.

2017-01-01

The chemical composition of a planetary body reflects its starting conditions modified by numerous processes during its formation and geological evolution. Measurements by X-ray, gamma-ray, and neutron spectrometers on the MESSENGER spacecraft revealed Mercury's surface to have surprisingly high abundances of the moderately volatile elements sodium, sulfur, potassium, chlorine, and thorium, and a low abundance of iron. This composition rules out some formation models for which high temperatur...

Chemical and sulphur isotope compositions of pyrite in the ...

Indian Academy of Sciences (India)

sulphide mineralization and their chemical evo- lution in relative .... properties and chemical compositions. Electron ..... from the sulphide lode provide clues to the chang- ing fluid ..... Raymond O L 1996 Pyrite composition and ore geneis in.

Quantum-chemical calculations and electron diffraction study of the equilibrium molecular structure of vitamin K3

Science.gov (United States)

Khaikin, L. S.; Tikhonov, D. S.; Grikina, O. E.; Rykov, A. N.; Stepanov, N. F.

2014-05-01

The equilibrium molecular structure of 2-methyl-1,4-naphthoquinone (vitamin K3) having C s symmetry is experimentally characterized for the first time by means of gas-phase electron diffraction using quantum-chemical calculations and data on the vibrational spectra of related compounds.

A phase-field model for non-equilibrium solidification of intermetallics

International Nuclear Information System (INIS)

Assadi, H.

2007-01-01

Intermetallics may exhibit unique solidification behaviour-including slow growth kinetics, anomalous partitioning and formation of unusual growth morphologies-because of departure from local equilibrium. A phase-field model is developed and used to illustrate these non-equilibrium effects in solidification of a prototype B2 intermetallic phase. The model takes sublattice compositions as primary field variables, from which chemical long-range order is derived. The diffusive reactions between the two sublattices, and those between each sublattice and the liquid phase are taken as 'internal' kinetic processes, which take place within control volumes of the system. The model can thus capture solute and disorder trapping effects, which are consistent-over a wide range of the solid/liquid interface thickness-with the predictions of the sharp-interface theory of solute and disorder trapping. The present model can also take account of solid-state ordering and thus illustrate the effects of chemical ordering on microstructure formation and crystal growth kinetics

The Lack of Chemical Equilibrium does not Preclude the Use of the Classical Nucleation Theory in Circumstellar Outflows

Science.gov (United States)

Paquette, John A.; Nuth, Joseph A., III

2011-01-01

Classical nucleation theory has been used in models of dust nucleation in circumstellar outflows around oxygen-rich asymptotic giant branch stars. One objection to the application of classical nucleation theory (CNT) to astrophysical systems of this sort is that an equilibrium distribution of clusters (assumed by CNT) is unlikely to exist in such conditions due to a low collision rate of condensable species. A model of silicate grain nucleation and growth was modified to evaluate the effect of a nucleation flux orders of magnitUde below the equilibrium value. The results show that a lack of chemical equilibrium has only a small effect on the ultimate grain distribution.

Spontaneity and Equilibrium: Why "?G Equilibrium" Are Incorrect

Science.gov (United States)

Raff, Lionel M.

2014-01-01

The fundamental criteria for chemical reactions to be spontaneous in a given direction are generally incorrectly stated as ?G equilibrium are also misstated as being ?G = 0 or ?A = 0. Following a brief review of the…

Exploring the Impact of Argumentation on Pre-Service Science Teachers' Conceptual Understanding of Chemical Equilibrium

Science.gov (United States)

Aydeniz, Mehmet; Dogan, Alev

2016-01-01

This study examines the impact of argumentation on pre-service science teachers' (PST) conceptual understanding of chemical equilibrium. The sample consisted of 57 first-year PSTs enrolled in a teacher education program in Turkey. Thirty two of the 57 PSTs who participated in this study were in the experimental group and 25 in the control group.…

Composition of hydrogenation products of Borodino brown coal

Energy Technology Data Exchange (ETDEWEB)

M.A. Gyul' malieva; A.S. Maloletnev; G.A. Kalabin; A.M. Gyul' maliev [Institute for Fossil Fuels, Moscow (Russian Federation)

2008-02-15

The composition of liquid products of hydrogenation of brown coal from the Borodino deposit was determined by means of {sup 13}C NMR spectroscopy and chemical thermodynamics methods. It was shown that the group composition of the liquid hydrogenation products at thermodynamic equilibrium is predictable from the elemental composition of the organic matter of parent coal. 9 refs., 5 figs., 6 tabs.

Selectivity and stoichiometry boosting of beta-cyclodextrin in cationic/anionic surfactant systems: when host-guest equilibrium meets biased aggregation equilibrium.

Science.gov (United States)

Jiang, Lingxiang; Yu, Caifang; Deng, Manli; Jin, Changwen; Wang, Yilin; Yan, Yun; Huang, Jianbin

2010-02-18

Cationic surfactant/anionic surfactant/beta-CD ternary aqueous systems provide a platform for the coexistence of the host-guest (beta-CD/surfactant) equilibrium and the biased aggregation (monomeric/aggregated surfactants) equilibrium. We report here that the interplay between the two equilibria dominates the systems as follows. (1) The biased aggregation equilibrium imposes an apparent selectivity on the host-guest equilibrium, namely, beta-CD has to always selectively bind the major surfactant (molar fraction > 0.5) even if binding constants of beta-CD to the pair of surfactants are quite similar. (2) In return, the host-guest equilibrium amplifies the bias of the aggregation equilibrium, that is, the selective binding partly removes the major surfactant from the aggregates and leaves the aggregate composition approaching the electroneutral mixing stoichiometry. (3) This composition variation enhances electrostatic attractions between oppositely charged surfactant head groups, thus resulting in less-curved aggregates. In particular, the present apparent host-guest selectivity is of remarkably high values, and the selectivity stems from the bias of the aggregation equilibrium rather than the difference in binding constants. Moreover, beta-CD is defined as a "stoichiometry booster" for the whole class of cationic/anionic surfactant systems, which provides an additional degree of freedom to directly adjust aggregate compositions of the systems. The stoichiometry boosting of the compositions can in turn affect or even determine microstructures and macroproperties of the systems.

Ceramic composites by chemical vapor infiltration

International Nuclear Information System (INIS)

Stinton, D.P.

1987-01-01

Composites consisting of silicon carbide matrices reinforced with continuous ceramic fibers are being developed for high-temperature structural applications. Chemical vapor deposition (CVD) techniques are very effective in fabricating composites with high strengths and exceptional fracture toughness. Mechanical properties of infiltrated composites are controlled by the strength of the interfacial bond between the fibers and matrix. This paper describes two CVD techniques and reviews the models being developed to better understand and control the infiltration process

Hot nuclear matter and thermodynamical equilibrium

International Nuclear Information System (INIS)

Borderie, B.; Bacri, C.O.; Dore, D.; Frankland, J.D.; Plagnol, E.; Rivet, M.F.; Tassan-Got, L.

1999-01-01

Quasi-complete events from collisions between 36 Ar and 58 Ni corresponding to vaporized sources have been detected with the multidetector INDRA over the excitation energy range 10 - 28 AMeV. For the first time complete information concerning kinematical properties of emitted particles and chemical composition (mean values but also variances) are derived. Despite the very extreme conditions in which such sources are produced (binary collisions with short reaction times and source life-times), their properties are in agreement with the results of a statistical model including a final state excluded volume interaction and describing a gas of fermions and bosons in thermodynamical equilibrium. (authors)

Remarkable nanoconfinement effects on chemical equilibrium manifested in nucleotide dimerization and H-D exchange reactions.

Science.gov (United States)

Polak, Micha; Rubinovich, Leonid

2011-10-06

Nanoconfinement entropic effects on chemical equilibrium involving a small number of molecules, which we term NCECE, are revealed by two widely diverse types of reactions. Employing statistical-mechanical principles, we show how the NCECE effect stabilizes nucleotide dimerization observed within self-assembled molecular cages. Furthermore, the effect provides the basis for dimerization even under an aqueous environment inside the nanocage. Likewise, the NCECE effect is pertinent to a longstanding issue in astrochemistry, namely the extra deuteration commonly observed for molecules reacting on interstellar dust grain surfaces. The origin of the NCECE effect is elucidated by means of the probability distributions of the reaction extent and related variations in the reactant-product mixing entropy. Theoretical modelling beyond our previous preliminary work highlights the role of the nanospace size in addition to that of the nanosystem size, namely the limited amount of molecules in the reaction mixture. Furthermore, the NCECE effect can depend also on the reaction mechanism, and on deviations from stoichiometry. The NCECE effect, leading to enhanced, greatly variable equilibrium "constants", constitutes a unique physical-chemical phenomenon, distinguished from the usual thermodynamical properties of macroscopically large systems. Being significant particularly for weakly exothermic reactions, the effects should stabilize products in other closed nanoscale structures, and thus can have notable implications for the growing nanotechnological utilization of chemical syntheses conducted within confined nanoreactors.

Passive dosing of polycyclic aromatic hydrocarbon (PAH) mixtures to terrestrial springtails: linking mixture toxicity to chemical activities, equilibrium lipid concentrations, and toxic units.

Science.gov (United States)

Schmidt, Stine N; Holmstrup, Martin; Smith, Kilian E C; Mayer, Philipp

2013-07-02

A 7-day mixture toxicity experiment with the terrestrial springtail Folsomia candida was conducted, and the effects were linked to three different mixture exposure parameters. Passive dosing from silicone was applied to tightly control exposure levels and compositions of 12 mixture treatments, containing the polycyclic aromatic hydrocarbons (PAHs) naphthalene, phenanthrene, and pyrene. Springtail lethality was then linked to sum chemical activities (∑a), sum equilibrium lipid concentrations (∑C(lipid eq.)), and sum toxic units (∑TU). In each case, the effects of all 12 mixture treatments could be fitted to one sigmoidal exposure-response relationship. The effective lethal chemical activity (La50) of 0.027 was well within the expected range for baseline toxicity of 0.01-0.1. Linking the effects to the lipid-based exposure parameter yielded an effective lethal concentration (LC(lipid eq 50)) of 133 mmol kg(-1) lipid in good correspondence with the lethal membrane burden for baseline toxicity (40-160 mmol kg(-1) lipid). Finally, the effective lethal toxic unit (LTU50) of 1.20 was rather close to the expected value of 1. Altogether, passive dosing provided tightly controlled mixture exposure in terms of both level and composition, while ∑a, ∑C(lipid eq.), and ∑TU allowed baseline toxicity to be linked to mixture exposure.

A Simple Method to Calculate the Temperature Dependence of the Gibbs Energy and Chemical Equilibrium Constants

Science.gov (United States)

Vargas, Francisco M.

2014-01-01

The temperature dependence of the Gibbs energy and important quantities such as Henry's law constants, activity coefficients, and chemical equilibrium constants is usually calculated by using the Gibbs-Helmholtz equation. Although, this is a well-known approach and traditionally covered as part of any physical chemistry course, the required…

Some Considerations on the Fundamentals of Chemical Kinetics: Steady State, Quasi-Equilibrium, and Transition State Theory

Science.gov (United States)

Perez-Benito, Joaquin F.

2017-01-01

The elementary reaction sequence A ? I ? Products is the simplest mechanism for which the steady-state and quasi-equilibrium kinetic approximations can be applied. The exact integrated solutions for this chemical system allow inferring the conditions that must fulfill the rate constants for the different approximations to hold. A graphical…

An unstructured shock-fitting solver for hypersonic plasma flows in chemical non-equilibrium

Science.gov (United States)

Pepe, R.; Bonfiglioli, A.; D'Angola, A.; Colonna, G.; Paciorri, R.

2015-11-01

A CFD solver, using Residual Distribution Schemes on unstructured grids, has been extended to deal with inviscid chemical non-equilibrium flows. The conservative equations have been coupled with a kinetic model for argon plasma which includes the argon metastable state as independent species, taking into account electron-atom and atom-atom processes. Results in the case of an hypersonic flow around an infinite cylinder, obtained by using both shock-capturing and shock-fitting approaches, show higher accuracy of the shock-fitting approach.

Chemical composition and antifungal activity of essential oils of ...

African Journals Online (AJOL)

The aim of this study was to determine the chemical composition of the essential oils of Algerian citrus. They were extracted by hydrodistillation from the leaves of citrus species (orange, Bigaradier, mandarin and lemon), using gas chromatography/mass spectrometry (GC/MS). Their chemical composition and antifungal ...

An interactive computer code for calculation of gas-phase chemical equilibrium (EQLBRM)

Science.gov (United States)

Pratt, B. S.; Pratt, D. T.

1984-01-01

A user friendly, menu driven, interactive computer program known as EQLBRM which calculates the adiabatic equilibrium temperature and product composition resulting from the combustion of hydrocarbon fuels with air, at specified constant pressure and enthalpy is discussed. The program is developed primarily as an instructional tool to be run on small computers to allow the user to economically and efficiency explore the effects of varying fuel type, air/fuel ratio, inlet air and/or fuel temperature, and operating pressure on the performance of continuous combustion devices such as gas turbine combustors, Stirling engine burners, and power generation furnaces.

Chemical potential of quasi-equilibrium magnon gas driven by pure spin current.

Science.gov (United States)

Demidov, V E; Urazhdin, S; Divinskiy, B; Bessonov, V D; Rinkevich, A B; Ustinov, V V; Demokritov, S O

2017-11-17

Pure spin currents provide the possibility to control the magnetization state of conducting and insulating magnetic materials. They allow one to increase or reduce the density of magnons, and achieve coherent dynamic states of magnetization reminiscent of the Bose-Einstein condensation. However, until now there was no direct evidence that the state of the magnon gas subjected to spin current can be treated thermodynamically. Here, we show experimentally that the spin current generated by the spin-Hall effect drives the magnon gas into a quasi-equilibrium state that can be described by the Bose-Einstein statistics. The magnon population function is characterized either by an increased effective chemical potential or by a reduced effective temperature, depending on the spin current polarization. In the former case, the chemical potential can closely approach, at large driving currents, the lowest-energy magnon state, indicating the possibility of spin current-driven Bose-Einstein condensation.

General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

Energy Technology Data Exchange (ETDEWEB)

Liu, Yen, E-mail: yen.liu@nasa.gov; Vinokur, Marcel [NASA Ames Research Center, Moffett Field, California 94035 (United States); Panesi, Marco; Sahai, Amal [University of Illinois, Urbana-Champaign, Illinois 61801 (United States)

2015-04-07

This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model’s accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

Science.gov (United States)

Liu, Yen; Panesi, Marco; Sahai, Amal; Vinokur, Marcel

2015-04-01

This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures.

Science.gov (United States)

Liu, Yen; Panesi, Marco; Sahai, Amal; Vinokur, Marcel

2015-04-07

This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model's accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

General multi-group macroscopic modeling for thermo-chemical non-equilibrium gas mixtures

International Nuclear Information System (INIS)

Liu, Yen; Vinokur, Marcel; Panesi, Marco; Sahai, Amal

2015-01-01

This paper opens a new door to macroscopic modeling for thermal and chemical non-equilibrium. In a game-changing approach, we discard conventional theories and practices stemming from the separation of internal energy modes and the Landau-Teller relaxation equation. Instead, we solve the fundamental microscopic equations in their moment forms but seek only optimum representations for the microscopic state distribution function that provides converged and time accurate solutions for certain macroscopic quantities at all times. The modeling makes no ad hoc assumptions or simplifications at the microscopic level and includes all possible collisional and radiative processes; it therefore retains all non-equilibrium fluid physics. We formulate the thermal and chemical non-equilibrium macroscopic equations and rate coefficients in a coupled and unified fashion for gases undergoing completely general transitions. All collisional partners can have internal structures and can change their internal energy states after transitions. The model is based on the reconstruction of the state distribution function. The internal energy space is subdivided into multiple groups in order to better describe non-equilibrium state distributions. The logarithm of the distribution function in each group is expressed as a power series in internal energy based on the maximum entropy principle. The method of weighted residuals is applied to the microscopic equations to obtain macroscopic moment equations and rate coefficients succinctly to any order. The model’s accuracy depends only on the assumed expression of the state distribution function and the number of groups used and can be self-checked for accuracy and convergence. We show that the macroscopic internal energy transfer, similar to mass and momentum transfers, occurs through nonlinear collisional processes and is not a simple relaxation process described by, e.g., the Landau-Teller equation. Unlike the classical vibrational energy

A Metastable Equilibrium Model for the Relative Abundances of Microbial Phyla in a Hot Spring

Science.gov (United States)

Dick, Jeffrey M.; Shock, Everett L.

2013-01-01

Many studies link the compositions of microbial communities to their environments, but the energetics of organism-specific biomass synthesis as a function of geochemical variables have rarely been assessed. We describe a thermodynamic model that integrates geochemical and metagenomic data for biofilms sampled at five sites along a thermal and chemical gradient in the outflow channel of the hot spring known as “Bison Pool” in Yellowstone National Park. The relative abundances of major phyla in individual communities sampled along the outflow channel are modeled by computing metastable equilibrium among model proteins with amino acid compositions derived from metagenomic sequences. Geochemical conditions are represented by temperature and activities of basis species, including pH and oxidation-reduction potential quantified as the activity of dissolved hydrogen. By adjusting the activity of hydrogen, the model can be tuned to closely approximate the relative abundances of the phyla observed in the community profiles generated from BLAST assignments. The findings reveal an inverse relationship between the energy demand to form the proteins at equal thermodynamic activities and the abundance of phyla in the community. The distance from metastable equilibrium of the communities, assessed using an equation derived from energetic considerations that is also consistent with the information-theoretic entropy change, decreases along the outflow channel. Specific divergences from metastable equilibrium, such as an underprediction of the relative abundances of phototrophic organisms at lower temperatures, can be explained by considering additional sources of energy and/or differences in growth efficiency. Although the metabolisms used by many members of these communities are driven by chemical disequilibria, the results support the possibility that higher-level patterns of chemotrophic microbial ecosystems are shaped by metastable equilibrium states that depend on both the

Viscous-shock-layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

Science.gov (United States)

Anderson, E. C.; Moss, J. N.

1975-01-01

The viscous-shock-layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially-symmetric flow fields. Solutions were obtained using an implicit finite-difference scheme and results are presented for hypersonic flow over spherically-blunted cone configurations at freestream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

Viscous shock layer solutions for turbulent flow of radiating gas mixtures in chemical equilibrium

Science.gov (United States)

Anderson, E. C.; Moss, J. N.

1975-01-01

The viscous shock layer equations for hypersonic laminar and turbulent flows of radiating or nonradiating gas mixtures in chemical equilibrium are presented for two-dimensional and axially symmetric flow fields. Solutions are obtained using an implicit finite difference scheme and results are presented for hypersonic flow over spherically blunted cone configurations at free stream conditions representative of entry into the atmosphere of Venus. These data are compared with solutions obtained using other methods of analysis.

Characterization of the conformational equilibrium between the two major substates of RNase A using NMR chemical shifts.

Science.gov (United States)

Camilloni, Carlo; Robustelli, Paul; De Simone, Alfonso; Cavalli, Andrea; Vendruscolo, Michele

2012-03-07

Following the recognition that NMR chemical shifts can be used for protein structure determination, rapid advances have recently been made in methods for extending this strategy for proteins and protein complexes of increasing size and complexity. A remaining major challenge is to develop approaches to exploit the information contained in the chemical shifts about conformational fluctuations in native states of proteins. In this work we show that it is possible to determine an ensemble of conformations representing the free energy surface of RNase A using chemical shifts as replica-averaged restraints in molecular dynamics simulations. Analysis of this surface indicates that chemical shifts can be used to characterize the conformational equilibrium between the two major substates of this protein. © 2012 American Chemical Society

Candidates Profile in FUVEST Exams from 2004 to 2013: Private and Public School Distribution, FUVEST Average Performance and Chemical Equilibrium Tasks Performance

Directory of Open Access Journals (Sweden)

R.S.A.P. Oliveira

2014-08-01

Full Text Available INTRODUCTION. Chemical equilibrium is recognized as a topic of several misconceptions. Its origins must be tracked from previous scholarship. Its impact on biochemistry learning is not fully described. A possible bulk of data is the FUVEST exam. OBJECTIVES: Identify students’ errors profile on chemical equilibrium tasks using public data from FUVEST exam. MATERIAL AND METHODS: Data analysis from FUVEST were: i Private and Public school distribution in Elementary and Middle School, and High School candidates of Pharmacy-Biochemistry course and total USP careers until the last call for enrollment (2004-2013; ii Average performance in 1st and 2nd parts of FUVEST exam of Pharmacy-Biochemistry, Chemistry, Engineering, Biological Sciences, Languages and Medicine courses and total enrolled candidates until 1st call for enrollment (2008- 2013; iii Performance of candidates of Pharmacy-Biochemistry, Chemistry, Engineering, Biological Sciences, Languages and Medicine courses and total USP careers in chemical equilibrium issues from 1st part of FUVEST (2011-2013. RESULTS AND DISCUSSION: i 66.2% of candidates came from private Elementary-Middle School courses and 71.8%, came from High School courses; ii Average grade over the period for 1st and 2nd FUVEST parts are respectively (in 100 points: Pharmacy-Biochemistry 66.7 and 61.2, Chemistry 65.9 and 58.9, Engineering 75.9 and 71.9, Biological Sciences 65.6 and 54.6, Languages 49.9 and 43.3, Medicine 83.5 and 79.5, total enrolled candidates 51,5 and 48.9; iii Four chemical equilibrium issues were found during 2011-2013 and the analysis of multiplechoice percentage distribution over the courses showed that there was a similar performance of students among them, except for Engineering and Medicine with higher grades, but the same proportional distribution among choices. CONCLUSION: Approved students came majorly from private schools. There was a different average performance among courses and similar on

The Effectiveness of Conceptual Change Texts in Remediating High School Students' Alternative Conceptions Concerning Chemical Equilibrium

Science.gov (United States)

Ozmen, Haluk

2007-01-01

This study investigated the effectiveness of conceptual change texts in remediating high school students' alternative conceptions concerning chemical equilibrium. A quasi-experimental design was used in this study. The subjects for this study consisted of a total 78 tenth-grade students, 38 of them in the experimental group and 40 of them in the…

Determination of Students' Alternative Conceptions about Chemical Equilibrium: A Review of Research and the Case of Turkey

Science.gov (United States)

Ozmen, Haluk

2008-01-01

This study aims to determine prospective science student teachers' alternative conceptions of the chemical equilibrium concept. A 13-item pencil and paper, two-tier multiple choice diagnostic instrument, the Test to Identify Students' Alternative Conceptions (TISAC), was developed and administered to 90 second-semester science student teachers…

Evaluation of chemical composition of defect wine distillates

OpenAIRE

Mihaljević Žulj, Marin; Posavec, Barbara; Škvorc, Melanija; Tupajić, Pavica

2016-01-01

The aim of this study was to evaluate the chemical composition of the distillate obtained from wine with off-flavour. The chemical composition of wine distillates obtained by distillation of Chardonnay wine with oxidation off-flavour was investigated. Distillation of wine was carried out using a simple distillation pot still by double distillation and separation the different portion of the first fraction. Volatile compounds of wine and wine distillates (acetaldehyde, ethyl acetate, methanol ...

Equilibrium sampling of environmental pollutants in fish: comparison with lipid-normalized concentrations and homogenization effects on chemical activity.

Science.gov (United States)

Jahnke, Annika; Mayer, Philipp; Adolfsson-Erici, Margaretha; McLachlan, Michael S

2011-07-01

Equilibrium sampling of organic pollutants into the silicone polydimethylsiloxane (PDMS) has recently been applied in biological tissues including fish. Pollutant concentrations in PDMS can then be multiplied with lipid/PDMS distribution coefficients (D(Lipid,PDMS) ) to obtain concentrations in fish lipids. In the present study, PDMS thin films were used for equilibrium sampling of polychlorinated biphenyls (PCBs) in intact tissue of two eels and one salmon. A classical exhaustive extraction technique to determine lipid-normalized PCB concentrations, which assigns the body burden of the chemical to the lipid fraction of the fish, was additionally applied. Lipid-based PCB concentrations obtained by equilibrium sampling were 85 to 106% (Norwegian Atlantic salmon), 108 to 128% (Baltic Sea eel), and 51 to 83% (Finnish lake eel) of those determined using total extraction. This supports the validity of the equilibrium sampling technique, while at the same time confirming that the fugacity capacity of these lipid-rich tissues for PCBs was dominated by the lipid fraction. Equilibrium sampling was also applied to homogenates of the same fish tissues. The PCB concentrations in the PDMS were 1.2 to 2.0 times higher in the homogenates (statistically significant in 18 of 21 cases, p equilibrium sampling and partition coefficients determined using tissue homogenates. Copyright © 2011 SETAC.

Predictions of the product compositions for combustion or gasification of biomass and others hydrocarbons

Energy Technology Data Exchange (ETDEWEB)

Rocha, Hendrick Maxil Zarate; Itai, Yuu; Nogueira, Manoel Fernandes Martins; Moraes, Sinfronio Brito; Rocha, Brigida Ramati Pereira da [Universidade Federal do Para (UFPA), Belem, PA (Brazil). Faculdade de Engenharia Mecanica]. E-mails: hendrick@ufpa.br; yuuitai@ufpa.br; mfmn@ufpa.br; sbrito@ufpa.br; brigida@ufpa.br

2008-07-01

Processes involving combustion and gasification are object of study of many researchers. To simulate these processes in a detailed way, it is necessary to solve equations for chemical kinetics whose resolution many times is difficult due lack of information in the literature a simples way to bypass tis problem is due the chemical equilibrium. Prediction of the flu gases composition through chemical equilibrium is an important step in the mathematical modelling for gasification and combustion processes. Some free programs exists to solve problems that involve the chemical equilibrium, such as STANJAN, CEA, GASEQ, CANTERA and others.These programs have difficulty for cases involving fuel such as: biomass, vegetable oils, biodiesel, natural gas, etc., because they do not have database with the fuel composition and is hard to supply their HHV and their elementary analysis. In this work, using numeric methods, a program was developed to predict the gases composition on equilibrium after combustion and gasification processes with the for constant pressure or volume. In the program the chemical formula of the fuel is defined as C{sub x}H{sub y}O{sub z}N{sub w}S{sub v}A{sub u} that reacts with an gaseous oxidizer composed by O{sub 2}, N{sub 2}, Ar, He, CO{sub 2} e H{sub 2}O to have as final result the composition of the products CO{sub 2}, CO, H{sub 2}O, H{sub 2}, H, OH, O{sub 2}, O, N{sub 2}, NO, SO{sub 2}, CH{sub 4}, Ar, He, and ash. To verify the accuracy of the calculated values, it was compared with the program CEA (developed by NASA) and with experimental data obtained from literature. (author)

Non-equilibrium synergistic effects in atmospheric pressure plasmas.

Science.gov (United States)

Guo, Heng; Zhang, Xiao-Ning; Chen, Jian; Li, He-Ping; Ostrikov, Kostya Ken

2018-03-19

Non-equilibrium is one of the important features of an atmospheric gas discharge plasma. It involves complicated physical-chemical processes and plays a key role in various actual plasma processing. In this report, a novel complete non-equilibrium model is developed to reveal the non-equilibrium synergistic effects for the atmospheric-pressure low-temperature plasmas (AP-LTPs). It combines a thermal-chemical non-equilibrium fluid model for the quasi-neutral plasma region and a simplified sheath model for the electrode sheath region. The free-burning argon arc is selected as a model system because both the electrical-thermal-chemical equilibrium and non-equilibrium regions are involved simultaneously in this arc plasma system. The modeling results indicate for the first time that it is the strong and synergistic interactions among the mass, momentum and energy transfer processes that determine the self-consistent non-equilibrium characteristics of the AP-LTPs. An energy transfer process related to the non-uniform spatial distributions of the electron-to-heavy-particle temperature ratio has also been discovered for the first time. It has a significant influence for self-consistently predicting the transition region between the "hot" and "cold" equilibrium regions of an AP-LTP system. The modeling results would provide an instructive guidance for predicting and possibly controlling the non-equilibrium particle-energy transportation process in various AP-LTPs in future.

Foundations of atmospheric pressure non-equilibrium plasmas

Science.gov (United States)

Bruggeman, Peter J.; Iza, Felipe; Brandenburg, Ronny

2017-12-01

Non-equilibrium plasmas have been intensively studied over the past century in the context of material processing, environmental remediation, ozone generation, excimer lamps and plasma display panels. Research on atmospheric pressure non-equilibrium plasmas intensified over the last two decades leading to a large variety of plasma sources that have been developed for an extended application range including chemical conversion, medicine, chemical analysis and disinfection. The fundamental understanding of these discharges is emerging but there remain a lot of unexplained phenomena in these intrinsically complex plasmas. The properties of non-equilibrium plasmas at atmospheric pressure span over a huge range of electron densities as well as heavy particle and electron temperatures. This paper provides an overview of the key underlying processes that are important for the generation and stabilization of atmospheric pressure non-equilibrium plasmas. The unique physical and chemical properties of theses discharges are also summarized.

Kinetics and equilibrium studies for sorption of Cu (II) and Cr (VI) ions onto polymeric composite resins

International Nuclear Information System (INIS)

El-Zahhhar, A.A.; Abdel-Aziz, H.M.; Siyam, T.

2005-01-01

The sorption behavior of Cu (II) and Cr (VI) ions from aqueous solutions was studied using polymeric composite resins. Batch sorption experiments were performed as a function of hydrogen ion concentration, complexing agent concentration, resin weight and ionic strength. Kinetic parameters as a function of initial ion concentration were determined to predict the sorption behavior of Cu (II) and Cr (VI) onto polymeric composite resins. The equilibrium data could be fitted by the frendlich adsorption isotherm equation

Thermodynamic Simulation of Equilibrium Composition of Reaction Products at Dehydration of a Technological Channel in a Uranium-Graphite Reactor

Science.gov (United States)

Pavliuk, A. O.; Zagumennov, V. S.; Kotlyarevskiy, S. G.; Bespala, E. V.

2018-01-01

The problems of accumulation of nuclear fuel spills in the graphite stack in the course of operation of uranium-graphite nuclear reactors are considered. The results of thermodynamic analysis of the processes in the graphite stack at dehydration of a technological channel, fuel element shell unsealing and migration of fission products, and activation of stable nuclides in structural elements of the reactor and actinides inside the graphite moderator are given. The main chemical reactions and compounds that are produced in these modes in the reactor channel during its operation and that may be hazardous after its shutdown and decommissioning are presented. Thermodynamic simulation of the equilibrium composition is performed using the specialized code TERRA. The results of thermodynamic simulation of the equilibrium composition in different cases of technological channel dehydration in the course of the reactor operation show that, if the temperature inside the active core of the nuclear reactor increases to the melting temperature of the fuel element, oxides and carbides of nuclear fuel are produced. The mathematical model of the nonstationary heat transfer in a graphite stack of a uranium-graphite reactor in the case of the technological channel dehydration is presented. The results of calculated temperature evolution at the center of the fuel element, the replaceable graphite element, the air gap, and in the surface layer of the block graphite are given. The numerical results show that, in the case of dehydration of the technological channel in the uranium-graphite reactor with metallic uranium, the main reaction product is uranium dioxide UO2 in the condensed phase. Low probability of production of pyrophoric uranium compounds (UH3) in the graphite stack is proven, which allows one to disassemble the graphite stack without the risk of spontaneous graphite ignition in the course of decommissioning of the uranium-graphite nuclear reactor.

A new material for chemical industry - wood polymer composites

International Nuclear Information System (INIS)

Majali, A.B.; Patil, N.D.

1979-01-01

The paper outlines the advantages of the radiation cured wood-polymer composites (WPC) for application in certain critical areas of chemical industry. The wood-polymer composite made filterpress frames and plates were tested in a chemical plant. The entire exercise is elaborated. The radiation cured wood exhibited a considerably extended useful life in alkaline and acidic solutions. Composites based on teak wood showed a remarkable improvement with a nominal polymer loading of 10%. The reports of accelerated aging test of WPC are also presented. (auth.)

An improved flux-split algorithm applied to hypersonic flows in chemical equilibrium

Science.gov (United States)

Palmer, Grant

1988-01-01

An explicit, finite-difference, shock-capturing numerical algorithm is presented and applied to hypersonic flows assumed to be in thermochemical equilibrium. Real-gas chemistry is either loosely coupled to the gasdynamics by way of a Gibbs free energy minimization package or fully coupled using species mass conservation equations with finite-rate chemical reactions. A scheme is developed that maintains stability in the explicit, finite-rate formulation while allowing relatively high time steps. The codes use flux vector splitting to difference the inviscid fluxes and employ real-gas corrections to viscosity and thermal conductivity. Numerical results are compared against existing ballistic range and flight data. Flows about complex geometries are also computed.

Chemical factors controlling actinide sorption in the environment

International Nuclear Information System (INIS)

Beall, G.W.; Allard, B.

1979-01-01

The solid geologic media and the aqueous phase are of equal importance for the retention of actinides in the environment. The composition of the water is largely determined by the mineralogical composition of the rock that it is in equilibrium with. The chemical form of the actinides and their sorption, are highly dependent on the composition of the water with respect to pH, redox potential, and concentration of anions like carbonate, phosphate, fluoride, and organic acids

Spontaneity and Equilibrium: Why "?G Equilibrium" Are Incorrect

Science.gov (United States)

Raff, Lionel M.

2014-01-01

The fundamental criteria for chemical reactions to be spontaneous in a given direction are generally incorrectly stated as ?G chemistry textbooks and even in some more advanced texts. Similarly, the criteria for equilibrium are also misstated as being ?G = 0 or ?A = 0. Following a brief review of the…

Comparative Analysis on Chemical Composition of Bentonite Clays ...

African Journals Online (AJOL)

2017-09-12

Sep 12, 2017 ... Comparative Analysis on Chemical Composition of Bentonite Clays. Obtained from Ashaka and ... versatile material for geotechnical engineering and as well as their demand for ..... A PhD thesis submitted to the Chemical ...

Effect of temperature on a free energy and equilibrium constants during dry flue gas desulphurisation chemical reactions

Directory of Open Access Journals (Sweden)

Kuburović Miloš

2002-01-01

Full Text Available During dry flue gas desulphurisation (FGD dry particles of reagents are inserted (injected in the stream of flue gas, where they bond SO2. As reagents, the most often are used compounds of calcium (CaCO3, CaO or Ca(OH2. Knowledge of free energy and equilibrium constants of chemical reactions during dry FGD is necessary for understanding of influence of flue gas temperature to course of these chemical reactions as well as to SO2 bonding from flue gases.

Chemical composition of Pechora Sea crude oil

Directory of Open Access Journals (Sweden)

Derkach S. R.

2017-03-01

Full Text Available The physicochemical properties of the Pechora Sea shelf oil and its chemical composition have been studied using the methods of refractometry, titrimetry, viscometry, rheometry and standard methods for the analysis of oil and petroleum products. The fractionation of oil is held at atmospheric pressure, some fractions boiling at the temperature below and above 211 °C have been received. Chemical structural-group composition of oil and its components has been investigated using a Fourier infrared (IR spectroscopy method. The density of oil has been obtained, it is equal to 24.2 API. The chemical composition analysis shows that water content in the investigated oil sample is about 0.03 % (by weight. The oil sample contains hydrocarbons (including alkanes, naphthenes, arenes and asphaltenes with resins; their content is equal to 89 and 10 % (by weight respectively. Alkane content is about 66 %, including alkanes of normal structure – about 37 %. The solidification temperature of oil sample is equal to –43 °C. This low temperature testifies obliquely low content of solid alkanes (paraffin. Bearing in mind the content of asphaltenes with resins we can refer the investigated oil sample to resinous oils. On the other hand spectral coefficient values (aromaticity quotient and aliphaticity quotient show that oil sample belongs to naphthenic oils. According to the data of Fourier IR spectroscopy contents of naphthenes and arenes are 5.9 and 17.8 % respectively. Thus, the obtained data of chemical structural-group composition of crude oil and its fractions indicate that this oil belongs to the heavy resinous naphthenic oils. The rheological parameters obtained at the shear deformation conditions characterize the crude oil as a visco-plastic medium.

Chemical kinetics and relaxation of non-equilibrium air plasma generated by energetic photon and electron beams

International Nuclear Information System (INIS)

Maulois, Melissa; Ribière, Maxime; Eichwald, Olivier; Yousfi, Mohammed; Azaïs, Bruno

2016-01-01

The comprehension of electromagnetic perturbations of electronic devices, due to air plasma-induced electromagnetic field, requires a thorough study on air plasma. In the aim to understand the phenomena at the origin of the formation of non-equilibrium air plasma, we simulate, using a volume average chemical kinetics model (0D model), the time evolution of a non-equilibrium air plasma generated by an energetic X-ray flash. The simulation is undertaken in synthetic air (80% N_2 and 20% O_2) at ambient temperature and atmospheric pressure. When the X-ray flash crosses the gas, non-relativistic Compton electrons (low energy) and a relativistic Compton electron beam (high energy) are simultaneously generated and interact with the gas. The considered chemical kinetics scheme involves 26 influent species (electrons, positive ions, negative ions, and neutral atoms and molecules in their ground or metastable excited states) reacting following 164 selected reactions. The kinetics model describing the plasma chemistry was coupled to the conservation equation of the electron mean energy, in order to calculate at each time step of the non-equilibrium plasma evolution, the coefficients of reactions involving electrons while the energy of the heavy species (positive and negative ions and neutral atoms and molecules) is assumed remaining close to ambient temperature. It has been shown that it is the relativistic Compton electron beam directly created by the X-ray flash which is mainly responsible for the non-equilibrium plasma formation. Indeed, the low energy electrons (i.e., the non-relativistic ones) directly ejected from molecules by Compton collisions contribute to less than 1% on the creation of electrons in the plasma. In our simulation conditions, a non-equilibrium plasma with a low electron mean energy close to 1 eV and a concentration of charged species close to 10"1"3" cm"−"3 is formed a few nanoseconds after the peak of X-ray flash intensity. 200 ns after the

Mathematical modeling of the radiation-chemical behavior of neptunium in HNO3. Equilibrium states

International Nuclear Information System (INIS)

Vladimirova, M.V.

1995-01-01

A mathematical model of the radiation-chemical behavior of neptunium is presented for a wide range of α-and γ-irradiation doses. Equations determining the equilibrium concentrations of NP(IV), Np(V), and Np(VI) are derived for various concentrations of HNO 3 and dose rates of the ionizing irradiation. The rate constants of the reactions NP(IV) + OH, Np(IV) + NO 3 , Np(V) + NO 2 , Np(V) + H, Np(IV), and Np(V) + Np(V) are obtained by the mathematical modeling

State-to-state modeling of non-equilibrium air nozzle flows

Science.gov (United States)

Nagnibeda, E.; Papina, K.; Kunova, O.

2018-05-01

One-dimensional non-equilibrium air flows in nozzles are studied on the basis of the state-to-state description of vibrational-chemical kinetics. Five-component mixture N2/O2/NO/N/O is considered taking into account Zeldovich exchange reactions of NO formation, dissociation, recombination and vibrational energy transitions. The equations for vibrational and chem-ical kinetics in a flow are coupled to the conservation equations of momentum and total energy and solved numerically for different conditions in a nozzle throat. The vibrational distributions of nitrogen and oxygen molecules, number densities of species as well as the gas temperature and flow velocity along a nozzle axis are analysed using the detailed state-to-state flow description and in the frame of the simplified one-temperature thermal equilibrium kinetic model. The comparison of the results showed the influence of non-equilibrium kinetics on macroscopic nozzle flow parameters. In the state-to-state approach, non-Boltzmann vibrational dis-tributions of N2 and O2 molecules with a plateau part at intermediate levels are found. The results are found with the use of the complete and simplified schemes of reactions and the impact of exchange reactions, dissociation and recombination on variation of vibrational level populations, mixture composition, gas velocity and temperature along a nozzle axis is shown.

The Effect of Context-Based Chemical Equilibrium on Grade 11 Students' Learning, Motivation and Constructivist Learning Environment

Science.gov (United States)

ilhan, Nail; Yildirim, Ali; Yilmaz, Sibel Sadi

2016-01-01

In recent years, many countries have adopted a context-based approach for designing science curricula for education at all levels. The aim of this study was to determine the effectiveness of a Context-Based Chemistry Course (CBCC) as compared with traditional/existing instruction, on 11th grade students' learning about chemical equilibrium,…

Determination of the chemical composition, the physicochemical ...

African Journals Online (AJOL)

The chemical composition of the seed of Telfairia occidentalis (fluted pumpkin), the physicochemical properties of the seed oil and the amino acids profiles of the seed protein have been determined. In proximate composition, the crude fat content of 58.41% indicates that the plant seed is an oil seed. Its protein content of ...

An ab initio chemical reaction model for the direct simulation Monte Carlo study of non-equilibrium nitrogen flows.

Science.gov (United States)

Mankodi, T K; Bhandarkar, U V; Puranik, B P

2017-08-28

A new ab initio based chemical model for a Direct Simulation Monte Carlo (DSMC) study suitable for simulating rarefied flows with a high degree of non-equilibrium is presented. To this end, Collision Induced Dissociation (CID) cross sections for N 2 +N 2 →N 2 +2N are calculated and published using a global complete active space self-consistent field-complete active space second order perturbation theory N 4 potential energy surface and quasi-classical trajectory algorithm for high energy collisions (up to 30 eV). CID cross sections are calculated for only a selected set of ro-vibrational combinations of the two nitrogen molecules, and a fitting scheme based on spectroscopic weights is presented to interpolate the CID cross section for all possible ro-vibrational combinations. The new chemical model is validated by calculating equilibrium reaction rate coefficients that can be compared well with existing shock tube and computational results. High-enthalpy hypersonic nitrogen flows around a cylinder in the transition flow regime are simulated using DSMC to compare the predictions of the current ab initio based chemical model with the prevailing phenomenological model (the total collision energy model). The differences in the predictions are discussed.

Study and interpretation of the chemical characteristics of natural water

Science.gov (United States)

Hem, John David

1985-01-01

The chemical composition of natural water is derived from many different sources of solutes, including gases and aerosols from the atmosphere, weathering and erosion of rocks and soil, solution or precipitation reactions occurring below the land surface, and cultural effects resulting from human activities. Broad interrelationships among these processes and their effects can be discerned by application of principles of chemical thermodynamics. Some of the processes of solution or precipitation of minerals can be closely evaluated by means of principles of chemical equilibrium, including the law of mass action and the Nernst equation. Other processes are irreversible and require consideration of reaction mechanisms and rates. The chemical composition of the crustal rocks of the Earth and the composition of the ocean and the atmosphere are significant in evaluating sources of solutes in natural freshwater.

Equilibrium statistical mechanics

CERN Document Server

Mayer, J E

1968-01-01

The International Encyclopedia of Physical Chemistry and Chemical Physics, Volume 1: Equilibrium Statistical Mechanics covers the fundamental principles and the development of theoretical aspects of equilibrium statistical mechanics. Statistical mechanical is the study of the connection between the macroscopic behavior of bulk matter and the microscopic properties of its constituent atoms and molecules. This book contains eight chapters, and begins with a presentation of the master equation used for the calculation of the fundamental thermodynamic functions. The succeeding chapters highlight t

Fabrication of Cf/SiC composite by chemical vapor infiltration

International Nuclear Information System (INIS)

Park, Ji Yeon; Kim, Weon Ju

2003-07-01

This technical report reviewed the fabrication process of fiber reinforced ceramic composites, characteristics of the chemical vapor infiltration process, and applications for C f /SiC composite to develop a carbon fiber reinforced silicon carbide composite. Infiltration process was performed by the chemical vapor infiltration process using methyltrichlorosilane and hydrogen gas as a source and a diluent, respectively. Infiltration behavior, phase analysis, microstructure observation were carried out. Parameter study results of C f /SiC composite fabricated with some variables such as reaction pressure, reaction temperature, input gas ratio and preform thickness were described

Chemical composition, antioxidant effects and antimicrobial ...

African Journals Online (AJOL)

Thymus vulgaris, Cinnamomum zeylanicum and Ocimum gratissimum are spices widely used as aroma enhancers and food preservatives. This work assessed the chemical composition, antioxidant and antimicrobial effect of their essential oils on some food pathogenic bacteria, namely, Staphylococcus aureus, Citrobacter ...

Chemical vapor deposited fiber coatings and chemical vapor infiltrated ceramic matrix composites

Energy Technology Data Exchange (ETDEWEB)

Kmetz, M.A.

1992-01-01

Conventional Chemical Vapor Deposition (CVD) and Organometallic Chemical Vapor Deposition (MOCVD) were employed to deposit a series of interfacial coatings on SiC and carbon yarn. Molybdenum, tungsten and chromium hexacarbonyls were utilized as precursors in a low temperature (350[degrees]C) MOCVD process to coat SiC yarn with Mo, W and Cr oxycarbides. Annealing studies performed on the MoOC and WOC coated SiC yarns in N[sub 2] to 1,000[degrees]C establish that further decomposition of the oxycarbides occurred, culminating in the formation of the metals. These metals were then found to react with Si to form Mo and W disilicide coatings. In the Cr system, heating in N[sub 2] above 800[degrees]C resulted in the formation of a mixture of carbides and oxides. Convention CVD was also employed to coat SiC and carbon yarn with C, Bn and a new interface designated BC (a carbon-boron alloy). The coated tows were then infiltrated with SiC, TiO[sub 2], SiO[sub 2] and B[sub 4]C by a chemical vapor infiltration process. The B-C coatings were found to provide advantageous interfacial properties over carbon and BN coatings in several different composite systems. The effectiveness of these different coatings to act as a chemically inert barrier layer and their relationship to the degree of interfacial debonding on the mechanical properties of the composites were examined. The effects of thermal stability and strength of the coated fibers and composites were also determined for several difference atmospheres. In addition, a new method for determining the tensile strength of the as-received and coated yarns was also developed. The coated fibers and composites were further characterized by AES, SEM, XPS, IR and X-ray diffraction analysis.

On generalized operator quasi-equilibrium problems

Science.gov (United States)

Kum, Sangho; Kim, Won Kyu

2008-09-01

In this paper, we will introduce the generalized operator equilibrium problem and generalized operator quasi-equilibrium problem which generalize the operator equilibrium problem due to Kazmi and Raouf [K.R. Kazmi, A. Raouf, A class of operator equilibrium problems, J. Math. Anal. Appl. 308 (2005) 554-564] into multi-valued and quasi-equilibrium problems. Using a Fan-Browder type fixed point theorem in [S. Park, Foundations of the KKM theory via coincidences of composites of upper semicontinuous maps, J. Korean Math. Soc. 31 (1994) 493-519] and an existence theorem of equilibrium for 1-person game in [X.-P. Ding, W.K. Kim, K.-K. Tan, Equilibria of non-compact generalized games with L*-majorized preferences, J. Math. Anal. Appl. 164 (1992) 508-517] as basic tools, we prove new existence theorems on generalized operator equilibrium problem and generalized operator quasi-equilibrium problem which includes operator equilibrium problems.

Chemical microsensors based on polymer fiber composites

Science.gov (United States)

Kessick, Royal F.; Levit, Natalia; Tepper, Gary C.

2005-05-01

There is an urgent need for new chemical sensors for defense and security applications. In particular, sensors are required that can provide higher sensitivity and faster response in the field than existing baseline technologies. We have been developing a new solid-state chemical sensor technology based on microscale polymer composite fiber arrays. The fibers consist of an insulating polymer doped with conducting particles and are electrospun directly onto the surface of an interdigitated microelectrode. The concentration of the conducting particles within the fiber is controlled and is near the percolation threshold. Thus, the electrical resistance of the polymer fiber composite is very sensitive to volumetric changes produced in the polymer by vapor absorption. Preliminary results are presented on the fabrication and testing of the new microsensor. The objective is to take advantage of the very high surface to volume ratio, low thermal mass and linear geometry of the composite fibers to produce sensors exhibiting an extremely high vapor sensitivity and rapid response. The simplicity and low cost of a resistance-based chemical microsensor makes this sensing approach an attractive alternative to devices requiring RF electronics or time-of-flight analysis. Potential applications of this technology include battlespace awareness, homeland security, environmental surveillance, medical diagnostics and food process monitoring.

[Bioinorganic chemical composition of the lens and methods of its investigation].

Science.gov (United States)

Avetisov, S E; Novikov, I A; Pakhomova, N A; Motalov, V G

2018-01-01

Bioinorganic chemical composition of the lens of human and experimental animals (cows, dogs, rats, rabbits) have been analyzed in various studies. In most cases, the studies employed different methods to determine the gross (total) composition of chemical elements and their concentrations in the examined samples. Less frequently, they included an assessment of the distribution of chemical elements in the lens and correlation of their concentration with its morphological changes. Chemical elements from all groups (series) of the periodic classification system were discovered in the lens substance. Despite similar investigation methods, different authors obtained contradicting results on the chemical composition of the lens. This article presents data suggesting possible correlation between inorganic chemical elements in the lens substance with the development and formation of lenticular opacities. All currently employed methods are known to only analyze limited number of select chemical elements in the tissues and do not consider the whole range of elements that can be analyzed with existing technology; furthermore, the majority of studies are conducted on the animal model lens. Therefore, it is feasible to continue the development of the chemical microanalysis method by increasing the sensitivity of Scanning Electron Microscopy with Energy Dispersive Spectroscopy (SEM/EDS) with the purpose of assessing the gross chemical composition and distribution of the elements in the lens substance, as well as revealing possible correlation between element concentration and morphological changes in the lens.

Copper adsorption on magnetite-loaded chitosan microspheres: A kinetic and equilibrium study

Energy Technology Data Exchange (ETDEWEB)

Podzus, P.E., E-mail: ppodzus@gmail.com [Grupo de Aplicaciones de Materiales Biocompatibles, Departamento de Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Paseo Colon 850, C1063ACV Buenos Aires (Argentina); Debandi, M.V. [Grupo de Aplicaciones de Materiales Biocompatibles, Departamento de Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Paseo Colon 850, C1063ACV Buenos Aires (Argentina); Daraio, M.E., E-mail: medit@fi.uba.ar [Grupo de Aplicaciones de Materiales Biocompatibles, Departamento de Quimica, Facultad de Ingenieria, Universidad de Buenos Aires, Paseo Colon 850, C1063ACV Buenos Aires (Argentina)

2012-08-15

A composite of Fe{sub 3}O{sub 4} nanoparticles and the biopolymer chitosan, chemically crosslinked, was prepared as microspheres and used to adsorb copper ions, which were chosen as a model of contaminant metal in water. The adsorption of copper on the magnetic microspheres was studied in a batch process, with different aqueous solutions of Cu (II) at concentrations ranging from 40 to 1100 ppm. Kinetic and equilibrium aspects of the adsorption process were studied. The time-dependent Cu (II) adsorption data were well described by a pseudo-second-order kinetic model. It was found that the equilibrium data follow the Langmuir isotherm, with a maximum adsorption capacity of around 500 mg Cu/g chitosan. The used microspheres were removed and after desorption the material was able to be reused as an adsorbent. The prepared microspheres proved efficient in the removal of copper ions through an adsorption process whose kinetic and equilibrium characteristics were analyzed.

Copper adsorption on magnetite-loaded chitosan microspheres: A kinetic and equilibrium study

International Nuclear Information System (INIS)

Podzus, P.E.; Debandi, M.V.; Daraio, M.E.

2012-01-01

A composite of Fe 3 O 4 nanoparticles and the biopolymer chitosan, chemically crosslinked, was prepared as microspheres and used to adsorb copper ions, which were chosen as a model of contaminant metal in water. The adsorption of copper on the magnetic microspheres was studied in a batch process, with different aqueous solutions of Cu (II) at concentrations ranging from 40 to 1100 ppm. Kinetic and equilibrium aspects of the adsorption process were studied. The time-dependent Cu (II) adsorption data were well described by a pseudo-second-order kinetic model. It was found that the equilibrium data follow the Langmuir isotherm, with a maximum adsorption capacity of around 500 mg Cu/g chitosan. The used microspheres were removed and after desorption the material was able to be reused as an adsorbent. The prepared microspheres proved efficient in the removal of copper ions through an adsorption process whose kinetic and equilibrium characteristics were analyzed.

Modelling Chemical Equilibrium Partitioning with the GEMS-PSI Code

Energy Technology Data Exchange (ETDEWEB)

Kulik, D.; Berner, U.; Curti, E

2004-03-01

Sorption, co-precipitation and re-crystallisation are important retention processes for dissolved contaminants (radionuclides) migrating through the sub-surface. The retention of elements is usually measured by empirical partition coefficients (Kd), which vary in response to many factors: temperature, solid/liquid ratio, total contaminant loading, water composition, host-mineral composition, etc. The Kd values can be predicted for in-situ conditions from thermodynamic modelling of solid solution, aqueous solution or sorption equilibria, provided that stoichiometry, thermodynamic stability and mixing properties of the pure components are known (Example 1). Unknown thermodynamic properties can be retrieved from experimental Kd values using inverse modelling techniques (Example 2). An efficient, advanced tool for performing both tasks is the Gibbs Energy Minimization (GEM) approach, implemented in the user-friendly GEM-Selector (GEMS) program package, which includes the Nagra-PSI chemical thermodynamic database. The package is being further developed at PSI and used extensively in studies relating to nuclear waste disposal. (author)

Modelling Chemical Equilibrium Partitioning with the GEMS-PSI Code

International Nuclear Information System (INIS)

Kulik, D.; Berner, U.; Curti, E.

2004-01-01

Sorption, co-precipitation and re-crystallisation are important retention processes for dissolved contaminants (radionuclides) migrating through the sub-surface. The retention of elements is usually measured by empirical partition coefficients (Kd), which vary in response to many factors: temperature, solid/liquid ratio, total contaminant loading, water composition, host-mineral composition, etc. The Kd values can be predicted for in-situ conditions from thermodynamic modelling of solid solution, aqueous solution or sorption equilibria, provided that stoichiometry, thermodynamic stability and mixing properties of the pure components are known (Example 1). Unknown thermodynamic properties can be retrieved from experimental Kd values using inverse modelling techniques (Example 2). An efficient, advanced tool for performing both tasks is the Gibbs Energy Minimization (GEM) approach, implemented in the user-friendly GEM-Selector (GEMS) program package, which includes the Nagra-PSI chemical thermodynamic database. The package is being further developed at PSI and used extensively in studies relating to nuclear waste disposal. (author)

Defluoridation using biomimetically synthesized nano zirconium chitosan composite: Kinetic and equilibrium studies

International Nuclear Information System (INIS)

Prasad, Kumar Suranjit; Amin, Yesha; Selvaraj, Kaliaperumal

2014-01-01

Highlights: • Colloidal Zr nanoparticles, synthesized using Aloe vera extract were entrapped in chitosan beads. • Zr loaded beads were employed for removal of F − ion and showed excellent removal efficiency. • Zr and chitosan are cost effective materials hence can be a good adsorbent for removal of fluoride. - Abstract: The present study reports a novel approach for synthesis of Zr nanoparticles using aqueous extract of Aloe vera. Resulting nanoparticles were embedded into chitosan biopolymer and termed as CNZr composite. The composite was subjected to detailed adsorption studies for removal of fluoride from aqueous solution. The synthesized Zr nanoparticles showed UV–vis absorption peak at 420 nm. TEM result showed the formation of polydispersed, nanoparticles ranging from 18 nm to 42 nm. SAED and XRD analysis suggested an fcc (face centered cubic) Zr crystallites. EDAX analysis suggested that Zr was an integral component of synthesized nanoparticles. FT-IR study indicated that functional group like -NH, -C=O, -C=N and -C=C were involved in particle formation. The adsorption of fluoride on to CNZr composite worked well at pH 7.0, where ∼99% of fluoride was found to be adsorbed on adsorbent. Langmuir isotherm model best fitted the equilibrium data since it presented higher R 2 value than Freundlich model. In comparison to pseudo-first order kinetic model, the pseudo-second order model could explain adsorption kinetic behavior of F − onto CNZr composite satisfactorily with a good correlation coefficient. The present study revealed that CNZr composite may work as an effective tool for removal of fluoride from contaminated water

The Effect of Cooperative Learning Approach Based on Conceptual Change Condition on Students' Understanding of Chemical Equilibrium Concepts

Science.gov (United States)

Bilgin, Ibrahim; Geban, Omer

2006-01-01

The purpose of this study is to investigate the effects of the cooperative learning approach based on conceptual change conditions over traditional instruction on 10th grade students' conceptual understanding and achievement of computational problems related to chemical equilibrium concepts. The subjects of this study consisted of 87 tenth grade…

Chemical composition of silica-based biocidal modifier

Directory of Open Access Journals (Sweden)

Grishina Anna Nikolaevna

2016-11-01

Full Text Available Increase of the amount of fungi spores and micotixines causes the increase in the number of different diseases. Because of this, ensuring the biological safety in buildings is becoming more and more important today. The preferred way to guarantee the biological safety of a building is to employ modern building materials that prevent the settlement of the fungi colonies on the inner surfaces of walls. Such building materials can be produced using novel biocidal modifiers that allow controlling the number of microorganisms on the surface and in the bulk of a composite construction. The precipitation product of zinc hydrosilicates and sodium sulfate is one of the mentioned modifiers. Till now, the exact chemical composition of such precipitation product is controversial; it is obvious, though, that the efficacy of the biocidal modifier is mostly determined by the type of the copper compounds. In the present work an integrated approach is used for the investigation of the chemical composition of the biocidal modifier. Such an approach consists in the examination of the modifier’s composition by means of different, yet complementary, research methods: X-ray diffraction, infrared spectroscopy and DTA. It is shown that the chemical composition of the modifier mainly depends on the amount of precipitant. X-ray diffraction reveals that the major part of the modifier is represented by amorphous phase. Along with the increase of the precipitant’s amount the crystalline phase Zn4SO4(OH6•xH2O formation takes place. Such a crystalline phase is not appropriate as a component of the biocidal modifier. Another two methods - DTA and IR spectroscopy - reveal that the amorphous phase consists essentially of zinc hydrosilicates.

Functional Fixedness and Functional Reduction as Common Sense Reasonings in Chemical Equilibrium and in Geometry and Polarity of Molecules.

Science.gov (United States)

Furio, C.; Calatayud, M. L.; Barcenas, S. L.; Padilla, O. M.

2000-01-01

Focuses on learning difficulties in procedural knowledge, and assesses the procedural difficulties of grade 12 and first- and third-year university students based on common sense reasoning in two areas of chemistry--chemical equilibrium and geometry, and polarity of molecules. (Contains 55 references.) (Author/YDS)

Chemical Equilibrium And Transport (CET)

Science.gov (United States)

Mcbride, B. J.

1991-01-01

Powerful, machine-independent program calculates theoretical thermodynamic properties of chemical systems. Aids in design of compressors, turbines, engines, heat exchangers, and chemical processing equipment.

Non-equilibrium plasma reactor for natrual gas processing

International Nuclear Information System (INIS)

Shair, F.H.; Ravimohan, A.L.

1974-01-01

A non-equilibrium plasma reactor for natural gas processing into ethane and ethylene comprising means of producing a non-equilibrium chemical plasma wherein selective conversion of the methane in natural gas to desired products of ethane and ethylene at a pre-determined ethane/ethylene ratio in the chemical process may be intimately controlled and optimized at a high electrical power efficiency rate by mixing with a recycling gas inert to the chemical process such as argon, helium, or hydrogen, reducing the residence time of the methane in the chemical plasma, selecting the gas pressure in the chemical plasma from a wide range of pressures, and utilizing pulsed electrical discharge producing the chemical plasma. (author)

Chemical composition and nutritional value of boiled Christmas ...

African Journals Online (AJOL)

A study was conducted to determine the chemical composition and the nutritive value of boiled Christmas bush (Alchornea cordifolia) for starter broiler chickens. Dried Christmas bush fruits (Capsules + seed) were boiled for 30 minutes, sundried and ground into meal. The meal was analyzed for proximate composition and ...

Chemical composition of black-watered rivers in the Amazons Region (Brazil)

International Nuclear Information System (INIS)

Horbe, Adriana M.C.; Santos, Ana G. da Silva

2009-01-01

Most investigations addressing Amazonian water chemistry are focused on the Solimoes, Amazonas and Negro rivers. Knowledge of the chemical composition of their smaller tributaries is restricted to some few, punctual data. The smaller rivers, that only present inputs from their catchments, are very important to understand the overall mechanisms controlling the chemistry of larger rivers of the region. With this objective the chemical composition of the principal Solimoes river black-watered tributaries in the western Brazilian Amazon during the low water period were determined. The data reveal the black water chemical composition to be highly variable and strongly influenced by the local geological environment: the Badajos basin being chemically more diluted; the Coari basin presenting higher SiO 2 contents, as well as smaller lakes having higher pH, conductivity, Ca 2+ , Mg 2+ and Sr, yet not as much as those found in the Solimoes river. The chemical composition of these waters is compatible with the low physical erosion and the region's highly leached tropical environment from which most soluble elements were quickly removed. (author)

Date fruit: chemical composition, nutritional and medicinal values, products.

Science.gov (United States)

Tang, Zhen-Xing; Shi, Lu-E; Aleid, Salah M

2013-08-15

Date fruit has served as a staple food in the Arab world for centuries. Worldwide production of date fruit has increased almost threefold over the last 40 years, reaching 7.68 million tons in 2010. Date fruit can provide many essential nutrients and potential health benefits to the consumer. Date fruit goes through four ripening stages named kimri, khalal, rutab and tamer. The main chemical components of date fruit include carbohydrates, dietary fibre, enzymes, protein, fat, minerals, vitamins, phenolic acids and carotenoids. The chemical composition of date fruit varies according to ripening stage, cultivar, growing environment, postharvest conditions, etc. The nutritional and medicinal activities of date fruit are related to its chemical composition. Many studies have shown that date fruit has antioxidant, antimutagenic, anti-inflammatory, gastroprotective, hepatoprotective, nephroprotective, anticancer and immunostimulant activities. Various date fruit-based products such as date syrup, date paste, date juice and their derived products are available. Date by-products can be used as raw materials for the production of value-added products such as organic acids, exopolysaccharides, antibiotics, date-flavoured probiotic-fermented dairy produce, bakery yeasts, etc. In this paper the chemical composition and nutritional and medicinal values of date fruit as well as date fruit-based products are reviewed. © 2013 Society of Chemical Industry.

Geochemical modelling of groundwater evolution using chemical equilibrium codes

International Nuclear Information System (INIS)

Pitkaenen, P.; Pirhonen, V.

1991-01-01

Geochemical equilibrium codes are a modern tool in studying interaction between groundwater and solid phases. The most common used programs and application subjects are shortly presented in this article. The main emphasis is laid on the approach method of using calculated results in evaluating groundwater evolution in hydrogeological system. At present in geochemical equilibrium modelling also kinetic as well as hydrologic constrains along a flow path are taken into consideration

Formation of nitric acid hydrates - A chemical equilibrium approach

Science.gov (United States)

Smith, Roland H.

1990-01-01

Published data are used to calculate equilibrium constants for reactions of the formation of nitric acid hydrates over the temperature range 190 to 205 K. Standard enthalpies of formation and standard entropies are calculated for the tri- and mono-hydrates. These are shown to be in reasonable agreement with earlier calorimetric measurements. The formation of nitric acid trihydrate in the polar stratosphere is discussed in terms of these equilibrium constants.

Study on Physical Properties and Chemical Composition of Some Myanmar Gems

International Nuclear Information System (INIS)

Kyaw Myint Htoo; Tun Khin; Sein Htoon

2004-05-01

Physical properties of some Myanmar gems were studied by using refractometer, dichroscope, polariscope, SG test, UV test and microscope. Then, chemical composition were investigated by XRF-technique. After that, gem identification, evaluation, colour improvement were studied according to these physical properties and chemical composition

Thermal non-equilibrium heat transfer in a porous cavity in the presence of bio-chemical heat source

Directory of Open Access Journals (Sweden)

Nazari Mohsen

2015-01-01

Full Text Available This paper is concerned with thermal non-equilibrium natural convection in a square cavity filled with a porous medium in the presence of a biomass which is transported in the cavity. The biomass can consume a secondary moving substrate. The physics of the presented problem is related to the analysis of heat and mass transfer in a composting process that controlled by internal heat generation. The intensity of the bio-heat source generated in the cavity is equal to the rate of consumption of the substrate by the biomass. It is assumed that the porous medium is homogeneous and isotropic. A two-field model that represents the fluid and solid phase temperature fields separately is used for energy equation. A simplified Monod model is introduced along with the governing equations to describe the consumption of the substrate by the biomass. In other word, the transient biochemical heat source which is dependent on a solute concentration is considered in the energy equations. Investigation of the biomass activity and bio-chemical heat generation in the case of thermal non-equilibrium assumption has not been considered in the literature and they are open research topics. The effects of thermal non-equilibrium model on heat transfer, flow pattern and biomass transfer are investigated. The effective parameters which have a direct impact on the generated bio-chemical heat source are also presented. The influences of the non-dimensional parameters such as fluid-to-solid conductivity ratio on the temperature distribution are presented.

Evaluating equilibrium and non-equilibrium transport of bromide and isoproturon in disturbed and undisturbed soil columns

Science.gov (United States)

Dousset, S.; Thevenot, M.; Pot, V.; Šimunek, J.; Andreux, F.

2007-12-01

In this study, displacement experiments of isoproturon were conducted in disturbed and undisturbed columns of a silty clay loam soil under similar rainfall intensities. Solute transport occurred under saturated conditions in the undisturbed soil and under unsaturated conditions in the sieved soil because of a greater bulk density of the compacted undisturbed soil compared to the sieved soil. The objective of this work was to determine transport characteristics of isoproturon relative to bromide tracer. Triplicate column experiments were performed with sieved (structure partially destroyed to simulate conventional tillage) and undisturbed (structure preserved) soils. Bromide experimental breakthrough curves were analyzed using convective-dispersive and dual-permeability (DP) models (HYDRUS-1D). Isoproturon breakthrough curves (BTCs) were analyzed using the DP model that considered either chemical equilibrium or non-equilibrium transport. The DP model described the bromide elution curves of the sieved soil columns well, whereas it overestimated the tailing of the bromide BTCs of the undisturbed soil columns. A higher degree of physical non-equilibrium was found in the undisturbed soil, where 56% of total water was contained in the slow-flow matrix, compared to 26% in the sieved soil. Isoproturon BTCs were best described in both sieved and undisturbed soil columns using the DP model combined with the chemical non-equilibrium. Higher degradation rates were obtained in the transport experiments than in batch studies, for both soils. This was likely caused by hysteresis in sorption of isoproturon. However, it cannot be ruled out that higher degradation rates were due, at least in part, to the adopted first-order model. Results showed that for similar rainfall intensity, physical and chemical non-equilibrium were greater in the saturated undisturbed soil than in the unsaturated sieved soil. Results also suggested faster transport of isoproturon in the undisturbed soil due

Chemical equilibrium of hydrogen and aqueous solutions of 1 : 1 bicarbonate and formate salts with a common cation

NARCIS (Netherlands)

Engel, D.C.; Versteeg, G.F.; Swaaij, W.P.M. van

1997-01-01

The chemical equilibrium of hydrogen and aqueous solutions of 1:1 bicarbonate and formate salts with a common cation has been investigated in an intensively stirred batch reactor: MHCO3(aq) + H2(aq) ↔ MOOCH(aq) + H2O(l) This was accomplished for the sodium (M = Na), potassium (M = K) and ammonium (M

Distance-dependent diffusion-controlled reaction of •NO and O2•- at chemical equilibrium with ONOO-.

Science.gov (United States)

Botti, Horacio; Möller, Matías N; Steinmann, Daniel; Nauser, Thomas; Koppenol, Willem H; Denicola, Ana; Radi, Rafael

2010-12-16

The fast reaction of (•)NO and O(2)(•-) to give ONOO(-) has been extensively studied at irreversible conditions, but the reasons for the wide variations in observed forward rate constants (3.8 ≤ k(f) ≤ 20 × 10(9) M(-1) s(-1)) remain unexplained. We characterized the diffusion-dependent aqueous (pH > 12) chemical equilibrium of the form (•)NO + O(2)(•-) = ONOO(-) with respect to its dependence on temperature, viscosity, and [ONOO(-)](eq) by determining [ONOO(-)](eq) and [(•)NO](eq). The equilibrium forward reaction rate constant (k(f)(eq)) has negative activation energy, in contrast to that found under irreversible conditions. In contradiction to the law of mass action, we demonstrate that the equilibrium constant depends on ONOO(-) concentration. Therefore, a wide range of k(f)(eq) values could be derived (7.5-21 × 10(9) M(-1) s(-1)). Of general interest, the variations in k(f) can thus be explained by its dependence on the distance between ONOO(-) particles (sites of generation of (•)NO and O(2)(•-)).

Thermodynamic Study of Solid-Liquid Equilibrium in NaCl-NaBr-H2O System at 288.15 K

Science.gov (United States)

Li, Dan; Meng, Ling-zong; Deng, Tian-long; Guo, Ya-fei; Fu, Qing-Tao

2018-06-01

The solubility data, composition of the solid solution and refractive indices of the NaCl-NaBr-H2O system at 288.15 K were studied with the isothermal equilibrium dissolution method. The solubility diagram and refractive index diagram of this system were plotted at 288.15 K. The solubility diagram consists of two crystallization zones for solid solution Na(Cl,Br) · 2H2O and Na(Cl,Br), one invariant points cosaturated with two solid solution and two univariant solubility isothermal curves. On the basis of Pitzer and Harvie-Weare (HW) chemical models, the composition equations and solubility equilibrium constant equations of the solid solutions at 288.15 K were acquired using the solubility data, the composition of solid solutions, and binary Pitzer parameters. The solubilities calculated using the new method combining the equations are in good agreement with the experimental data.

Equilibrium Partitioning Sediment Benchmarks (ESBs) for the ...

Science.gov (United States)

This document describes procedures to determine the concentrations of nonionic organic chemicals in sediment interstitial waters. In previous ESB documents, the general equilibrium partitioning (EqP) approach was chosen for the derivation of sediment benchmarks because it accounts for the varying bioavailability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms.  This equilibrium partitioning sediment benchmark (ESB) document was prepared by scientists from the Atlantic Ecology Division, Mid-Continent Ecology Division, and Western Ecology Division, the Office of Water, and private consultants. The document describes procedures to determine the interstitial water concentrations of nonionic organic chemicals in contaminated sediments. Based on these concentrations, guidance is provided on the derivation of toxic units to assess whether the sediments are likely to cause adverse effects to benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it is based on the concentrations of chemical(s) that are known to be harmful and bioavailable in the environment.  This document, and five others published over the last nine years, will be useful for the Program Offices, including Superfund, a

Uranium mineral - groundwater equilibrium at the Palmottu natural analogue study site, Finland

International Nuclear Information System (INIS)

Ahonen, L.; Ruskeeniemi, T.; Blomqvist, R.; Ervanne, H.; Jaakkola, T.

1993-01-01

The redox-potential, pH, chemical composition of fracture waters, and uraninite alteration associated with the Palmottu uranium mineralization (a natural analogue study site for radioactive waste disposal in southwestern Finland), have been studied. The data have been interpreted by means of thermodynamic calculations. The results indicate equilibrium between uraninite, ferric hydroxide and groundwater in the bedrock of the study site. Partially oxidized uraninite (UO 2 .33) and ferric hydroxide are in equilibrium with fresh, slightly acidic and oxidized water type, while primary uraninite is stable with deeper waters that have a higher pH and lower Eh. Measured Eh-pH values of groundwater cluster within a relatively narrow range indicating buffering by heterogenous redox-processes. A good consistency between measured Eh and analyzed uranium oxidation states was observed

Near-equilibrium chemical vapor deposition of high-quality single-crystal graphene directly on various dielectric substrates.

Science.gov (United States)

Chen, Jianyi; Guo, Yunlong; Jiang, Lili; Xu, Zhiping; Huang, Liping; Xue, Yunzhou; Geng, Dechao; Wu, Bin; Hu, Wenping; Yu, Gui; Liu, Yunqi

2014-03-05

By using near-equilibrium chemical vapor deposition, it is demonstrated that high-quality single-crystal graphene can be grown on dielectric substrates. The maximum size is about 11 μm. The carrier mobility can reach about 5650 cm(2) V(-1) s(-1) , which is comparable to those of some metal-catalyzed graphene crystals, reflecting the good quality of the graphene lattice. © 2013 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Influence of the precursor chemical composition on heavy metal adsorption properties of hemp (Cannabis Sativa fibers based biocarbon

Directory of Open Access Journals (Sweden)

Vukčević Marija M.

2017-01-01

Full Text Available Waste hemp (Cannabis sativa fibers were used as sustainable and renewable raw materials for production of low-cost biocarbon sorbent for heavy metals removal. Carbon precursors of different chemical composition were obtained by oxidative and alkaline treatments of hemp fibers. Influence of lignocellulosic precursor chemical composition on hemp fibers-based biocarbon (HFB characteristics was examined by BET surface area measurement, scanning electron microscopy and mass titration. It was found that lignin content and polymorphic transformation of cellulose increase the SBET of microporous HFBs, while hemicelluloses induce more homogeneous distribution of adsorption active sites. Heavy metal ions adsorption onto HFBs is primarily influenced by the amount of surface oxygen groups, while specific surface area plays a secondary role. Equilibrium data obtained for lead ions adsorption were analyzed by different nonlinear adsorption isotherms, and the best fitting model was chosen using standard deviation and Akaike information criterion (AICC. The maximum adsorption capacities of HFBs ranged from 103.1 to 116.3 mg Pb/g. Thermodynamic parameters showed that Pb2+ adsorption onto HFBs is a spontaneous and complex endothermic process, suggesting the coexistence of physisorption and chemisorption mechanisms. [Project of the Serbian Ministry of Education, Science and Technological Development, Grant no. 172007 and Grant no. 172029

Defluoridation using biomimetically synthesized nano zirconium chitosan composite: Kinetic and equilibrium studies

Energy Technology Data Exchange (ETDEWEB)

Prasad, Kumar Suranjit, E-mail: suranjit@gmail.com [Department of Environmental Biotechnology, Ashok and Rita Patel Institute of Integrated Study and Research in Biotechnology and Allied Sciences (ARIBAS), New Vallabh Vidyanagar, Anand, 388121 Gujarat (India); Amin, Yesha, E-mail: yesha_2879@yahoo.co.in [Department of Environmental Biotechnology, Ashok and Rita Patel Institute of Integrated Study and Research in Biotechnology and Allied Sciences (ARIBAS), New Vallabh Vidyanagar, Anand, 388121 Gujarat (India); Selvaraj, Kaliaperumal, E-mail: k.selvaraj@ncl.res.in [Nano and Computational Materials Lab, Catalysis Division, National Chemical Laboratory, Council of Scientific and Industrial Research, Pune 411008 (India)

2014-07-15

Highlights: • Colloidal Zr nanoparticles, synthesized using Aloe vera extract were entrapped in chitosan beads. • Zr loaded beads were employed for removal of F{sup −} ion and showed excellent removal efficiency. • Zr and chitosan are cost effective materials hence can be a good adsorbent for removal of fluoride. - Abstract: The present study reports a novel approach for synthesis of Zr nanoparticles using aqueous extract of Aloe vera. Resulting nanoparticles were embedded into chitosan biopolymer and termed as CNZr composite. The composite was subjected to detailed adsorption studies for removal of fluoride from aqueous solution. The synthesized Zr nanoparticles showed UV–vis absorption peak at 420 nm. TEM result showed the formation of polydispersed, nanoparticles ranging from 18 nm to 42 nm. SAED and XRD analysis suggested an fcc (face centered cubic) Zr crystallites. EDAX analysis suggested that Zr was an integral component of synthesized nanoparticles. FT-IR study indicated that functional group like -NH, -C=O, -C=N and -C=C were involved in particle formation. The adsorption of fluoride on to CNZr composite worked well at pH 7.0, where ∼99% of fluoride was found to be adsorbed on adsorbent. Langmuir isotherm model best fitted the equilibrium data since it presented higher R{sup 2} value than Freundlich model. In comparison to pseudo-first order kinetic model, the pseudo-second order model could explain adsorption kinetic behavior of F{sup −} onto CNZr composite satisfactorily with a good correlation coefficient. The present study revealed that CNZr composite may work as an effective tool for removal of fluoride from contaminated water.

Reviewing Some Crucial Concepts of Gibbs Energy in Chemical Equilibrium Using a Computer-Assisted, Guided-Problem-Solving Approach

Science.gov (United States)

Borge, Javier

2015-01-01

G, G°, [delta][subscript r]G, [delta][subscript r]G°, [delta]G, and [delta]G° are essential quantities to master the chemical equilibrium. Although the number of publications devoted to explaining these items is extremely high, it seems that they do not produce the desired effect because some articles and textbooks are still being written with…

Variations in chemical and isotopic compositions of groundwaters from the Otobaru landslide in the area of hydrothermal alteration, Beppu City

Energy Technology Data Exchange (ETDEWEB)

Yoshioka, Ryuma; Kitaoka, Koichi; Kamiyama, Kokichi [Kyoto Univ., Uji (Japan). Disaster Prevention Research Inst.

1989-10-01

The landslide at the Otobaru area, Beppu City, occurred twice in 1943 and 1969. A part of this area, even now, is affected considerably by thermal activities. Variations in chemical and isotopic compositions of waters from the Otobaru area and its vicinity were investigated from 1977 to 1983 and 1986 to 1987. The results are as follows: (1) electric conductivity data suggest that the two kinds of low-concentration water and high-concentration water exist in the landslide area, (2) the existence-of two groundwater aquifer in the landslide area and its vicinity is inferred from tritium data, (3) variations chemical composition of waters from the horizontal borehole are accompanied by the rise and decline of water table, (4) the waters from the landslide area and its vicinity are in equilibrium with montmorillonite, (5) the most waters under 10{sup -1} atm. of P{sub co2} are saturated or supersaturated with calcite, and (6) there is no detectable contribution of geothermal water to the waters from the landslide and its vicinity. And our hypothesis on the mechanism for the formation of calcium sulfate type water is also presented. (author).

Variations in chemical and isotopic compositions of groundwaters from the Otobaru landslide in the area of hydrothermal alteration, Beppu City

International Nuclear Information System (INIS)

Yoshioka, Ryuma; Kitaoka, Koichi; Kamiyama, Kokichi

1989-01-01

The landslide at the Otobaru area, Beppu City, occurred twice in 1943 and 1969. A part of this area, even now, is affected considerably by thermal activities. Variations in chemical and isotopic compositions of waters from the Otobaru area and its vicinity were investigated from 1977 to 1983 and 1986 to 1987. The results are as follows: (1) electric conductivity data suggest that the two kinds of low-concentration water and high-concentration water exist in the landslide area, (2) the existence-of two groundwater aquifer in the landslide area and its vicinity is inferred from tritium data, (3) variations chemical composition of waters from the horizontal borehole are accompanied by the rise and decline of water table, (4) the waters from the landslide area and its vicinity are in equilibrium with montmorillonite, (5) the most waters under 10 -1 atm. of P co2 are saturated or supersaturated with calcite, and (6) there is no detectable contribution of geothermal water to the waters from the landslide and its vicinity. And our hypothesis on the mechanism for the formation of calcium sulfate type water is also presented. (author)

Chemical composition of wildland fire emissions

Science.gov (United States)

Shawn P. Urbanski; Wei Min Hao; Stephen Baker

2009-01-01

Wildland fires are major sources of trace gases and aerosol, and these emissions are believed to significantly influence the chemical composition of the atmosphere and the earth's climate system. The wide variety of pollutants released by wildland fire include greenhouse gases, photochemically reactive compounds, and fine and coarse particulate matter. Through...

Chemical cosmology

CERN Document Server

Boeyens, Jan CA

2010-01-01

The composition of the most remote objects brought into view by the Hubble telescope can no longer be reconciled with the nucleogenesis of standard cosmology and the alternative explanation, in terms of the LAMBDA-Cold-Dark-Matter model, has no recognizable chemical basis. A more rational scheme, based on the chemistry and periodicity of atomic matter, opens up an exciting new interpretation of the cosmos in terms of projective geometry and general relativity. The response of atomic structure to environmental pressure predicts non-Doppler cosmical redshifts and equilibrium nucleogenesis by alp

Indirect Determination of Chemical Composition and Fuel Characteristics of Solid Waste

DEFF Research Database (Denmark)

Riber, Christian; Christensen, Thomas Højlund

Determination of chemical composition of solid waste can be performed directly or indirectly by analysis of combustion products. The indirect methodology instrumented by a full scale incinerator is the only method that can conclude on elements in trace concentrations. These elements are of great...... interest in evaluating waste management options by for example LCA modeling. A methodology description of indirect determination of chemical composition and fuel properties of waste is provided and validated by examples. Indirect analysis of different waste types shows that the chemical composition...... is significantly dependent on waste type. And the analysis concludes that the transfer of substances in the incinerator is a function of waste chemical content, incinerator technology and waste physical properties. The importance of correct representation of rare items in the waste with high concentrations...

Chemical composition of lunar material.

Science.gov (United States)

Maxwell, J A; Abbey, S; Champ, W H

1970-01-30

Chemical and emission spectrographic analyses of three Apollo 11 samples, 10017-29, 10020-30, and 10084-132, are given. Major and minor constituents were determined both by conventional rock analysis methods and by a new composite scheme utilizing a lithium fluoborate method for dissolution of the samples and atomic absorption spectroscopy and colorimetry. Trace constituents were determined by optical emission spectroscopy involving a d-c arc, air-jet controlled.

Measurement and Modelling of Phase Equilibrium of Oil - Water - Polar Chemicals

DEFF Research Database (Denmark)

Frost, Michael Grynnerup

in the temperature range of 303-323 K at atmospheric pressure. In the second part of this work, the CPA EoS has been used for modeling hydrocarbon systemcontaining polar chemicals, such as water and gas hydrate inhibitor MEG or methanol. All the experimental data measured in this work have been investigated using...... with the measurement of newexperimental data, but through the development of new experimental equipment for the study ofmulti-phase equilibrium. In addition to measurement of well-defined systems, LLE have beenmeasured for North Sea oils with MEG and water. The work can be split up into two parts: Experimental: VLE...... systems presented, confirming the quality of theequipment. The equipment is used for measurement of VLE for several systems of interest; methane+ water, methane + methanol, methane + methanol + water and methane + MEG. Details dealing with the design, assembling and testing of new experimental equipment...

The microstructure and composition of equilibrium phases formed in hypoeutectic Te-In alloy during solidification

Energy Technology Data Exchange (ETDEWEB)

Wang, Baoguang [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Hu, Jinwu [Center of Failure Analysis, Central Iron and Steel Research Institute, Beijing 100081 (China); Wang, Chongyun; Yang, Wenhui [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China); Tian, Wenhuai, E-mail: wenhuaitian@ustb.edu.cn [Department of Materials Physics and Chemistry, University of Science and Technology Beijing, Beijing 100083 (China)

2017-03-15

As a key tellurium atoms evaporation source for ultraviolet detection photocathode, the hypoeutectic Te{sub 75}In{sub 25} alloy was prepared by employing a slow solidification speed of about 10{sup −2} K/s. The microstructure and chemical composition of the equilibrium phases formed in the as-prepared alloy were studied in this research work. The experimental results show that the as-prepared Te-In alloy was constituted by primary In{sub 2}Te{sub 5} phase and eutectic In{sub 2}Te{sub 5}/Te phases. The eutectic In{sub 2}Te{sub 5}/Te phases are distributed in the grain boundaries of primary In{sub 2}Te{sub 5} phase. With the slow solidification speed, a pure eutectic Te phase without any excessive indium solute was obtained, where Te content of eutectic Te phase is 100 mass%. Moreover, it can be considered that the stress between the In{sub 2}Te{sub 5} and Te phases plays an important role in reducing the tellurium vapor pressure in Te{sub 75}In{sub 25} alloy. - Highlights: • The microstructure of Te-In alloy as an evaporation source was analyzed. • A pure eutectic Te phase was obtained by using a slow solidification speed method. • The relation between vapor pressure and inner-stress in the alloy was discussed.

Molecular equilibrium with condensation

International Nuclear Information System (INIS)

Sharp, C.M.; Huebner, W.F.

1990-01-01

Minimization of the Gibbs energy of formation for species of chemical elements and compounds in their gas and condensed phases determines their relative abundances in a mixture in chemical equilibrium. The procedure is more general and more powerful than previous abundance determinations in multiphase astrophysical mixtures. Some results for astrophysical equations of state are presented, and the effects of condensation on opacity are briefly indicated. 18 refs

Phase Equilibrium of TiO2 Nanocrystals in Flame-Assisted Chemical Vapor Deposition.

Science.gov (United States)

Liu, Changran; Camacho, Joaquin; Wang, Hai

2018-01-19

Nano-scale titanium oxide (TiO 2 ) is a material useful for a wide range of applications. In a previous study, we showed that TiO 2 nanoparticles of both rutile and anatase crystal phases could be synthesized over the size range of 5 to 20 nm in flame-assisted chemical vapor deposition. Rutile was unexpectedly dominant in oxygen-lean synthesis conditions, whereas anatase is the preferred phase in oxygen-rich gases. The observation is in contrast to the 14 nm rutile-anatase crossover size derived from the existing crystal-phase equilibrium model. In the present work, we made additional measurements over a wider range of synthesis conditions; the results confirm the earlier observations. We propose an improved model for the surface energy that considers the role of oxygen desorption at high temperatures. The model successfully explains the observations made in the current and previous work. The current results provide a useful path to designing flame-assisted chemical vapor deposition of TiO 2 nanocrystals with controllable crystal phases. © 2018 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim.

Research on the neutron flux, secular equilibrium of chlorine-36 and groundwater age of the deep quaternary sediments, Hebei plain

International Nuclear Information System (INIS)

Dong Yuean; He Ming; Jiang Songsheng; Wu Shaoyong; Jiang Shan

2001-01-01

For the study of the neutron flux, secular equilibrium of chlorine-36 in the deep quaternary sediments of Hebei plain, the main chemical composition of water sand and confining bed was determined by neutron activation analysis. The mean neutron flux is 2.79 x 10 -5 cm -2 s -1 which was calculated by the chemical composition of the strata. The mean 36 Cl/Cl ratio in secular equilibrium is 1.27 x 10 -14 in the deep quaternary sediments, Hebei Plain. For the study of the groundwater age of the deep Quaternary sediments of Hebei Plain, the 36 Cl/Cl ratio of groundwater samples were determined by tandem accelerator mass spectrometry. The mixed groundwater 36 Cl/Cl ratio of the second and the third aquifer of Quaternary sediments in Baoding district is 247 x 10 -15 , that of the fourth aquifer in Baoding city is 224 x 10 -15 and the third aquifer in Cangzhou district is 40.5 x 10 -15 . The groundwater age of Baoding district was young and that of the third aquifer in Cangzhou was 229.2 ka

Modeling the Non-Equilibrium Process of the Chemical Adsorption of Ammonia on GaN(0001) Reconstructed Surfaces Based on Steepest-Entropy-Ascent Quantum Thermodynamics.

Science.gov (United States)

Kusaba, Akira; Li, Guanchen; von Spakovsky, Michael R; Kangawa, Yoshihiro; Kakimoto, Koichi

2017-08-15

Clearly understanding elementary growth processes that depend on surface reconstruction is essential to controlling vapor-phase epitaxy more precisely. In this study, ammonia chemical adsorption on GaN(0001) reconstructed surfaces under metalorganic vapor phase epitaxy (MOVPE) conditions (3Ga-H and N ad -H + Ga-H on a 2 × 2 unit cell) is investigated using steepest-entropy-ascent quantum thermodynamics (SEAQT). SEAQT is a thermodynamic-ensemble based, first-principles framework that can predict the behavior of non-equilibrium processes, even those far from equilibrium where the state evolution is a combination of reversible and irreversible dynamics. SEAQT is an ideal choice to handle this problem on a first-principles basis since the chemical adsorption process starts from a highly non-equilibrium state. A result of the analysis shows that the probability of adsorption on 3Ga-H is significantly higher than that on N ad -H + Ga-H. Additionally, the growth temperature dependence of these adsorption probabilities and the temperature increase due to the heat of reaction is determined. The non-equilibrium thermodynamic modeling applied can lead to better control of the MOVPE process through the selection of preferable reconstructed surfaces. The modeling also demonstrates the efficacy of DFT-SEAQT coupling for determining detailed non-equilibrium process characteristics with a much smaller computational burden than would be entailed with mechanics-based, microscopic-mesoscopic approaches.

EVALUATION OF BIOMASS AND COAL CO-GASIFICATION OF BRAZILIAN FEEDSTOCK USING A CHEMICAL EQUILIBRIUM MODEL

Directory of Open Access Journals (Sweden)

R. Rodrigues

Full Text Available Abstract Coal and biomass are energy sources with great potential for use in Brazil. Coal-biomass co-gasification enables the combination of the positive characteristics of each fuel, besides leading to a cleaner use of coal. The present study evaluates the potential of co-gasification of binary coal-biomass blends using sources widely available in Brazil. This analysis employs computational simulations using a reliable thermodynamic equilibrium model. Favorable operational conditions at high temperatures are determined in order to obtain gaseous products suitable for energy cogeneration and chemical synthesis. This study shows that blends with biomass ratios of 5% and equivalence ratios ≤ 0.3 lead to high cold gas efficiencies. Suitable gaseous products for chemical synthesis were identified at biomass ratios ≤ 35% and moisture contents ≥ 40%. Formation of undesirable nitrogen and sulfur compounds was also analyzed.

Chemical composition of water extracts from shungite and shungite water

International Nuclear Information System (INIS)

Charykova, M.V.; Bornyakova, I.I.; Polekhovskij, Yu.S.; Charykov, N.A.; Kustova, E.V.; Arapov, O.V.

2006-01-01

Chemical analysis of water extracts from shungite-3 of Zagozhino deposit (Karelia) and natural water contacting with shungite rocks are done. Chemical composition and bactericide properties of shungite water are studied [ru

Equilibrium unfolding of A. niger RNase: pH dependence of chemical and thermal denaturation.

Science.gov (United States)

Kumar, Gundampati Ravi; Sharma, Anurag; Kumari, Moni; Jagannadham, Medicherla V; Debnath, Mira

2011-08-01

Equilibrium unfolding of A. niger RNase with chemical denaturants, for example GuHCl and urea, and thermal unfolding have been studied as a function of pH using fluorescence, far-UV, near-UV, and absorbance spectroscopy. Because of their ability to affect electrostatic interactions, pH and chemical denaturants have a marked effect on the stability, structure, and function of many globular proteins. ANS binding studies have been conducted to enable understanding of the folding mechanism of the protein in the presence of the denaturants. Spectroscopic studies by absorbance, fluorescence, and circular dichroism and use of K2D software revealed that the enzyme has α + β type secondary structure with approximately 29% α-helix, 24% β-sheet, and 47% random coil. Under neutral conditions the enzyme is stable in urea whereas GuHCl-induced equilibrium unfolding was cooperative. A. niger RNase has little ANS binding even under neutral conditions. Multiple intermediates were populated during the pH-induced unfolding of A. niger RNase. Urea and temperature-induced unfolding of A. niger RNase into the molten globule-like state is non-cooperative, in contrast to the cooperativity seen with the native protein, suggesting the presence of two parts/domains, in the molecular structure of A. niger RNase, with different stability that unfolds in steps. Interestingly, the GuHCl-induced unfolding of the A state (molten globule state) of A. niger RNase is unique, because a low concentration of denaturant not only induces structural change but also facilitates transition from one molten globule like state (A(MG1)) into another (I(MG2)).

Studying Equilibrium in the Chemical Reaction between Ferric and Iodide Ions in Solution Using a Simple and Inexpensive Approach

Science.gov (United States)

Nikolaychuk, Pavel Anatolyevich; Kuvaeva, Alyona Olegovna

2016-01-01

A laboratory experiment on the study of the chemical equilibrium based on the reaction between ferric and iodide ions in solution with the formation of ferrous ions, free iodine, and triiodide ions is developed. The total concentration of iodide and triiodide ions in the reaction mixture during the reaction is determined by the argentometric…

Chemical composition analysis of simulated waste glass T10-G-16A

Energy Technology Data Exchange (ETDEWEB)

Fox, K. M. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2015-08-01

In this report, SRNL provides chemical composition analyses of a simulated LAW glass designated T10-G-16A.The measured chemical composition data are reported and compared with the targeted values for each component. No issues were identified in reviewing the analytical data.

Numerical method for partial equilibrium flow

International Nuclear Information System (INIS)

Ramshaw, J.D.; Cloutman, L.D.; Los Alamos, New Mexico 87545)

1981-01-01

A numerical method is presented for chemically reactive fluid flow in which equilibrium and nonequilibrium reactions occur simultaneously. The equilibrium constraints on the species concentrations are established by a quadratic iterative procedure. If the equilibrium reactions are uncoupled and of second or lower order, the procedure converges in a single step. In general, convergence is most rapid when the reactions are weakly coupled. This can frequently be achieved by a judicious choice of the independent reactions. In typical transient calculations, satisfactory accuracy has been achieved with about five iterations per time step

Chemical composition of essential oil of Psidium cattleianum var ...

African Journals Online (AJOL)

The aim of this study was to investigate the essential oil composition of Psidium cattleianum var. lucidum from South Africa. The essential oils were extracted by hydrodistillation and the components were identified by gas chromatography coupled to mass spectrometry (GC-MS) to determine the chemical composition of the ...

Composites Based on Polytetrafluoroethylene and Detonation Nanodiamonds: Filler-Matrix Chemical Interaction and Its Effect on a Composite's Properties

Science.gov (United States)

Koshcheev, A. P.; Perov, A. A.; Gorokhov, P. V.; Zaripov, N. V.; Tereshenkov, A. V.; Khatipov, S. A.

2018-06-01

Specific properties of PTFE composites filled with ultradisperse detonation diamonds (UDDs) with different surface chemistries are studied. It is found for the first time that filler in the form of UDDs affects not only the rate of PTFE thermal decomposition in vacuum pyrolysis, but also the chemical composition of the products of degradation. The wear resistance of UDD/PTFE composites is shown to depend strongly on the UDD surface chemistry. The presence of UDDs in a PTFE composite is found to result in perfluorocarbon telomeres, released as a readily condensable fraction upon composite pyrolysis. The chemical interaction between PTFE and UDDs, characterized by an increase in the rate of gas evolution and a change in the desorbed gas's composition, is found to occur at temperature as low as 380°C. It is shown that the intensity of this interaction depends on the concentration of oxygen-containing surface groups, the efficiency of UDDs in terms of the composite's wear resistance being reduced due to the presence of these groups. Based on the experimental data, a conclusion is reached about the chemical interaction between UDDs and a PTFE matrix, its dependence on the nanodiamond surface chemistry, and its effect on a composite's tribology.

Characterization of Low-Symmetry Structures from Phase Equilibrium of Fe-Al System-Microstructures and Mechanical Properties.

Science.gov (United States)

Matysik, Piotr; Jóźwiak, Stanisław; Czujko, Tomasz

2015-03-04

Fe-Al intermetallic alloys with aluminum content over 60 at% are in the area of the phase equilibrium diagram that is considerably less investigated in comparison to the high-symmetry Fe₃Al and FeAl phases. Ambiguous crystallographic information and incoherent data referring to the phase equilibrium diagrams placed in a high-aluminum range have caused confusions and misinformation. Nowadays unequivocal material properties description of FeAl₂, Fe₂Al₅ and FeAl₃ intermetallic alloys is still incomplete. In this paper, the influence of aluminum content and processing parameters on phase composition is presented. The occurrence of low-symmetry FeAl₂, Fe₂Al₅ and FeAl₃ structures determined by chemical composition and phase transformations was defined by scanning electron microscopy (SEM) and energy-dispersive X-ray spectroscopy (EDS) examinations. These results served to verify diffraction investigations (XRD) and to explain the mechanical properties of cast materials such as: hardness, Young's modulus and fracture toughness evaluated using the nano-indentation technique.

Chemical weathering from the CoDA (Compositional Data Analysis) point of view: new insights for the Alpine rivers geochemistry

Science.gov (United States)

Gozzi, Caterina; Buccianti, Antonella; Frondini, Francesco

2017-04-01

The aim of this contribution is to explore the relationship among weathering reactions, the sample space of compositional data and fractals by means of distributional analysis. Weathering reactions represent the transfer of heat and entropy to the environment in geochemical cycles. Chemical weathering is a key process for understanding the global cycle of elements, both on long and short-terms and chemical weathering rates are complex functions of many factors including dissolution kinetics of minerals, mechanical erosion, lithology. Compositional data express the relative (proportional) abundance of chemical elements/species in a given total (i.e. volume or weight) so that compositions pertaining to the peculiar geometry of the simplex sample space. Fractals are temporal or spatial objects with self-similarity and scale invariance, so that internal structures repeat themselves over multiple levels of magnification or scales of measurement. Gibbs's free energy and the application of the Law Mass Action can be used to model weathering reactions, under the hypothesis of chemical equilibrium. Compositional data are obtained in the analytical phase after the determination of the concentrations of chemicals in sampled solid, liquid or gaseous materials. Fractals can be measured by using their fractal dimensions. The presence of fractal structures can be observed when the frequency distribution of isometric log-ratio coordinates is investigated, showing the logarithm of the cumulative number of samples exceeding a certain coordinate value plotted against the coordinate value itself. Isometric log-ratio coordinates (or balances) can be constructed by using the sequential binary partition (SBP) method. The balances can be identified to maintain, as far as possible, the similarity with a corresponding weathering reaction (Buccianti & Zuo, 2016). As an alternative, balances can be derived after the multivariate investigation of the variance-covariance structure of the

CHEMICAL COMPOSITION AND ANTIOXIDANT ACTIVITY OF APIS ...

African Journals Online (AJOL)

CHEMICAL COMPOSITION AND ANTIOXIDANT ACTIVITY OF APIS. MELLIFERA BEE POLLEN FROM NORTHWEST ALGERIA. A. Rebiai* and T.Lanez. University of El Oued, VTRS Laboratory, P.O. Box 789, 39000, El Oued, Algeria. Received: 08 November 2012 / Accepted: 23 December 2012 / Published online: 31 ...

Chemical composition, true metabolisable energy content and ...

African Journals Online (AJOL)

The physical characteristics (thousand seed and hectolitre mass), chemical composition (dry matter, ash, crude protein (CP), ether extract, acid detergent fibre, neutral detergent fibre and mineral content), energy values (nitrogen corrected true metabolisable energy content (TMEn for roosters)) as well as the lysine and ...

Pb(II) adsorption by a novel activated carbon - alginate composite material. A kinetic and equilibrium study.

Science.gov (United States)

Cataldo, Salvatore; Gianguzza, Antonio; Milea, Demetrio; Muratore, Nicola; Pettignano, Alberto

2016-11-01

The adsorption capacity of an activated carbon - calcium alginate composite material (ACAA-Ca) has been tested with the aim of developing a new and more efficient adsorbent material to remove Pb(II) ion from aqueous solution. The study was carried out at pH=5, in NaCl medium and in the ionic strength range 0.1-0.75molL -1 . Differential Pulse Anodic Stripping Voltammetry (DP-ASV) technique was used to check the amount of Pb(II) ion removed during kinetic and equilibrium experiments. Different kinetic (pseudo first order, pseudo second order and Vermuelen) and equilibrium (Langmuir and Freundlich) models were used to fit experimental data, and were statistically compared. Calcium alginate (AA-Ca) improves the adsorption capacity (q m ) of active carbon (AC) in the ACAA-Ca adsorbent material (e.g., q m =15.7 and 10.5mgg -1 at I=0.25molL -1 , for ACAA-Ca and AC, respectively). SEM-EDX and thermogravimetric (TGA) measurements were carried out in order to characterize the composite material. The results of the speciation study on the Pb(II) solution and of the characterization of the ACAA-Ca and of the pristine AA-Ca and AC were evaluated in order to explain the specific contribution of AC and AA-Ca to the adsorption of the metal ion. Copyright © 2016 Elsevier B.V. All rights reserved.

Development of Bi-phase sodium-oxygen-hydrogen chemical equilibrium calculation program (BISHOP) using Gibbs free energy minimization method

International Nuclear Information System (INIS)

Okano, Yasushi

1999-08-01

In order to analyze the reaction heat and compounds due to sodium combustion, the multiphase chemical equilibrium calculation program for chemical reaction among sodium, oxygen and hydrogen is developed in this study. The developed numerical program is named BISHOP; which denotes Bi-Phase, Sodium - Oxygen - Hydrogen, Chemical Equilibrium Calculation Program'. Gibbs free energy minimization method is used because of the special merits that easily add and change chemical species, and generally deal many thermochemical reaction systems in addition to constant temperature and pressure one. Three new methods are developed for solving multi-phase sodium reaction system in this study. One is to construct equation system by simplifying phase, and the other is to expand the Gibbs free energy minimization method into multi-phase system, and the last is to establish the effective searching method for the minimum value. Chemical compounds by the combustion of sodium in the air are calculated using BISHOP. The Calculated temperature and moisture conditions where sodium-oxide and hydroxide are formed qualitatively agree with the experiments. Deformation of sodium hydride is calculated by the program. The estimated result of the relationship between the deformation temperature and pressure closely agree with the well known experimental equation of Roy and Rodgers. It is concluded that BISHOP can be used for evaluated the combustion and deformation behaviors of sodium and its compounds. Hydrogen formation condition of the dump-tank room at the sodium leak event of FBR is quantitatively evaluated by BISHOP. It can be concluded that to keep the temperature of dump-tank room lower is effective method to suppress the formation of hydrogen. In case of choosing the lower inflammability limit of 4.1 mol% as the hydrogen concentration criterion, formation reaction of sodium hydride from sodium and hydrogen is facilitated below the room temperature of 800 K, and concentration of hydrogen

Chemical composition of cigarette smoke

Energy Technology Data Exchange (ETDEWEB)

Guerin, M. R.

1979-01-01

Cigarette smoke is a concentrated aerosol of liquid particles suspended in an atmosphere consisting mainly of nitrogen, oxygen, and carbon dioxide. While the precise chemical composition of the particulate and gaseous phases is dependent on the characteristics of the cigarette and the manner in which it is smoked, both phases contain tens of hundreds of individual constitutents. Notable among potentially hazardous constituents of smoke are tar, nicotine, carbon monoxide, nitric oxide, hydrogen cyanide, acrolein, benzo(a)pyrene, and N-nitrosamines.

The effects of using screencasting as a multimedia pre-training tool to manage the intrinsic cognitive load of chemical equilibrium instruction for advanced high school chemistry students

Science.gov (United States)

Musallam, Ramsey

Chemistry is a complex knowledge domain. Specifically, research notes that Chemical Equilibrium presents greater cognitive challenges than other topics in chemistry. Cognitive Load Theory describes the impact a subject, and the learning environment, have on working memory. Intrinsic load is the facet of Cognitive Load Theory that explains the complexity innate to complex subjects. The purpose of this study was to build on the limited research into intrinsic cognitive load, by examining the effects of using multimedia screencasts as a pre-training technique to manage the intrinsic cognitive load of chemical equilibrium instruction for advanced high school chemistry students. A convenience sample of 62 fourth-year high school students enrolled in an advanced chemistry course from a co-ed high school in urban San Francisco were given a chemical equilibrium concept pre-test. Upon conclusion of the pre-test, students were randomly assigned to two groups: pre-training and no pre-training. The pre-training group received a 10 minute and 52 second pre-training screencast that provided definitions, concepts and an overview of chemical equilibrium. After pre-training both group received the same 50-minute instructional lecture. After instruction, all students were given a chemical equilibrium concept post-test. Independent sample t-tests were conducted to examine differences in performance and intrinsic load. No significant differences in performance or intrinsic load, as measured by ratings of mental effort, were observed on the pre-test. Significant differences in performance, t(60)=3.70, p=.0005, and intrinsic load, t(60)=5.34, p=.0001, were observed on the post-test. A significant correlation between total performance scores and total mental effort ratings was also observed, r(60)=-0.44, p=.0003. Because no significant differences in prior knowledge were observed, it can be concluded that pre-training was successful at reducing intrinsic load. Moreover, a significant

Variation in the chemical composition, physical characteristics and ...

African Journals Online (AJOL)

Variation in the chemical composition, physical characteristics and energy values of cereal grains produced in the Western Cape area of South Africa. TS Brand, CW Cruywagen, DA Brandt, M Viljoen, WW Burger ...

Relationship between bacterial density and chemical composition of ...

African Journals Online (AJOL)

TUOYO

Key words: Bacterial density, chemical composition, oxidation pond, sewage, tropics. INTRODUCTION ... pond for about two weeks during which algae, bacteria and other organisms act ..... Chloride can serve as nutrient for micro- organisms ...

On the vapor-liquid equilibrium in hydroprocessing reactors

Energy Technology Data Exchange (ETDEWEB)

Chen, J.; Munteanu, M.; Farooqi, H. [National Centre for Upgrading Technology, Devon, AB (Canada)

2009-07-01

When petroleum distillates undergo hydrotreating and hydrocracking, the feedstock and hydrogen pass through trickle-bed catalytic reactors at high temperatures and pressures with large hydrogen flow. As such, the oil is partially vaporized and the hydrogen is partially dissolved in liquid to form a vapor-liquid equilibrium (VLE) system with both vapor and liquid phases containing oil and hydrogen. This may result in considerable changes in flow rates, physical properties and chemical compositions of both phases. Flow dynamics, mass transfer, heat transfer and reaction kinetics may also be modified. Experimental observations of VLE behaviours in distillates with different feedstocks under a range of operating conditions were presented. In addition, VLE was predicted along with its effects on distillates in pilot and commercial scale plants. tabs., figs.

Chemical Composition Measurements of LAWA44 Glass Samples

Energy Technology Data Exchange (ETDEWEB)

Fox, K. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Edwards, T. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL); Riley, W. [Savannah River Site (SRS), Aiken, SC (United States). Savannah River National Lab. (SRNL)

2016-11-15

DOE is building the Hanford Tank Waste Treatment and Immobilization Plant (WTP) at the Hanford Site in Washington to remediate 55 million gallons of radioactive waste that is temporarily stored in 177 underground tanks. Both low-activity and high-level wastes will then be vitrified into borosilicate glass using Joule-heated ceramic melters. Efforts are being made to increase the loading of Hanford tank wastes in the glass. One area of work is enhancing waste glass composition/property models and broadening the compositional regions over which those models are applicable. In this report, the Savannah River National Laboratory provides chemical analysis results for several samples of a simulated low-activity waste glass, LAWA44, provided by the Pacific Northwest National Laboratory as part of an ongoing development task. The measured chemical composition data are reported and compared with the targeted values for each component for each glass. A detailed review showed no indications of errors in the preparation or measurement of the study glasses. All of the measured sums of oxides for the study glasses fell within the interval of 97.9 to 102.6 wt %, indicating acceptable recovery of the glass components. Comparisons of the targeted and measured chemical compositions showed that the measured values for the glasses met the targeted concentrations within 10% for those components present at more than 5 wt %. It was noted that the measured B₂O₃ concentrations are somewhat above the targeted values for the study glasses. No obvious trends were observed with regard to the multiple melting steps used to prepare the study glasses, indicating that any potential effects of volatility were below measurable thresholds.

Identifying apparent local stable isotope equilibrium in a complex non-equilibrium system.

Science.gov (United States)

He, Yuyang; Cao, Xiaobin; Wang, Jianwei; Bao, Huiming

2018-02-28

Although being out of equilibrium, biomolecules in organisms have the potential to approach isotope equilibrium locally because enzymatic reactions are intrinsically reversible. A rigorous approach that can describe isotope distribution among biomolecules and their apparent deviation from equilibrium state is lacking, however. Applying the concept of distance matrix in graph theory, we propose that apparent local isotope equilibrium among a subset of biomolecules can be assessed using an apparent fractionation difference (|Δα|) matrix, in which the differences between the observed isotope composition (δ') and the calculated equilibrium fractionation factor (1000lnβ) can be more rigorously evaluated than by using a previous approach for multiple biomolecules. We tested our |Δα| matrix approach by re-analyzing published data of different amino acids (AAs) in potato and in green alga. Our re-analysis shows that biosynthesis pathways could be the reason for an apparently close-to-equilibrium relationship inside AA families in potato leaves. Different biosynthesis/degradation pathways in tubers may have led to the observed isotope distribution difference between potato leaves and tubers. The analysis of data from green algae does not support the conclusion that AAs are further from equilibrium in glucose-cultured green algae than in the autotrophic ones. Application of the |Δα| matrix can help us to locate potential reversible reactions or reaction networks in a complex system such as a metabolic system. The same approach can be broadly applied to all complex systems that have multiple components, e.g. geochemical or atmospheric systems of early Earth or other planets. Copyright © 2017 John Wiley & Sons, Ltd.

Chemical composition, physicochemical and functional properties of ...

African Journals Online (AJOL)

The results of chemical composition, physicochemical and functional properties for both lupin samples indicated that lupins can be used as a raw material for various food products manufacturing and provide consistency in food processing, analogous to other food legumes. Therefore, the research findings can be used by ...

Proximate chemical composition of giant ipil-ipil wood from different sources

Energy Technology Data Exchange (ETDEWEB)

Escolano, E U; Gonzales, E V; Semana, J A

1978-01-01

Studies of the chemical composition of seven samples of giant ipil-ipil (Leucaena leucocephala) yielded holocellulose, 69.8 to 73.9%; pentosans, 8.9 to 20.1%; lignin, 21.8 to 26%; alcohol-benzene solubles, 1.4 to 3.0%; caustic soda solubles, 13.0 to 16.4%; and ash, 0.7 to 0.9%. Based on chemical composition, this should be a suitable species for pulp and paper. (Refs. 11).

Silicone passive equilibrium samplers as ‘chemometers’ in eels and sediments of a Swedish lake

DEFF Research Database (Denmark)

Jahnke, Annika; Mayer, Philipp; McLachlan, Michael S.

2014-01-01

Passive equilibrium samplers deployed in two or more media of a system and allowed to come to equilibrium can be viewed as ‘chemometers’ that reflect the difference in chemical activities of contaminants between the media. We applied silicone-based equilibrium samplers to measure relative chemica...... diagenesis and sorption to phytoplankton. The ‘chemometer’ approach has the potential to become a powerful tool to study the thermodynamic controls on persistent organic chemicals in the environment and should be extended to other environmental compartments.......Passive equilibrium samplers deployed in two or more media of a system and allowed to come to equilibrium can be viewed as ‘chemometers’ that reflect the difference in chemical activities of contaminants between the media. We applied silicone-based equilibrium samplers to measure relative chemical...... activities of seven ‘indicator’ polychlorinated biphenyls (PCBs) and hexachlorobenzene in eels and sediments from a Swedish lake. Chemical concentrations in eels and sediments were also measured using exhaustive extraction methods. Lipid-normalized concentrations in eels were higher than organic carbon...

Combustion of hydrogen-air jets in local chemical equilibrium: A guide to the CHARNAL computer program

Science.gov (United States)

Spalding, D. B.; Launder, B. E.; Morse, A. P.; Maples, G.

1974-01-01

A guide to a computer program, written in FORTRAN 4, for predicting the flow properties of turbulent mixing with combustion of a circular jet of hydrogen into a co-flowing stream of air is presented. The program, which is based upon the Imperial College group's PASSA series, solves differential equations for diffusion and dissipation of turbulent kinetic energy and also of the R.M.S. fluctuation of hydrogen concentration. The effective turbulent viscosity for use in the shear stress equation is computed. Chemical equilibrium is assumed throughout the flow.

Antimicrobial activity and chemical compositions of Turkish propolis ...

African Journals Online (AJOL)

negative bacteria and its chemical composition were evaluated by the method of agar-well diffusion and GC-MS, respectively. Some typical compounds samples were identified in the propolis samples. Principal component analysis revealed that the ...

Chemical compositions and antimicrobial activity of twig essential ...

African Journals Online (AJOL)

Aghomotsegin

2016-03-09

Mar 9, 2016 ... The chemical composition of twig essential oils of Xylopia malayana, Xylopia elliptica and Xylopia fusca were analyzed ... brown or dark green in colors and fragrant. .... extraction used and geographic origin of plant studied.

A long-term variation of chemical composition in precipitation

International Nuclear Information System (INIS)

Yoshioka, Ryuma; Okimura, Takashi; Okumura, Takenobu

1991-01-01

Precipitation samples are collected at the six localities in the southwestern Japan weekly or monthly over a long period of time (1978-1989) in order to estimate chemical weathering rates and amount of weathered materials through chemical composition in natural waters. Major chemical composition is determined for the precipitation samples. Together with the data available in the literature, the following characteristics are recognized : 1) Most pH values fall in the narrow range of 4.4 to 5.4, 2) Systematic variations in pH values are observed among the precipitation samples of different geologic environments, 3) pH values become almost constant from 1984 to 1989, 4) NO 3 - concentrations gradually decrease to an almost constant value with time, and 5) ΔSO 4 2- concentrations gradually have a tendency to decrease from 1978 to 1985. The mechanism of phenomena described above is also presented. (author)

Petrological Geodynamics of Mantle Melting I. AlphaMELTS + Multiphase Flow: Dynamic Equilibrium Melting, Method and Results

Directory of Open Access Journals (Sweden)

Massimiliano Tirone

2017-10-01

Full Text Available The complex process of melting in the Earth's interior is studied by combining a multiphase numerical flow model with the program AlphaMELTS which provides a petrological description based on thermodynamic principles. The objective is to address the fundamental question of the effect of the mantle and melt dynamics on the composition and abundance of the melt and the residual solid. The conceptual idea is based on a 1-D description of the melting process that develops along an ideal vertical column where local chemical equilibrium is assumed to apply at some level in space and time. By coupling together the transport model and the chemical thermodynamic model, the evolution of the melting process can be described in terms of melt distribution, temperature, pressure and solid and melt velocities but also variation of melt and residual solid composition and mineralogical abundance at any depth over time. In this first installment of a series of three contributions, a two-phase flow model (melt and solid assemblage is developed under the assumption of complete local equilibrium between melt and a peridotitic mantle (dynamic equilibrium melting, DEM. The solid mantle is also assumed to be completely dry. The present study addresses some but not all the potential factors affecting the melting process. The influence of permeability and viscosity of the solid matrix are considered in some detail. The essential features of the dynamic model and how it is interfaced with AlphaMELTS are clearly outlined. A detailed and explicit description of the numerical procedure should make this type of numerical models less obscure. The general observation that can be made from the outcome of several simulations carried out for this work is that the melt composition varies with depth, however the melt abundance not necessarily always increases moving upwards. When a quasi-steady state condition is achieved, that is when melt abundance does not varies significantly

Paper spray mass spectrometry applied in the monitoring of a chemical system in dynamic chemical equilibrium: the redox process of methylene blue.

Science.gov (United States)

de Paula, Camila Cristina Almeida; Valadares, Alberto; Jurisch, Marina; Piccin, Evandro; Augusti, Rodinei

2016-05-15

The monitoring of chemical systems in dynamic equilibrium is not an easy task. This is due to the high rate at which the system returns to equilibrium after being perturbed, which hampers the possibility of following the aftereffects of the disturbance. In this context, it is necessary to use a fast analytical technique that requires no (or minimal) sample preparation, and which is capable of monitoring the species constituting the system in equilibrium. Paper spray ionization mass spectrometry (PS-MS), a recently introduced ambient ionization technique, has such characteristics and hence was chosen for monitoring a model system: the redox process of methylene blue. The model system evaluated herein was composed of three cationic species of methylene blue (MB), which coexist in a dynamic redox system: (1) [MB](+) of m/z 284 (cationic MB); (2) [MB + H + e](+•) of m/z 285 (the protonated form of a transient species resulting from the reduction of [MB](+) ); (3) [MB + 2H + 2e](+) or [leuco-MB + H](+) of m/z 286 (the protonated leuco form of MB). Aliquots of a MB solution were collected before and after the addition of a reducing agent (metallic zinc) and directly analyzed by PS-MS for identification of the predominant cationic species at different conditions. The mass spectra revealed that before the addition of the reducing agent the ion of m/z 284 (cationic MB) is the unique species. Upon the addition of the reducing agent and acid, however, the solution continuously undergo discoloration while reduced species derived directly from cationic MB (m/z 285 and 286) are detected in the mass spectra with increasing intensities. Fragmentation patterns obtained for each ionic species, i.e. [MB](+) , [MB + H + e](+•) and [leuco-MB + H](+) , shown to be consistent with the proposed structures. The PS-MS technique proved to be suitable for an in situ and 'near' real-time analysis of the dynamic equilibrium involving the redox of MB in aqueous medium. The data clearly

A new particle-like method for high-speed flows with chemical non-equilibrium

Directory of Open Access Journals (Sweden)

Fábio Rodrigues Guzzo

2010-04-01

Full Text Available The present work is concerned with the numerical simulation of hypersonic blunt body flows with chemical non-equilibrium. New theoretical and numerical formulations for coupling the chemical reaction to the fluid dynamics are presented and validated. The fluid dynamics is defined for a stationary unstructured mesh and the chemical reaction process is defined for “finite quantities” moving through the stationary mesh. The fluid dynamics is modeled by the Euler equations and the chemical reaction rates by the Arrhenius law. Ideal gases are considered. The thermodynamical data are based on JANNAF tables and Burcat’s database. The algorithm proposed by Liou, known as AUSM+, is implemented in a cell-centered based finite volume method and in an unstructured mesh context. Multidimensional limited MUSCL interpolation method is used to perform property reconstructions and to achieve second-order accuracy in space. The minmod limiter is used. The second order accuracy, five stage, Runge-Kutta time-stepping scheme is employed to perform the time march for the fluid dynamics. The numerical code VODE, which is part of the CHEMKIN-II package, is adopted to perform the time integration for the chemical reaction equations. The freestream reacting fluid is composed of H2 and air at the stoichiometric ratio. The emphasis of the present paper is on the description of the new methodology for handling the coupling of chemical and fluid mechanic processes, and its validation by comparison with the standard time-splitting procedure. The configurations considered are the hypersonic flow over a wedge, in which the oblique detonation wave is induced by an oblique shock wave, and the hypersonic flow over a blunt body. Differences between the solutions obtained with each formulation are presented and discussed, including the effects of grid refinement in each case. The primary objective of such comparisons is the validation of the proposed methodology. Moreover, for

Vapor pressures and vapor compositions in equilibrium with hypostoichiometric uranium-plutonium dioxide at high temperatures

International Nuclear Information System (INIS)

Green, D.W.; Fink, J.K.; Leibowitz, L.

1982-01-01

Vapor pressures and vapor compositions in equilibrium with a hypostoichiometric uranium-plutonium dioxide condensed phase (U/sub 1-y/Pu/sub y/)O/sub 2-x/, as functions of T, x, and y, have been calculated for 0.0 less than or equal to x less than or equal to 0.1, 0.0 less than or equal to y less than or equal to 0.3, and for the temperature range 2500 less than or equal to T less than or equal to 6000 K. The range of compositions and temperatures was limited to the region of interest to reactor safety analysis. Thermodynamic functions for the condensed phase and for each of the gaseous species were combined with an oxygen potential model to obtain partial pressures of O, O 2 , Pu, PuO, PuO 2 , U, UO, UO 2 , and UO 3 as functions of T, x, and y

Operating mechanisms of electrolytes in magnesium ion batteries: chemical equilibrium, magnesium deposition, and electrolyte oxidation.

Science.gov (United States)

Kim, Dong Young; Lim, Younhee; Roy, Basab; Ryu, Young-Gyoon; Lee, Seok-Soo

2014-12-21

Since the early nineties there have been a number of reports on the experimental development of Mg electrolytes based on organo/amide-magnesium chlorides and their transmetalations. However, there are no theoretical papers describing the underlying operating mechanisms of Mg electrolytes, and there is no clear understanding of these mechanisms. We have therefore attempted to clarify the operating mechanisms of Mg electrolytes by studying the characteristics of Mg complexes, solvation, chemical equilibrium, Mg-deposition processes, electrolyte-oxidation processes, and oxidative degradation mechanism of RMgCl-based electrolytes, using ab initio calculations. The formation and solvation energies of Mg complexes highly depend on the characteristics of R groups. Thus, changes in R groups of RMgCl lead to changes in the equilibrium position and the electrochemical reduction and oxidation pathways and energies. We first provide a methodological scheme for calculating Mg reduction potential values in non-aqueous electrolytes and electrochemical windows. We also describe a strategy for designing Mg electrolytes to maximize the electrochemical windows and oxidative stabilities. These results will be useful not only for designing improved Mg electrolytes, but also for developing new electrolytes in the future.

WOOD STOVE EMISSIONS: PARTICLE SIZE AND CHEMICAL COMPOSITION

Science.gov (United States)

The report summarizes wood stove particle size and chemical composition data gathered to date. [NOTE: In 1995, EPA estimated that residential wood combustion (RWC), including fireplaces, accounted for a significant fraction of national particulate matter with aerodynamic diameter...

Identification and analysis of student conceptions used to solve chemical equilibrium problems

Science.gov (United States)

Voska, Kirk William

This study identified and quantified chemistry conceptions students use when solving chemical equilibrium problems requiring the application of Le Chatelier's principle, and explored the feasibility of designing a paper and pencil test for this purpose. It also demonstrated the utility of conditional probabilities to assess test quality. A 10-item pencil-and-paper, two-tier diagnostic instrument, the Test to Identify Student Conceptualizations (TISC) was developed and administered to 95 second-semester university general chemistry students after they received regular course instruction concerning equilibrium in homogeneous aqueous, heterogeneous aqueous, and homogeneous gaseous systems. The content validity of TISC was established through a review of TISC by a panel of experts; construct validity was established through semi-structured interviews and conditional probabilities. Nine students were then selected from a stratified random sample for interviews to validate TISC. The probability that TISC correctly identified an answer given by a student in an interview was p = .64, while the probability that TISC correctly identified a reason given by a student in an interview was p=.49. Each TISC item contained two parts. In the first part the student selected the correct answer to a problem from a set of four choices. In the second part students wrote reasons for their answer to the first part. TISC questions were designed to identify students' conceptions concerning the application of Le Chatelier's principle, the constancy of the equilibrium constant, K, and the effect of a catalyst. Eleven prevalent incorrect conceptions were identified. This study found students consistently selected correct answers more frequently (53% of the time) than they provided correct reasons (33% of the time). The association between student answers and respective reasons on each TISC item was quantified using conditional probabilities calculated from logistic regression coefficients. The

PROCEDURES FOR THE DERIVATION OF EQUILIBRIUM ...

Science.gov (United States)

This equilibrium partitioning sediment benchmark (ESB) document describes procedures to derive concentrations for 32 nonionic organic chemicals in sediment which are protective of the presence of freshwater and marine benthic organisms. The equilibrium partitioning (EqP) approach was chosen because it accounts for the varying biological availability of chemicals in different sediments and allows for the incorporation of the appropriate biological effects concentration. This provides for the derivation of benchmarks that are causally linked to the specific chemical, applicable across sediments, and appropriately protective of benthic organisms. EqP can be used to calculate ESBs for any toxicity endpoint for which there are water-only toxicity data; it is not limited to any single effect endpoint. For the purposes of this document, ESBs for 32 nonionic organic chemicals, including several low molecular weight aliphatic and aromatic compounds, pesticides, and phthalates, were derived using Final Chronic Values (FCV) from Water Quality Criteria (WQC) or Secondary Chronic Values (SCV) derived from existing toxicological data using the Great Lakes Water Quality Initiative (GLI) or narcosis theory approaches. These values are intended to be the concentration of each chemical in water that is protective of the presence of aquatic life. For nonionic organic chemicals demonstrating a narcotic mode of action, ESBs derived using the GLI approach specifically for fres

The equilibrium crystal shape of nickel

International Nuclear Information System (INIS)

Meltzman, Hila; Chatain, Dominique; Avizemer, Dan; Besmann, Theodore M.; Kaplan, Wayne D.

2011-01-01

Highlights: → The ECS of pure Ni is completely facetted with both dense and high-index planes. → The partial pressure of oxygen has a significant effect on the surface anisotropy. → The addition of Fe decreased the anisotropy and de-stabilized high-index planes. → During solid dewetting nucleation barriers prevent equilibration of the top facet. - Abstract: The crystal shape of Ni particles, dewetted in the solid state on sapphire substrates, was examined as a function of the partial pressure of oxygen (P(O 2 )) and iron content using scanning and transmission electron microscopy. The chemical composition of the surface was characterized by atom-probe tomography. Unlike other face-centered cubic (fcc) equilibrium crystal shapes, the Ni crystals containing little or no impurities exhibited a faceted shape, indicating large surface anisotropy. In addition to the {1 1 1}, {1 0 0} and {1 1 0} facets, which are usually present in the equilibrium crystal shape of fcc metals, high-index facets were identified such as {1 3 5} and {1 3 8} at low P(O 2 ), and {0 1 2} and {0 1 3} at higher P(O 2 ). The presence of iron altered the crystal shape into a truncated sphere with only facets parallel to denser planes. The issue of particle equilibration is discussed specifically for the case of solid-state dewetting.

Non-Equilibrium Thermodynamics of Self-Replicating Protocells

DEFF Research Database (Denmark)

Fellermann, Harold; Corominas-Murtra, Bernat; Hansen, Per Lyngs

2018-01-01

We provide a non-equilibrium thermodynamic description of the life-cycle of a droplet based, chemically feasible, system of protocells. By coupling the protocells metabolic kinetics with its thermodynamics, we demonstrate how the system can be driven out of equilibrium to ensure protocell growth...... and replication. This coupling allows us to derive the equations of evolution and to rigorously demonstrate how growth and replication life-cycle can be understood as a non-equilibrium thermodynamic cycle. The process does not appeal to genetic information or inheritance, and is based only on non......-equilibrium physics considerations. Our non-equilibrium thermodynamic description of simple, yet realistic, processes of protocell growth and replication, represents an advance in our physical understanding of a central biological phenomenon both in connection to the origin of life and for modern biology....

Non-equilibrium quantum heat machines

Science.gov (United States)

Alicki, Robert; Gelbwaser-Klimovsky, David

2015-11-01

Standard heat machines (engine, heat pump, refrigerator) are composed of a system (working fluid) coupled to at least two equilibrium baths at different temperatures and periodically driven by an external device (piston or rotor) sometimes called the work reservoir. The aim of this paper is to go beyond this scheme by considering environments which are stationary but cannot be decomposed into a few baths at thermal equilibrium. Such situations are important, for example in solar cells, chemical machines in biology, various realizations of laser cooling or nanoscopic machines driven by laser radiation. We classify non-equilibrium baths depending on their thermodynamic behavior and show that the efficiency of heat machines powered by them is limited by the generalized Carnot bound.

Non-equilibrium quantum heat machines

International Nuclear Information System (INIS)

Alicki, Robert; Gelbwaser-Klimovsky, David

2015-01-01

Standard heat machines (engine, heat pump, refrigerator) are composed of a system (working fluid) coupled to at least two equilibrium baths at different temperatures and periodically driven by an external device (piston or rotor) sometimes called the work reservoir. The aim of this paper is to go beyond this scheme by considering environments which are stationary but cannot be decomposed into a few baths at thermal equilibrium. Such situations are important, for example in solar cells, chemical machines in biology, various realizations of laser cooling or nanoscopic machines driven by laser radiation. We classify non-equilibrium baths depending on their thermodynamic behavior and show that the efficiency of heat machines powered by them is limited by the generalized Carnot bound. (paper)

In vitro CT evaluation of intrahepatic stones: correlation with chemical composition

International Nuclear Information System (INIS)

Kim, Young Jun; Han, Joon Koo; Jeong, Jun Yong; Lee, Kyoung Ho; Kim, Se Hyung; Kim, Young Il; Lee, Jeong Min; Choi, Byung Ihn; Park, Youn-Chan; Kim, Sun-Whe

2005-01-01

Objective: To describe in vitro CT features of intrahepatic stones and to correlate CT attenuation with chemical composition. Materials and methods: Of the patients who underwent choledochoscopic intrahepatic stone removal between 1998 and 2001, 54 patients with stones larger than 3 mm were enrolled in this study. In each case, a chemical compositional analysis was performed to determine calcium, cholesterol, total bilirubin, and inorganic phosphorus compositions. The three largest stones obtained from each patient were imaged by CT. CT attenuation numbers were measured in the center images of each stone by drawing free-hand region of interest (ROI). The measured CT attenuation numbers were correlated with their chemical composition. Also, CT attenuation numbers of stones were compared with that of the liver on non-contrast CT (50-70 HU). Results: Stone size ranged from 3.1 to 10.5 mm (mean ± S.D.: 6.0 ± 1.4). The CT attenuation numbers (HU) of stones ranged from 36.4 to 410.19 (mean ± S.D.: 94.6 ± 49.9). CT numbers of stones were below 70 HU in 11 patients (20.4%), and below 90 HU in 33 patients (59.3%). The chemical analysis data of the stones were as follows: calcium (0.5-6.5 wt.%; mean ± S.D., 2.6 ± 1.4), total bilirubin (0.45-24.4 wt.%; 13.1 ± 6.2), cholesterol (5.4-73.9 wt.%; 29.3 ± 17.4), phosphorus (0.1-1.2 wt.%; 0.6 ± 0.3), and non-soluble residue (17.6-85.4 wt.%; 57.0 ± 22.6). There was a weak but significant correlation between calcium composition and CT attenuation (r = 0.38, P 0.01; total bilirubin, r = 0.05, P > 0.01; phosphorus, r = 0.01, P > 0.01). Conclusion: On non-contrast CT, intrahepatic stones would not be hyperattenuating with respect to liver parenchyma in about one fifth of patients. The CT attenuation of stones correlates with calcium and does not correlate with any other chemical composition

Chemical composition, true metabolisable energy content and ...

African Journals Online (AJOL)

aneldavh

116. Chemical composition, true metabolisable energy content and amino acid availability of grain legumes for poultry. T.S. Brand. 1, 2,3#. , D.A. Brandt. 1, 2,4 and C.W. ... alternatives (Wiseman, 1987; Brand et al., 1995). ..... The Ca, P and trace element concentrations for lupins, faba beans and peas recorded in the present.

Kinetics and equilibrium models for the sorption of tributyltin to nZnO, activated carbon and nZnO/activated carbon composite in artificial seawater

International Nuclear Information System (INIS)

Ayanda, Olushola S.; Fatoki, Olalekan S.; Adekola, Folahan A.; Ximba, Bhekumusa J.

2013-01-01

Highlights: • Removal of tributyltin from artificial seawater using nZnO/activated carbon and its precursors was studied. • Detailed equilibrium and kinetic studies were reported. • Adsorption conditions were optimized and applied to natural seawater. • Higher removal efficiency of TBT was obtained for the composite and activated carbon except nZnO. • TBT concentration was determine by GC-FPD following derivatization. -- Abstract: The removal of tributyltin (TBT) from artificial seawater using nZnO, activated carbon and nZnO/activated carbon composite was systematically studied. The equilibrium and kinetics of adsorption were investigated in a batch adsorption system. Equilibrium adsorption data were analyzed using Langmuir, Freundlich, Temkin and Dubinin–Radushkevich (D–R) isotherm models. Pseudo first- and second-order, Elovich, fractional power and intraparticle diffusion models were applied to test the kinetic data. Thermodynamic parameters such as ΔG°, ΔS° and ΔH° were also calculated to understand the mechanisms of adsorption. Optimal conditions for the adsorption of TBT from artificial seawater were then applied to TBT removal from natural seawater. A higher removal efficiency of TBT (>99%) was obtained for the nZnO/activated carbon composite material and for activated carbon but not for nZnO

Numerical Validation of Chemical Compositional Model for Wettability Alteration Processes

Science.gov (United States)

Bekbauov, Bakhbergen; Berdyshev, Abdumauvlen; Baishemirov, Zharasbek; Bau, Domenico

2017-12-01

Chemical compositional simulation of enhanced oil recovery and surfactant enhanced aquifer remediation processes is a complex task that involves solving dozens of equations for all grid blocks representing a reservoir. In the present work, we perform a numerical validation of the newly developed mathematical formulation which satisfies the conservation laws of mass and energy and allows applying a sequential solution approach to solve the governing equations separately and implicitly. Through its application to the numerical experiment using a wettability alteration model and comparisons with existing chemical compositional model's numerical results, the new model has proven to be practical, reliable and stable.

Global chemical composition of ambient fine particulate matter for exposure assessment.

Science.gov (United States)

Philip, Sajeev; Martin, Randall V; van Donkelaar, Aaron; Lo, Jason Wai-Ho; Wang, Yuxuan; Chen, Dan; Zhang, Lin; Kasibhatla, Prasad S; Wang, Siwen; Zhang, Qiang; Lu, Zifeng; Streets, David G; Bittman, Shabtai; Macdonald, Douglas J

2014-11-18

Epidemiologic and health impact studies are inhibited by the paucity of global, long-term measurements of the chemical composition of fine particulate matter. We inferred PM2.5 chemical composition at 0.1° × 0.1° spatial resolution for 2004-2008 by combining aerosol optical depth retrieved from the MODIS and MISR satellite instruments, with coincident profile and composition information from the GEOS-Chem global chemical transport model. Evaluation of the satellite-model PM2.5 composition data set with North American in situ measurements indicated significant spatial agreement for secondary inorganic aerosol, particulate organic mass, black carbon, mineral dust, and sea salt. We found that global population-weighted PM2.5 concentrations were dominated by particulate organic mass (11.9 ± 7.3 μg/m(3)), secondary inorganic aerosol (11.1 ± 5.0 μg/m(3)), and mineral dust (11.1 ± 7.9 μg/m(3)). Secondary inorganic PM2.5 concentrations exceeded 30 μg/m(3) over East China. Sensitivity simulations suggested that population-weighted ambient PM2.5 from biofuel burning (11 μg/m(3)) could be almost as large as from fossil fuel combustion sources (17 μg/m(3)). These estimates offer information about global population exposure to the chemical components and sources of PM2.5.

Biosorption of Cu (II onto chemically modified waste mycelium of Aspergillus awamori: Equilibrium, kinetics and modeling studies

Directory of Open Access Journals (Sweden)

ZDRAVKA VELKOVA

2012-01-01

Full Text Available The biosorption potential of chemically modified waste mycelium of industrial xylanase-producing strain Aspergillus awamori for Cu (II removal from aqueous solutions was evaluated. The influence of pH, contact time and initial Cu (II concentration on the removal efficiency was evaluated. Maximum biosorption capacity was reached by sodium hydroxide treated waste fungal mycelium at pH 5.0. The Langmuir adsorption equation matched very well the adsorption equilibrium data in the studied conditions. The process kinetic followed the pseudo-firs order model.

Silicon Oxysulfide, OSiS: Rotational Spectrum, Quantum-Chemical Calculations, and Equilibrium Structure.

Science.gov (United States)

Thorwirth, Sven; Mück, Leonie Anna; Gauss, Jürgen; Tamassia, Filippo; Lattanzi, Valerio; McCarthy, Michael C

2011-06-02

Silicon oxysulfide, OSiS, and seven of its minor isotopic species have been characterized for the first time in the gas phase at high spectral resolution by means of Fourier transform microwave spectroscopy. The equilibrium structure of OSiS has been determined from the experimental data using calculated vibration-rotation interaction constants. The structural parameters (rO-Si = 1.5064 Å and rSi-S = 1.9133 Å) are in very good agreement with values from high-level quantum chemical calculations using coupled-cluster techniques together with sophisticated additivity and extrapolation schemes. The bond distances in OSiS are very short in comparison with those in SiO and SiS. This unexpected finding is explained by the partial charges calculated for OSiS via a natural population analysis. The results suggest that electrostatic effects rather than multiple bonding are the key factors in determining bonding in this triatomic molecule. The data presented provide the spectroscopic information needed for radio astronomical searches for OSiS.

The influence of macronutrient deficiencies on chemical composition ...

African Journals Online (AJOL)

The influence of macronutrient deficiencies on chemical composition of dwarf green coconut (Cocu nucifera linn) seedling. ... Elimination of magnesium also leads to reduction in the concentration of chlorophyll. starch and sugar concentrations improved with nitrogen and potassium but decreased with were more ...

Chemical composition and antimicrobial activity of the essential oils of Pinus pinaster

OpenAIRE

Nouara Ait Mimoune; Djouher Ait Mimoune; Aziza Yataghene

2013-01-01

Objective: To investigate the antimicrobial activity and chemical composition of essential oils of Pinus pinaster. Methods: Essential oils were extracted from the needles by hydrodistillation. The chemical composition of the obtained essential oils was analyzed using GC-MS technique. The antimicrobial potential has been tested against six microorganisms performing the disc diffusion assay. Results: Twenty-three components have been identified. β-caryophyllene (30.9%) and β-seli...

Innovating in the teaching of Chemical Equilibrium: Taking effective advantage of Information and Communication Technologies

Science.gov (United States)

Fonseca, Susana Cristina Morais da

Chemical Equilibrium (CE) is a good example of the specific nature of chemistry. The understanding of this theme requires the conceptualization of macroscopic events, as well as explanations of sub microscopic nature, application of symbolic language and mathematics. CE is commonly identified as a topic suitable for the pedagogical use of Information and Communication Technologies (ICT). However, the growth in the roll of digital resources for the teaching of CE, that took place in the last decades, was not accompanied by a decrease in the signalling of students' difficulties and misconceptions in the subject. This fact, points out the relevance of clarifying the circumstances under which digital resources turn out to be useful in the teaching of CE and develop educative modules that take into account the findings and recommendations from the literature. This project aims to bring a contribution to take advantage form ICT potential in the teaching of CE. The objectives underlying the main purpose of the project were defined according to literature review, which crosses three fundamental dimensions (scientific, pedagogical and technological). The project also benefited from the previous experience of the group and the collaboration with an European project (CROSSNET). The level of abstraction necessary for the understanding of the scientific model is pointed out as the major source of difficulties in the learning of CE, while also referred as a privileged target for the intervention of ICT. In this context, we introduce the expression "facilitating abstraction" to summarize the idea of supporting students' abstract thinking process during the learning of formal concepts. This idea has gained importance throughout the project leading to the development of a pedagogical approach to facilitate abstraction in the learning of CE. Although based on the use of ICT, the main purpose wasn't to introduce new digital resources in the saturated field of CE. Instead, the

Thermodynamics of open, nonisothermal chemical systems far from equilibrium

International Nuclear Information System (INIS)

Yoshida, Nobuo

1992-01-01

The thermodynamic behavior of kinetic models based on a continuously stirred tank reactor (CSTR) is studied in an attempt to seek general trends in the thermodynamic properties of open nonlinear systems. The models consist of two reversible reactions, A + nB rightleftharpoons (n + 1) B (n = 0,1,or 2) and B rightleftharpoons C, taking place in an adiabatic CSTR. The heat of reaction is incorporated, and the rate constants are assumed to follow an Arrhenius temperature dependence. The models give rise to multiple stationary states and sustained oscillations (limit cycles). The entropy difference between stationary or oscillatory states and equilibrium and the rate of entropy production in the these states are calculated as a function of the residence time in the reactor. The entropy difference and entropy production may be taken, to some extent, as indicative of the influence of irreversible processes, which disappears at equilibrium. The results of the calculations reveal the following systematic trends: (I) The entropy difference or entropy production for stable states or both always increase as the residence time is shortened, namely, as the system is displaced further from equilibrium. (II) If stable and unstable states (stationary or oscillatory) coexist under identical conditions, then the stable state invariably has a smaller value of the entropy difference or entropy production or both than the corresponding unstable state. 26 refs., 3 figs

Chemical Composition Variability of Essential Oils of Daucus gracilis Steinh. from Algeria.

Science.gov (United States)

Benyelles, Batoul; Allali, Hocine; Dib, Mohamed El Amine; Djabou, Nassim; Paolini, Julien; Costa, Jean

2017-06-01

The chemical compositions of 20 Algerian Daucus gracilis essential oils were investigated using GC-FID, GC/MS, and NMR analyses. Altogether, 47 compounds were identified, accounting for 90 - 99% of the total oil compositions. The main components were linalool (18; 12.5 - 22.6%), 2-methylbutyl 2-methylbutyrate (20; 9.2 - 20.2%), 2-methylbutyl isobutyrate (10; 4.2 - 12.2%), ammimajane (47; 2.6 - 37.1%), (E)-β-ocimene (15; 0.2 - 12.8%) and 3-methylbutyl isovalerate (19; 3.3 - 9.6%). The chemical composition of the essential oils obtained from separate organs was also studied. GC and GC/MS analysis of D. gracilis leaves and flowers allowed identifying 47 compounds, amounting to 92.3% and 94.1% of total oil composition, respectively. GC and GC/MS analysis of D. gracilis leaf and flower oils allowed identifying linalool (22.7%), 2-methylbutyl 2-methylbutyrate (18.9%), 2-methylbutyl isovalerate (13.6%), ammimajane (10.4%), 3-methylbutyl isovalerate (10.3%), (E)-β-ocimene (8.4%) and isopentyl 2-methylbutyrate (8.1%) as main components. The chemical variability of the Algerian oil samples was studied using statistical analysis, which allowed the discrimination of three main Groups. A direct correlation between the altitudes, nature of soils and the chemical compositions of the D. gracilis essential oils was evidenced. © 2017 Wiley-VHCA AG, Zurich, Switzerland.

Chemical and Oxygen Isotopic Composition of Roman and Late Antique Glass from Northern Greece

Directory of Open Access Journals (Sweden)

Alberta Silvestri

2017-01-01

Full Text Available The present paper emphasizes the importance of measuring the oxygen isotopic and chemical compositions of ancient glass, in order to constrain some features such as age, raw materials, and production technologies and to identify the “fingerprint” of local productions. In this context, thirty-nine Roman and late Antique glass samples and eight chert samples from northern Greece were selected and analysed for their oxygen isotopic and chemical compositions. Results show that the majority of glass samples are produced using natron as flux and have δ18O values of about 15.5‰, plus or minus a few tenths of one per mil, suggesting that raw materials probably come from Levantine area. Four samples are heavily enriched in 18O, and their chemical composition clearly shows that they were made with soda plant ash as flux. Isotopic and chemical data of Greek chert samples support the hypothesis of local production of the above samples. About half of the glass samples have chemical compositions, which allow their age to be constrained to the late Antique period. For the remaining glass, similarities with literature compositional groups are reported and discussed.

Characterization of Low-Symmetry Structures from Phase Equilibrium of Fe-Al System—Microstructures and Mechanical Properties

Directory of Open Access Journals (Sweden)

Piotr Matysik

2015-03-01

Full Text Available Fe-Al intermetallic alloys with aluminum content over 60 at% are in the area of the phase equilibrium diagram that is considerably less investigated in comparison to the high-symmetry Fe3Al and FeAl phases. Ambiguous crystallographic information and incoherent data referring to the phase equilibrium diagrams placed in a high-aluminum range have caused confusions and misinformation. Nowadays unequivocal material properties description of FeAl2, Fe2Al5 and FeAl3 intermetallic alloys is still incomplete. In this paper, the influence of aluminum content and processing parameters on phase composition is presented. The occurrence of low-symmetry FeAl2, Fe2Al5 and FeAl3 structures determined by chemical composition and phase transformations was defined by scanning electron microscopy (SEM and energy-dispersive X-ray spectroscopy (EDS examinations. These results served to verify diffraction investigations (XRD and to explain the mechanical properties of cast materials such as: hardness, Young’s modulus and fracture toughness evaluated using the nano-indentation technique.

Effect of chemical treatment of Kevlar fibers on mechanical interfacial properties of composites.

Science.gov (United States)

Park, Soo-Jin; Seo, Min-Kang; Ma, Tae-Jun; Lee, Douk-Rae

2002-08-01

In this work, the effects of chemical treatment on Kevlar 29 fibers have been studied in a composite system. The surface characteristics of Kevlar 29 fibers were characterized by pH, acid-base value, X-ray photoelectron spectroscopy (XPS), and FT-IR. The mechanical interfacial properties of the final composites were studied by interlaminar shear strength (ILSS), critical stress intensity factor (K(IC)), and specific fracture energy (G(IC)). Also, impact properties of the composites were investigated in the context of differentiating between initiation and propagation energies and ductile index (DI) along with maximum force and total energy. As a result, it was found that chemical treatment with phosphoric acid solution significantly affected the degree of adhesion at interfaces between fibers and resin matrix, resulting in improved mechanical interfacial strength in the composites. This was probably due to the presence of chemical polar groups on Kevlar surfaces, leading to an increment of interfacial binding force between fibers and matrix in a composite system.

Designing of the chemical composition of steels basing on the hardenability of constructional steels

International Nuclear Information System (INIS)

Dobrzanski, L.A.; Sitek, W.

2003-01-01

The paper presents the original method of modelling of the relationships between chemical composition of alloy constructional steel and its hardenability, employing neural networks. Basing on the experimental results of the hardenability investigations, which employed Jominy method, the model of the neural networks was developed and fully verified experimentally. The model makes it possible to obtain Jominy hardenability curves basing on the steel chemical composition. The model of neural networks, making it possible to design the steel chemical composition, basing on the known Jominy hardenability curve shape, was developed also and fully verified numerically. (author)

Applications of non-equilibrium plasma in chemical processes

International Nuclear Information System (INIS)

Patino, P.; Castro, A.

2003-01-01

By means of optical emission spectroscopy the population of O( 3 P) in a non-equilibrium, high voltage, oxygen plasma, and O( 3 P), H and OH in another of steam in radio frequency, have been followed. Reactions of both plasmas with liquid hydrocarbons have produced oxidation and/or hydrogenation, depending on the conditions of each one. (Author)

The chemical composition and industrial quality of Barite ...

African Journals Online (AJOL)

... that the mineralization is of high industrial quality and compares favourably with the Azara barite deposits of the Benue Trough. The quality of the barite meets American Petroleum institute (API) requirements for use as drilling mud. KEYWORDS: Barite, mineralization, quality, chemical composition, southeastern Nigeria.

NMR spectroscopic studies of a TAT-derived model peptide in imidazolium-based ILs: influence on chemical shifts and the cis/trans equilibrium state.

Science.gov (United States)

Wiedemann, Christoph; Ohlenschläger, Oliver; Mrestani-Klaus, Carmen; Bordusa, Frank

2017-09-13

NMR spectroscopy was used to study systematically the impact of imidazolium-based ionic liquid (IL) solutions on a TAT-derived model peptide containing Xaa-Pro peptide bonds. The selected IL anions cover a wide range of the Hofmeister series of ions. Based on highly resolved one- and two-dimensional NMR spectra individual 1 H and 13 C peptide chemical shift differences were analysed and a classification of IL anions according to the Hofmeister series was derived. The observed chemical shift changes indicate significant interactions between the peptide and the ILs. In addition, we examined the impact of different ILs towards the cis/trans equilibrium state of the Xaa-Pro peptide bonds. In this context, the IL cations appear to be of exceptional importance for inducing an alteration of the native cis/trans equilibrium state of Xaa-Pro bonds in favour of the trans-isomers.

Isothermal equilibrium pressures of Y-Th alloy-H2 system

International Nuclear Information System (INIS)

Tanase, M.; Fisher, P.W.

1985-01-01

Isothermal equilibrium pressures of the Y 4 Th (3:2 by weight) alloy-H 2 system were measured as a function of atomic composition [H]/[Y + Th] in the temperature range 580-1160 K. The isotherms have two plateaux in the pressure range 10 -2 -10 3 Pa. The first plateau region is attributed to the formation of YH 2 , and the equilibrium pressure P in pascals was found to be log P = 12.36 - 11300/T where T is in kelvins. The second plateau is attributed to the formation of ThH 2 , and the equilibrium pressure was found to be log P = 10.66 - 6891/T. In low atomic composition region the system obeys Sieverts' law. (Auth.)

Viscosity of SiO2-"FeO"-Al2O3 System in Equilibrium with Metallic Fe

Science.gov (United States)

Chen, Mao; Raghunath, Sreekanth; Zhao, Baojun

2013-08-01

The present study delivered the measurements of viscosities in SiO2-"FeO"-Al2O3 system in equilibrium with metallic Fe. The rotational spindle technique was used in the measurements at the temperature range of 1473 K to 1773 K (1200 °C to 1500 °C). Molybdenum crucibles and spindles were employed in all measurements. The Fe saturation condition was maintained by an iron plate placed at the bottom of the crucible. The equilibrium compositions of the slags were measured by EPMA after the viscosity measurements. The effect of up to 20 mol. pct Al2O3 on the viscosity of the SiO2-"FeO" slag was investigated. The "charge compensation effect" of the Al2O3 and FeO association has been discussed. The modified quasi-chemical viscosity model has been optimized in the SiO2-"FeO"-Al2O3 system in equilibrium with metallic Fe to describe the viscosity measurements of the present study.

Statistical fluctuations and correlations in hadronic equilibrium systems

International Nuclear Information System (INIS)

Hauer, Michael

2010-01-01

This thesis is dedicated to the study of fluctuation and correlation observables of hadronic equilibrium systems. The statistical hadronization model of high energy physics, in its ideal, i.e. non-interacting, gas approximation is investigated in different ensemble formulations. The hypothesis of thermal and chemical equilibrium in high energy interaction is tested against qualitative and quantitative predictions. (orig.)

Statistical fluctuations and correlations in hadronic equilibrium systems

Energy Technology Data Exchange (ETDEWEB)

Hauer, Michael

2010-06-17

This thesis is dedicated to the study of fluctuation and correlation observables of hadronic equilibrium systems. The statistical hadronization model of high energy physics, in its ideal, i.e. non-interacting, gas approximation is investigated in different ensemble formulations. The hypothesis of thermal and chemical equilibrium in high energy interaction is tested against qualitative and quantitative predictions. (orig.)

Capillary Condensation of Binary and Ternary Mixtures of n-Pentane-Isopentane-CO2 in Nanopores: An Experimental Study on the Effects of Composition and Equilibrium.

Science.gov (United States)

Barsotti, Elizabeth; Saraji, Soheil; Tan, Sugata P; Piri, Mohammad

2018-02-06

Confinement in nanopores can significantly impact the chemical and physical behavior of fluids. While some quantitative understanding is available for how pure fluids behave in nanopores, there is little such insight for mixtures. This study aims to shed light on how nanoporosity impacts the phase behavior and composition of confined mixtures through comparison of the effects of static and dynamic equilibrium on experimentally measured isotherms and chromatographic analysis of the experimental fluids. To this end, a novel gravimetric apparatus is introduced and validated. Unlike apparatuses that have been previously used to study the confinement-induced phase behavior of fluids, this apparatus employs a gravimetric technique capable of discerning phase transitions in a wide variety of nanoporous media under both static and dynamic conditions. The apparatus was successfully validated against data in the literature for pure carbon dioxide and n-pentane. Then, isotherms were generated for binary mixtures of carbon dioxide and n-pentane using static and flow-through methods. Finally, two ternary mixtures of carbon dioxide, n-pentane, and isopentane were measured using the static method. While the equilibrium time was found important for determination of confined phase transitions, flow rate in the dynamic method was not found to affect the confined phase behavior. For all measurements, the results indicate qualitative transferability of the bulk phase behavior to the confined fluid.

Changes in chemical composition and bioassay assessment of ...

African Journals Online (AJOL)

Changes in chemical composition and bioassay assessment of nutritional potentials of almond fruit waste as an alternative feedstuff for livestock. ... AFW using day-old cockerels and considering performance parameters showed that treated AFW improved feed intake, body weight gain and feed conversion ratio even better ...

Solvent Isotope-induced Equilibrium Perturbation for Isocitrate Lyase

Science.gov (United States)

Quartararo, Christine E.; Hadi, Timin; Cahill, Sean M.; Blanchard, John S.

2014-01-01

Isocitrate lyase (ICL) catalyzes the reversible retro-aldol cleavage of isocitrate to generate glyoxylate and succinate. ICL is the first enzyme of the glyoxylate shunt, which allows for the anaplerosis of citric acid cycle intermediates under nutrient limiting conditions. In Mycobacterium tuberculosis, the source of ICL for these studies, ICL is vital for the persistence phase of the bacteria’s life cycle. Solvent kinetic isotope effects (KIEs) in the direction of isocitrate cleavage of D2OV = 2.0 ± 0.1 and D2O[V/Kisocitrate] = 2.2 ± 0.3 arise from the initial deprotonation of the C2 hydroxyl group of isocitrate or the protonation of the aci-acid of succinate product of the isocitrate aldol cleavage by a solvent-derived proton. This KIE suggested that an equilibrium mixture of all protiated isocitrate, glyoxylate and succinate prepared in D2O, would undergo transient changes in equilibrium concentrations as a result of the solvent KIE and solvent-derived deuterium incorporation into both succinate and isocitrate. No change in the isotopic composition of glyoxylate was expected or observed. We have directly monitored the changing concentrations of all isotopic species of all reactants and products using a combination of NMR spectroscopy and mass spectrometry. Continuous monitoring of glyoxylate by 1H NMR spectroscopy shows a clear equilibrium perturbation in D2O. The final equilibrium isotopic composition of reactants in D2O revealed di-deuterated succinate, protiated glyoxylate, and mono-deuterated isocitrate, with the transient appearance and disappearance of mono-deuterated succinate. A model for the equilibrium perturbation of substrate species, and their time-dependent isotopic composition is presented. PMID:24261638

Criterion for selection of quasi-equilibrium and quasi-frozen flows of chemically reacting mixture N2O4 reversible 2NO2reversible 2NO+O2 with heat isobaric supply (removal)

International Nuclear Information System (INIS)

Kostik, G.Eh.; Shiryaeva, N.M.

1979-01-01

Is suggested the criterion of quasi-equilibrium and quasi-frozen flows with isobaric heat supply (removal), including the basic external factors, which affect on the kinetics of chemical process. This criterion is the complex [g/Fq], where g is the coolant rate, F is the channel cross-section, q is the heat flow. Estimated formulae for quasi-equilibrium [g/Fq]sub(e) and quasi-frozen [g/Fq]sub(f) flows are obtained. The states of deviation from equilibrium and frozen conditions in linear region are considered, are listed graphical dependences lg[g/Fq]sub(e), lg[g/Fq]sub(el), lg[g/Fq]sub(f), lg[g/Eq]sub(fl), as functions of equilibrium parameter Tsub(e), pressure and frozen coordinate of epsilonsub(2f) reaction. This graphs give the possibility to estimate rapidly and obviously the flow character of chemically reacting coolant

Equilibrium sampling of hydrophobic organic chemicals in sediments: challenges and new approaches

DEFF Research Database (Denmark)

Schaefer, S.; Mayer, Philipp; Becker, B.

2015-01-01

) are considered to be the effective concentrations for diffusive uptake and partitioning, and they can be measured by equilibrium sampling. We have thus applied glass jars with multiple coating thicknesses for equilibrium sampling of HOCs in sediment samples from various sites in different German rivers...

The procedure and results of calculations of the equilibrium isotopic composition of a demonstration subcritical molten salt reactor

Energy Technology Data Exchange (ETDEWEB)

Nevinitsa, V. A., E-mail: Neviniza-VA@nrcki.ru; Dudnikov, A. A.; Blandinskiy, V. Yu.; Balanin, A. L.; Alekseev, P. N. [National Research Centre Kurchatov Institute (Russian Federation); Titarenko, Yu. E.; Batyaev, V. F.; Pavlov, K. V.; Titarenko, A. Yu., E-mail: yuri.titarenko@itep.ru [Institute for Theoretical and Experimental Physics (Russian Federation)

2015-12-15

A subcritical molten salt reactor with an external neutron source is studied computationally as a facility for incineration and transmutation of minor actinides from spent nuclear fuel of reactors of VVER-1000 type and for producing {sup 233}U from {sup 232}Th. The reactor configuration is chosen, the requirements to be imposed on the external neutron source are formulated, and the equilibrium isotopic composition of heavy nuclides and the key parameters of the fuel cycle are calculated.

The empirical equilibrium structure of diacetylene

OpenAIRE

Thorwirth, S.; Harding, M. E.; Muders, D.; Gauss, J.

2008-01-01

High-level quantum-chemical calculations are reported at the MP2 and CCSD(T) levels of theory for the equilibrium structure and the harmonic and anharmonic force fields of diacetylene, HCCCCH. The calculations were performed employing Dunning's hierarchy of correlation-consistent basis sets cc-pVXZ, cc-pCVXZ, and cc-pwCVXZ, as well as the ANO2 basis set of Almloef and Taylor. An empirical equilibrium structure based on experimental rotational constants for thirteen isotopic species of diacety...

Noise-Induced Modulation of the Relaxation Kinetics around a Non-Equilibrium Steady State of Non-Linear Chemical Reaction Networks

OpenAIRE

Ramaswamy, Rajesh; Sbalzarini, Ivo F; González-Segredo, Nélido

2011-01-01

Stochastic effects from correlated noise non-trivially modulate the kinetics of non-linear chemical reaction networks. This is especially important in systems where reactions are confined to small volumes and reactants are delivered in bursts. We characterise how the two noise sources confinement and burst modulate the relaxation kinetics of a non-linear reaction network around a non-equilibrium steady state. We find that the lifetimes of species change with burst input and confinement. Confi...

Glutamate Induced Thermal Equilibrium Intermediate and Counteracting Effect on Chemical Denaturation of Proteins.

Science.gov (United States)

Anumalla, Bramhini; Prabhu, N Prakash

2018-01-25

When organisms are subjected to stress conditions, one of their adaptive responses is accumulation of small organic molecules called osmolytes. These osmolytes affect the structure and stability of the biological macromolecules including proteins. The present study examines the effect of a negatively charged amino acid osmolyte, glutamate (Glu), on two model proteins, ribonuclease A (RNase A) and α-lactalbumin (α-LA), which have positive and negative surface charges at pH 7, respectively. These proteins follow two-state unfolding transitions during both heat and chemical induced denaturation processes. The addition of Glu stabilizes the proteins against temperature and induces an early equilibrium intermediate during unfolding. The stability is found to be enthalpy-driven, and the free energy of stabilization is more for α-LA compared to RNase A. The decrease in the partial molar volume and compressibility of both of the proteins in the presence of Glu suggests that the proteins attain a more compact state through surface hydration which could provide a more stable conformation. This is also supported by molecule dynamic simulation studies which demonstrate that the water density around the proteins is increased upon the addition of Glu. Further, the intermediates could be completely destabilized by lower concentrations (∼0.5 M) of guanidinium chloride and salt. However, urea subverts the Glu-induced intermediate formed by α-LA, whereas it only slightly destabilizes in the case of RNase A which has a positive surface charge and could possess charge-charge interactions with Glu. This suggests that, apart from hydration, columbic interactions might also contribute to the stability of the intermediate. Gdm-induced denaturation of RNase A and α-LA in the absence and the presence of Glu at different temperatures was carried out. These results also show the Glu-induced stabilization of both of the proteins; however, all of the unfolding transitions followed two

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

Science.gov (United States)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-08-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found ( p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

Energy Technology Data Exchange (ETDEWEB)

Lou, Leo [Orthodontic Graduate Program, Faculty of Medicine and Dentistry, University of Alberta (Canada); Nelson, Alan E. [Department of Chemical and Materials Engineering, University of Alberta (Canada)], E-mail: aenelson@dow.com; Heo, Giseon [Department of Statistics, Department of Dentistry, University of Alberta (Canada); Major, Paul W. [Orthodontic Graduate Program, Faculty of Medicine and Dentistry, University of Alberta (Canada)

2008-08-30

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found (p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength.

Surface chemical composition of human maxillary first premolar as assessed by X-ray photoelectron spectroscopy (XPS)

International Nuclear Information System (INIS)

Lou, Leo; Nelson, Alan E.; Heo, Giseon; Major, Paul W.

2008-01-01

The surface chemical composition of dental enamel has been postulated as a contributing factor in the variation of bond strength of brackets bonded to teeth, and hence, the probability of bracket failure during orthodontic treatment. This study systematically investigated the chemical composition of 98 bonding surfaces of human maxillary premolars using X-ray photoelectron spectroscopy (XPS) to ascertain compositional differences between right and left first premolars. The major elements detected in all samples were calcium, phosphorus, oxygen, nitrogen and carbon. Surface compositions were highly variable between samples and several elements were found to be highly correlated. No statistical significant difference in the chemical composition of the maxillary right and left first premolars was found (p > 0.05). Knowledge of the chemical composition of enamel surfaces will facilitate future studies that relate this information to the variations in dental enamel bond strength

A New Multiphase Equation of State for Composition B

Energy Technology Data Exchange (ETDEWEB)

Coe, Joshua Damon [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division; Margevicius, Madeline Alma [Los Alamos National Lab. (LANL), Los Alamos, NM (United States). Theoretical Division

2016-07-25

We describe the construction of a complete equation of state for the high explosive Composition B in its unreacted (inert) form, as well as chemical equilibrium calculations of its detonation products. The multiphase reactant EOS is of SESAME type, and was calibrated to ambient thermal and mechanical data, the shock initiation experiments of Dattelbaum, et al., and the melt line of trinitrotoluene (TNT).

The Chemical Composition of Grape Fibre

Directory of Open Access Journals (Sweden)

Jolana Karovičová

2015-05-01

Full Text Available Dietary fibres from cereals are much more used than dietary fibres from fruits; however, dietary fibres from fruits have better quality. In recent years, for economic and environmental reasons, there has been a growing pressure to recover and exploit food wastes. Grape fibre is used to fortify baked goods, because the fibre can lower blood sugar, cut cholesterol and may even prevent colon cancer. Grape pomace is a functional ingredient in bakery goods to increase total phenolic content and dietary fibre in nourishment. The aim of this study was to determine the chemical composition of commercial fibres, obtained from different Grape sources concerning their chemical properties such as moisture, ash, fat, protein, total dietary fibre. The chemical composition of Grape fibre is known to vary depending on the Grape cultivar, growth climates, and processing conditions. The obliged characteristics of the fibre product are: total dietary fibre content above 50%, moisture lower than 9%, low content of lipids, a low energy value and neutral flavour and taste. Grape pomace represents a rich source of various high-value products such as ethanol, tartrates and malates, citric acid, Grape seed oil, hydrocolloids and dietary fibre. Used commercial Grape fibres have as a main characteristic, the high content of total dietary fibre. Amount of total dietary fibre depends on the variety of Grapes. Total dietary fibre content (TDF in our samples of Grape fibre varied from 56.8% to 83.6%. There were also determined low contents of moisture (below 9%. In the samples of Grape fibre were determined higher amount of protein (8.6 - 10.8%, mineral (1.3 - 3.8% and fat (2.8 - 8.6%. This fact opens the possibility of using both initial by-products as ingredients in the food industry, due to the effects associated with the high total dietary fibre content.

Chemical equilibrium models of interstellar gas clouds

International Nuclear Information System (INIS)

Freeman, A.

1982-10-01

This thesis contains work which helps towards our understanding of the chemical processes and astrophysical conditions in interstellar clouds, across the whole range of cloud types. The object of the exercise is to construct a mathematical model representing a large system of two-body chemical reactions in order to deduce astrophysical parameters and predict molecular abundances and chemical pathways. Comparison with observations shows that this type of model is valid but also indicates that our knowledge of some chemical reactions is incomplete. (author)

Chemical composition and larvicidal activity of Zanthoxylum gilletii ...

African Journals Online (AJOL)

The essential oil was extracted by hydro-distillation, and its chemical compositions determined by gas chromatography mass spectrometry. The oil was dominated by sesquiterpenes and monoterpenes which accounted for 38.30 and 34.00%, respectively. The oil showed good activity against A. gambiae and recorded LC50 ...

Actinide solubility in deep groundwaters - estimates for upper limits based on chemical equilibrium calculations

International Nuclear Information System (INIS)

Schweingruber, M.

1983-12-01

A chemical equilibrium model is used to estimate maximum upper concentration limits for some actinides (Th, U, Np, Pu, Am) in groundwaters. Eh/pH diagrams for solubility isopleths, dominant dissolved species and limiting solids are constructed for fixed parameter sets including temperature, thermodynamic database, ionic strength and total concentrations of most important inorganic ligands (carbonate, fluoride, phosphate, sulphate, chloride). In order to assess conservative conditions, a reference water is defined with high ligand content and ionic strength, but without competing cations. In addition, actinide oxides and hydroxides are the only solid phases considered. Recommendations for 'safe' upper actinide solubility limits for deep groundwaters are derived from such diagrams, based on the predicted Eh/pH domain. The model results are validated as far as the scarce experimental data permit. (Auth.)

Mineral and chemical composition of rock core and surface gas composition in Horonobe Underground Research Laboratory project. Phase 1

International Nuclear Information System (INIS)

Hiraga, Naoto; Ishii, Eiichi

2008-02-01

The following three kinds of analyses were conducted for the 1st phase of the Horonobe Underground Research Laboratory Project. Mineral composition analysis of core sample. Whole rock chemical composition analysis of core sample. Surface gas composition analysis. This document summarizes the results of these analyses. (author)

Chemical composition and microbial load of cheese produced using ...

African Journals Online (AJOL)

Aframomum sceptrum) on the chemical composition and microbial load of cheese was evaluated in a Completely Randomized Design. Cheese produced with 1% bear berry (Aframomum sceptrum) had the highest (P < 0.05) crude protein content ...

Self-assembly and transformation of hybrid nano-objects and nanostructures under equilibrium and non-equilibrium conditions

Science.gov (United States)

Mann, Stephen

2009-10-01

Understanding how chemically derived processes control the construction and organization of matter across extended and multiple length scales is of growing interest in many areas of materials research. Here we review present equilibrium and non-equilibrium self-assembly approaches to the synthetic construction of discrete hybrid (inorganic-organic) nano-objects and higher-level nanostructured networks. We examine a range of synthetic modalities under equilibrium conditions that give rise to integrative self-assembly (supramolecular wrapping, nanoscale incarceration and nanostructure templating) or higher-order self-assembly (programmed/directed aggregation). We contrast these strategies with processes of transformative self-assembly that use self-organizing media, reaction-diffusion systems and coupled mesophases to produce higher-level hybrid structures under non-equilibrium conditions. Key elements of the constructional codes associated with these processes are identified with regard to existing theoretical knowledge, and presented as a heuristic guideline for the rational design of hybrid nano-objects and nanomaterials.

Chemical Composition, antioxidant activity, functional properties and ...

African Journals Online (AJOL)

Chemical Composition, antioxidant activity, functional properties and inhibitory action of unripe plantain ( M. Paradisiacae ) flour. ... of dry matter (48.00 ± 3.96%) and starch (31.10 ± 0.44%) but was low in phenol (1.42 ± 0.03%), protein (3.15 ± 0.042%), ash (5.50 ± 0.42%) and total soluble sugar (0.64 ± 0.001%) (p < 0.05).

Equilibrium chemistry down to 100 K. Impact of silicates and phyllosilicates on the carbon to oxygen ratio

Science.gov (United States)

Woitke, P.; Helling, Ch.; Hunter, G. H.; Millard, J. D.; Turner, G. E.; Worters, M.; Blecic, J.; Stock, J. W.

2018-06-01

We have introduced a fast and versatile computer code, GGCHEM, to determine the chemical composition of gases in thermo-chemical equilibrium down to 100 K, with or without equilibrium condensation. We have reviewed the data for molecular equilibrium constants, kp(T), from several sources and discussed which functional fits are most suitable for low temperatures. We benchmarked our results against another chemical equilibrium code. We collected Gibbs free energies, ΔGf⊖, for about 200 solid and liquid species from the NIST-JANAF database and the geophysical database SUPCRTBL. We discussed the condensation sequence of the elements with solar abundances in phase equilibrium down to 100 K. Once the major magnesium silicates Mg2SiO4[s] and MgSiO3[s] have formed, the dust to gas mass ratio jumps to a value of about 0.0045 which is significantly lower than the often assumed value of 0.01. Silicate condensation is found to increase the carbon to oxygen ratio (C/O) in the gas from its solar value of 0.55 up to 0.71, and, by the additional intake of water and hydroxyl into the solid matrix, the formation of phyllosilicates at temperatures below 400 K increases the gaseous C/O further to about 0.83. Metallic tungsten (W) is the first condensate found to become thermodynamically stable around 1600-2200 K (depending on pressure), several hundreds of Kelvin before subsequent materials such as zirconium dioxide (ZrO2) or corundum (Al2O3) can condense. We briefly discuss whether tungsten, despite its low abundance of 2 × 10-7 times the silicon abundance, could provide the first seed particles for astrophysical dust formation. GGCHEM code is publicly available at http://https://github.com/pw31/GGchemTable D.1 is only available at the CDS via anonymous ftp to http://cdsarc.u-strasbg.fr (http://130.79.128.5) or via http://cdsarc.u-strasbg.fr/viz-bin/qcat?J/A+A/614/A1

Chemical compositions and antimicrobial activity of twig essential ...

African Journals Online (AJOL)

Aghomotsegin

2016-03-09

Mar 9, 2016 ... The chemical composition of twig essential oils of Xylopia malayana, Xylopia elliptica and Xylopia fusca ... Volatile constituents and bioactivity studies are available in the literature on Xylopia aethiopica (Issakou et al., 2014;. Sylvain et al, 2014; Vyry et al, 2014), Xylopia longifolia. (Fourier et al, 1993), ...

Antimicrobial properties and chemical compositions of the petroleum ...

African Journals Online (AJOL)

The study was designed to investigate the antimicrobial and chemical compositions of the petroleum ether extract of theaerial parts of Rauvolfia vomitoria. The aerial parts of the plant were air dried under shade, pounded using wooden mortar and pestle into coarse powder. The coarse powder was extracted in aSoxhlet ...

Equilibrium and non-equilibrium controls on the abundances of clumped isotopologues of methane during thermogenic formation in laboratory experiments: Implications for the chemistry of pyrolysis and the origins of natural gases

Science.gov (United States)

Shuai, Yanhua; Douglas, Peter M. J.; Zhang, Shuichang; Stolper, Daniel A.; Ellis, Geoffrey S.; Lawson, Michael; Lewan, Michael D.; Formolo, Michael; Mi, Jingkui; He, Kun; Hu, Guoyi; Eiler, John M.

2018-02-01

Multiply isotopically substituted molecules ('clumped' isotopologues) can be used as geothermometers because their proportions at isotopic equilibrium relative to a random distribution of isotopes amongst all isotopologues are functions of temperature. This has allowed measurements of clumped-isotope abundances to be used to constrain formation temperatures of several natural materials. However, kinetic processes during generation, modification, or transport of natural materials can also affect their clumped-isotope compositions. Herein, we show that methane generated experimentally by closed-system hydrous pyrolysis of shale or nonhydrous pyrolysis of coal yields clumped-isotope compositions consistent with an equilibrium distribution of isotopologues under some experimental conditions (temperature-time conditions corresponding to 'low,' 'mature,' and 'over-mature' stages of catagenesis), but can have non-equilibrium (i.e., kinetically controlled) distributions under other experimental conditions ('high' to 'over-mature' stages), particularly for pyrolysis of coal. Non-equilibrium compositions, when present, lead the measured proportions of clumped species to be lower than expected for equilibrium at the experimental temperature, and in some cases to be lower than a random distribution of isotopes (i.e., negative Δ18 values). We propose that the consistency with equilibrium for methane formed by relatively low temperature pyrolysis reflects local reversibility of isotope exchange reactions involving a reactant or transition state species during demethylation of one or more components of kerogen. Non-equilibrium clumped-isotope compositions occur under conditions where 'secondary' cracking of retained oil in shale or wet gas hydrocarbons (C2-5, especially ethane) in coal is prominent. We suggest these non-equilibrium isotopic compositions are the result of the expression of kinetic isotope effects during the irreversible generation of methane from an alkyl

EquilTheTA: Thermodynamic and transport properties of complex equilibrium plasmas

International Nuclear Information System (INIS)

Colonna, G.; D'Angola, A.

2012-01-01

EquilTheTA (EQUILibrium for plasma THErmodynamics and Transport Applications) is a web-based software which calculates chemical equilibrium product concentrations from any set of reactants and determines thermodynamic and transport properties for the product mixture in wide temperature and pressure ranges. The program calculates chemical equilibrium by using a hierarchical approach, thermodynamic properties and transport coefficients starting from recent and accurate databases of atomic and molecular energy levels and collision integrals. In the calculations, Debye length and cut-off are consistently updated and virial corrections (up to third order) can be considered. Transport coefficients are calculated by using high order approximations of the Chapman-Enskog method.

Ethylene vinylacetate copolymer and nanographite composite as chemical vapour sensor

International Nuclear Information System (INIS)

Stepina, Santa; Sakale, Gita; Knite, Maris

2013-01-01

Polymer-nanostructured carbon composite as chemical vapour sensor is described, made by the dissolution method of a non-conductive polymer, ethylene vinylacetate copolymer, mixed with conductive nanographite particles (carbon black). Sensor exhibits relative electrical resistance change in chemical vapours, like ethanol and toluene. Since the sensor is relatively cheap, easy to fabricate, it can be used in air quality monitoring and at industries to control hazardous substance concentration in the air, for example, to protect workers from exposure to chemical spills

Stochastic approach to equilibrium and nonequilibrium thermodynamics.

Science.gov (United States)

Tomé, Tânia; de Oliveira, Mário J

2015-04-01

We develop the stochastic approach to thermodynamics based on stochastic dynamics, which can be discrete (master equation) and continuous (Fokker-Planck equation), and on two assumptions concerning entropy. The first is the definition of entropy itself and the second the definition of entropy production rate, which is non-negative and vanishes in thermodynamic equilibrium. Based on these assumptions, we study interacting systems with many degrees of freedom in equilibrium or out of thermodynamic equilibrium and how the macroscopic laws are derived from the stochastic dynamics. These studies include the quasiequilibrium processes; the convexity of the equilibrium surface; the monotonic time behavior of thermodynamic potentials, including entropy; the bilinear form of the entropy production rate; the Onsager coefficients and reciprocal relations; and the nonequilibrium steady states of chemical reactions.

CHEMICAL COMPOSITION VARIABILITY IN THE Uncaria tomentosa (cat’s claw WILD POPULATION

Directory of Open Access Journals (Sweden)

Evelyn Maribel Condori Peñaloza

2015-03-01

Full Text Available Uncaria tomentosa (cat's claw is a vine widely distributed throughout the South-American rainforest. Many studies investigating the chemical composition of cat's claw have focused on the pentacyclic (POA and tetracyclic oxindole alkaloids (TOA, quinovic acid glycosides (QAG, and polyphenols (PPH. Nevertheless, it is still uncertain how environmental factors affect chemical groups. The aim of this work was to better understand the influence of environmental factors (geographic origin, altitude, and season on cat's claw chemical composition. Stem bark, branches and leaf samples were extracted and analyzed by HPLC-PDA. The data obtained were explored by multivariate analysis (HCA and PCA. Higher amounts of oxindole alkaloids and PPH were found in leaves, followed by stem bark and branches. No clear relationship was verified among geographic origin or altitude and chemical composition, which remained unchanged regardless of season (dry or rainy. However, three oxindole alkaloid chemotypes were clearly recognized: chemotype I (POA with cis D/E ring junction; chemotype II (POA with trans D/E ring junction; and chemotype III (TOA. Thus, environmental factors appear to have only a minor influence on the chemical heterogeneity of the cat's claw wild population. Nevertheless, the occurrence of different chemotypes based on alkaloid profiles seems to be clear.

Kinetics of transformation of deformation processed gold-matrix composite

Science.gov (United States)

Wongpreedee, Kageeporn

Gold matrix Ḏeformation-processed M&barbelow;etal M&barbelow;etal C&barbelow;omposites (DMMC) have been developed that have better strength and conductivity than conventional gold alloys. However, DMMC possess metastable two-phase microstructures, and their strength and conductivity decrease after prolonged exposure to elevated temperatures. The kinetics of the transformation from the metastable two-phase microstructure to the equilibrium single-phase solid solution is of interest. This document describes a study of the elevated temperature stability of Au DMMC's and the relationship between microstructure and resistivity of three compositions: Au-7 vol %Ag, Au-14 vol %Ag, and Au-vol 7%Pt. DMMC samples were prepared by a powder metallurgy technique and mechanical processes. The smallest final diameter of these wires was 120 mum. Avrami and Arrhenius relations were used to evaluate the kinetic transformation. The extensive deformation used to produce these composites reshaped the initially equi-axed powder particles into a nanofilamentary composite. Electrical resistivity measurements were used to determine the degree of transformation from the initial metastable nano-filamentary composite to the equilibrium solid solution condition. These measurements indicated that this transformation in Au-14 at%Ag, Au-7 at %Ag Au and Au-7 at %Pt DMMC wires proceeded with activation energies of 141, 156, and 167 kJ/mol, respectively. It is thought that these empirically determined activation energies differ from those determined in single crystal, planar interface Au-Ag and Au-Pt diffusion couples due to chemical potential, surface curvature, and strain effects. The DMMC systems reach the equilibrium solid solution condition faster than single crystal, planar interface systems for two reasons: (1) far more defects (dislocations, grain boundaries, vacancies from non-conservative dislocation motion, etc.) are present in the Au-Ag and Au-Pt DMMC composites, and (2) the small

Chemical Composition of Defatted Cottonseed and Soy Meal Products

Science.gov (United States)

He, Zhongqi; Zhang, Hailin; Olk, Dan C.

2015-01-01

Chemical composition is critical information for product quality and exploration of new use. Hence defatted cottonseed meals from both glanded (with gossypol) and glandless (without gossypol) cotton seeds were separated into water soluble and insoluble fractions, or water soluble, alkali soluble as well as total protein isolates. The contents of gossypol, total protein and amino acids, fiber and carbohydrates, and selected macro and trace elements in these products were determined and compared with each other and with those of soy meal products. Data reported in this work improved our understanding on the chemical composition of different cottonseed meal products that is helpful for more economical utilization of these products. These data would also provide a basic reference for product standards and quality control when the production of the cottonseed meal products comes to pilot and industrial scales. PMID:26079931

Cometary Coma Chemical Composition (C4) Mission

Science.gov (United States)

Carle, Glenn C.; Clark, Benton C.; Knocke, Philip C.; OHara, Bonnie J.; Adams, Larry; Niemann, Hasso B.; Alexander, Merle; Veverka, Joseph; Goldstein, Raymond; Huebner, Walter;

Equilibrium sampling to determine the thermodynamic potential for bioaccumulation of persistent organic pollutants from sediment.

Science.gov (United States)

Jahnke, Annika; MacLeod, Matthew; Wickström, Håkan; Mayer, Philipp

2014-10-07

Equilibrium partitioning (EqP) theory is currently the most widely used approach for linking sediment pollution by persistent hydrophobic organic chemicals to bioaccumulation. Most applications of the EqP approach assume (I) a generic relationship between organic carbon-normalized chemical concentrations in sediments and lipid-normalized concentrations in biota and (II) that bioaccumulation does not induce levels exceeding those expected from equilibrium partitioning. Here, we demonstrate that assumption I can be obviated by equilibrating a silicone sampler with chemicals in sediment, measuring chemical concentrations in the silicone, and applying lipid/silicone partition ratios to yield concentrations in lipid at thermodynamic equilibrium with the sediment (CLip⇌Sed). Furthermore, we evaluated the validity of assumption II by comparing CLip⇌Sed of selected persistent, bioaccumulative and toxic pollutants (polychlorinated biphenyls (PCBs) and hexachlorobenzene (HCB)) to lipid-normalized concentrations for a range of biota from a Swedish background lake. PCBs in duck mussels, roach, eel, pikeperch, perch and pike were mostly below the equilibrium partitioning level relative to the sediment, i.e., lipid-normalized concentrations were ≤CLip⇌Sed, whereas HCB was near equilibrium between biota and sediment. Equilibrium sampling allows straightforward, sensitive and precise measurement of CLip⇌Sed. We propose CLip⇌Sed as a metric of the thermodynamic potential for bioaccumulation of persistent organic chemicals from sediment useful to prioritize management actions to remediate contaminated sites.

The Effect of Composition on Spinel Crystals Equilibrium in Low-Silica High-Level Waste Glasses

International Nuclear Information System (INIS)

Jiricka, Milos; Hrma, Pavel R.; Vienna, John D.

2003-01-01

The liquidus temperature (TL) and the equilibrium mass fraction of spinel were measured in the regions of low-silica (less than 42 mass% SiO2) high-level waste borosilicate glasses within the spinel primary phase field as functions of glass composition. The components that varied, one at a time, were Al2O3, B2O3, Cr2O3, Fe2O3, Li2O, MnO, Na2O, NiO, SiO2, and ZrO2. The effects of Al2O3, B2O3, Fe2O3, NiO, SiO2, and ZrO2 on the TL in this region and in glasses with 42 to 56 mass% SiO2 were similar. However, in the low-silica region, Cr2O3 increased the TL substantially less, and Li2O and Na2O decreased the TL significantly less than in the region with 42 to 56 mass% SiO2. The effect of MnO on the TL of the higher SiO2 glasses is not yet understood with sufficient accuracy. The temperature at which the equilibrium mass fraction of spinel was 1 mass% was 25C to 64C below the TL

Predicting the Chemical composition of herbaceous legumes using ...

African Journals Online (AJOL)

Predicting the Chemical composition of herbaceous legumes using Near Infrared Reflectance Spectroscopy. J F Mupangwa, N Berardo, N T Ngongoni, J H Topps, H Hamudikuwanda, M Ordoardi. Abstract. (Journal of Applied Science in Southern Africa: 2000 6(2): 107-114). http://dx.doi.org/10.4314/jassa.v6i2.16844.

Changes in the chemical composition of the light crude by short-term weathering

International Nuclear Information System (INIS)

Luo, X.; Ma, Q.M.

2006-01-01

In the event of an oil spill, it is important to unambiguously identify the oil and link it to the known source in order to determine environmental impact and legal liability. The fate and behaviour of spilled oil depends on several physical, chemical and biological factors such as evaporation, dissolution, microbial degradation and photooxidation. The chemical composition of the spilled oil changes with weathering. The changes can have a significant effect on the oil's toxicity and can add to the difficulty of identifying spilled oil. This paper presents the results of changes in chemical composition of light crude oil by weathering under natural environmental conditions. Oil samples were analyzed on a gas chromatograph equipped with a mass selective detector. Light crude oil was obtained from the oil cabin of a tanker which spilled oil near the Dalian Sea near China in April 2005. It was shown that the saturated hydrocarbons of light crude oil distribute between n-C 8 and n-C 23 . The most abundant n-alkanes are found in the n-C 10 to n-C 16 . The main chemical compositions of the light crude oil are the n-alkanes and the isoprenoids. The aromatic compounds are subordinate chemical compositions of the light crude oil. A simulated weathering experiment showed that less than n-C 12 of the n-alkanes, toluene, 1,3-dimethyl benzene is lost after 1 day of weathering. The n-C 13 , n-C 14 , naphthalene and 2-methyl-naphthalene are lost on the fifth day of weathering. N-C 15 alkane composition indicates some weatherproof capability. The ratios of n-C 17 /pristine and n-C 18 /phytane were unchanged and useful in identifying the source of the light crude oil during the first 8-day weathering period. By the twenty-first day of weathering, the chemical composition underwent extreme alteration, and the source of the pollution could not be determined by the ratios of pristine/phytane. 12 refs., 3 tabs., 7 figs

Measurement of vapor-liquid-liquid phase equilibrium-Equipment and results

DEFF Research Database (Denmark)

Frost, Michael Grynnerup; von Solms, Nicolas; Richon, Dominique

2015-01-01

There exists a need for new accurate and reliable experimental data, preferably with full characterization of all the phases present in equilibrium. The need for high-quality experimental phase equilibrium data is the case for the chemical industry in general. All areas deal with processes whose ...

Line radiative transfer and statistical equilibrium

NARCIS (Netherlands)

Kamp, Inga

Atomic and molecular line emission from protoplanetary disks contains key information of their detailed physical and chemical structures. To unravel those structures, we need to understand line radiative transfer in dusty media and the statistical equilibrium, especially of molecules. I describe

Toxicological characterization of chemicals produced from laser irradiation of graphite composite materials

International Nuclear Information System (INIS)

Kwan, J.

1990-11-01

One of the major potential hazards associated with laser machining of graphite composite materials is the toxic fumes and gases that are generated. When exposed to the intense energy of the laser beam, the organic polymer matrix of the composite material may decompose into various toxic by-products. To advance the understanding of the laser machining process from a health and safety viewpoint, this particular study consisted of the following steps: collect and analyze gaseous by-products generated during laser machining; collect particulates generated during laser machining and chemically extract them to determine the chemical species that may have absorbed or recondensed onto these particles; and review and evaluate the toxicity of the identified chemical species

Application of electron-chemical curing in the production of thin composite materials

International Nuclear Information System (INIS)

Kopetchenov, V.; Shik, V.; Konev, V.; Kurapov, A.; Misin, I.; Gavrilov, V.; Malik, V.

1993-01-01

Thousands of tons of various thin composite materials in rolls for electrotechnical and domestic application including a whole range of electrical insulating materials, such as varnished and polymer fabrics, glass-micatapes, prepregs, thin laminated plastics and clad laminates, materials for decorative and domestic purposes - pressure sensitive adhesive tape and laminates, covering and finishing compositions based on fabrics, films and papers are produced. An important advantage of the electron-chemical processing in the production of composite materials is an essential energy saving (reduction of energy consumption 3-5 times). Absence of the organic diluents in binders decreases fire and explosion hazards of the production and sufficiently decreases danger for the environment of the technology used. Research and Production Company ''Polyrad'' is engaged in the development of technologies and equipment for the production of thin composite materials by the Electron-Chemical Method. (author)

Prebiotic Potential and Chemical Composition of Seven Culinary Spice Extracts

OpenAIRE

Lu, Qing‐Yi; Summanen, Paula H.; Lee, Ru‐Po; Huang, Jianjun; Henning, Susanne M.; Heber, David; Finegold, Sydney M.; Li, Zhaoping

2017-01-01

Abstract The objective of this study was to investigate prebiotic potential, chemical composition, and antioxidant capacity of spice extracts. Seven culinary spices including black pepper, cayenne pepper, cinnamon, ginger, Mediterranean oregano, rosemary, and turmeric were extracted with boiling water. Major chemical constituents were characterized by RP‐HPLC‐DAD method and antioxidant capacity was determined by measuring colorimetrically the extent to scavenge ABTS radical cations. Effects o...

Quantifying differences in the impact of variable chemistry on equilibrium Uranium(VI) adsorption properties of aquifer sediments.

Science.gov (United States)

Stoliker, Deborah L; Kent, Douglas B; Zachara, John M

2011-10-15

Uranium adsorption-desorption on sediment samples collected from the Hanford 300-Area, Richland, WA varied extensively over a range of field-relevant chemical conditions, complicating assessment of possible differences in equilibrium adsorption properties. Adsorption equilibrium was achieved in 500-1000 h although dissolved uranium concentrations increased over thousands of hours owing to changes in aqueous chemical composition driven by sediment-water reactions. A nonelectrostatic surface complexation reaction, >SOH + UO₂²⁺ + 2CO₃²⁻ = >SOUO₂(CO₃HCO₃)²⁻, provided the best fit to experimental data for each sediment sample resulting in a range of conditional equilibrium constants (logK(c)) from 21.49 to 21.76. Potential differences in uranium adsorption properties could be assessed in plots based on the generalized mass-action expressions yielding linear trends displaced vertically by differences in logK(c) values. Using this approach, logK(c) values for seven sediment samples were not significantly different. However, a significant difference in adsorption properties between one sediment sample and the fines (< 0.063 mm) of another could be demonstrated despite the fines requiring a different reaction stoichiometry. Estimates of logK(c) uncertainty were improved by capturing all data points within experimental errors. The mass-action expression plots demonstrate that applying models outside the range of conditions used in model calibration greatly increases potential errors.

Estimation of chemical carcass composition from 8th rib characteristics with Belgian blue double-muscled bulls.

Science.gov (United States)

De Campeneere, S; Fiems, L O; Van de Voorde, G; Vanacker, J M; Boucque, C V; Demeyer, D I

1999-01-01

Characteristics from the 8th rib cut: chemical composition, tissue composition after dissection, specific gravity (SG) and m. longissimus thoracis (LT) composition, collected on 17 Belgian Blue double-muscled fattening bulls were used to generate equations for predicting chemical carcass composition. Carcass composition was best predicted from chemical analysis of the 8th rib cut and the empty body weight (EBW) of the bull. Carcass chemical fat content (CCF, kg) was predicted from the 8th rib cut fat content (ether extract, 8RF, kg) by the following regression: CCF=1.94+27.37 8RF (R(2)=0.957, RSD =9.89%). A higher coefficient was found for carcass water (CCW, kg) predicted from 8RF and EBW: CCW=-2.26+0.28 EBW-34.28 8RF (R(2)=0.997, RSD=1.48%). No parameter was found to improve the prediction of CCP from EBW solely: CCP=-0.86+0.08 EBW (R(2) =0.992, RSD=2.61%). Prediction equations based solely on LT composition had low R(2) values of between 0.38 and 0.67, whereas no significant equations were found using SG. However, equations based on EBW had R(2) values between 0.78 and 0.99. Chemical components of the 8th rib cut in combination with EBW are most useful in predicting the chemical composition of the carcass of Belgian-Blue double-muscled bulls.

Has Chemical Education Reached Equilibrium?

Science.gov (United States)

Moore, John W.

1997-06-01

The other day I got to thinking about whether something akin to Le Chatelier's principle operates in chemical education. That is, whenever someone alters the conditions under which we interact with students, there is a shift in the system that attempts to minimize or counteract the change.

Global phase equilibrium calculations: Critical lines, critical end points and liquid-liquid-vapour equilibrium in binary mixtures

DEFF Research Database (Denmark)

Cismondi, Martin; Michelsen, Michael Locht

2007-01-01

A general strategy for global phase equilibrium calculations (GPEC) in binary mixtures is presented in this work along with specific methods for calculation of the different parts involved. A Newton procedure using composition, temperature and Volume as independent variables is used for calculation...

MOFwich: Sandwiched Metal-Organic Framework-Containing Mixed Matrix Composites for Chemical Warfare Agent Removal.

Science.gov (United States)

Peterson, Gregory W; Lu, Annie X; Hall, Morgan G; Browe, Matthew A; Tovar, Trenton; Epps, Thomas H

2018-02-28

This work describes a new strategy for fabricating mixed matrix composites containing layered metal-organic framework (MOF)/polymer films as functional barriers for chemical warfare agent protection. Through the use of mechanically robust polymers as the top and bottom encasing layers, a high-MOF-loading, high-performance-core layer can be sandwiched within. We term this multifunctional composite "MOFwich". We found that the use of elastomeric encasing layers enabled core layer reformation after breakage, an important feature for composites and membranes alike. The incorporation of MOFs into the core layer led to enhanced removal of chemical warfare agents while simultaneously promoting moisture vapor transport through the composite, showcasing the promise of these composites for protection applications.

Whole system chemical geothermometry

International Nuclear Information System (INIS)

Pang Zhonghe

1999-01-01

Chemical and isotopic geothermometers are equations or models based on temperature dependent chemical reactions or isotope equilibrium fractionation reactions from which equilibrium temperatures of these reactions can be calculated. The major drawback of all the conventional geothermometry methods lies in their incapability on making a judgement on the equilibrium status of the studied systems. This review will focus on two of recent approaches in this field. Zhangzhou Geothermal Field in SE China will be used as an example to demonstrate the applications

In vivo ultrasound and biometric measurements predict the empty body chemical composition in Nellore cattle.

Science.gov (United States)

Castilhos, A M; Francisco, C L; Branco, R H; Bonilha, S F M; Mercadante, M E Z; Meirelles, P R L; Pariz, C M; Jorge, A M

2018-05-04

Evaluation of the body chemical composition of beef cattle can only be measured postmortem and those data cannot be used in real production scenarios to adjust nutritional plans. The objective of this study was to develop multiple linear regression equations from in vivo measurements, such as ultrasound parameters [backfat thickness (uBFT, mm), rump fat thickness (uRF, mm), and ribeye area (uLMA, cm2)], shrunk body weight (SBW, kg), age (AG, d), hip height (HH, m), as well as from postmortem measurements (composition of the 9th to 11th rib section) to predict the empty body and carcass chemical composition for Nellore cattle. Thirty-three young bulls were used (339 ± 36.15 kg and 448 ± 17.78 d for initial weight and age, respectively). Empty body chemical composition (protein, fat, water, and ash in kg) was obtained by combining noncarcass and carcass components. Data were analyzed using the PROC REG procedure of SAS software. Mallows' Cp values were close to the ideal value of number of independent variables in the prediction equations plus one. Equations to predict chemical components of both empty body and carcass using in vivo measurements presented higher R2 values than those determined by postmortem measurements. Chemical composition of the empty body using in vivo measurements was predicted with R2 > 0.73. Equations to predict chemical composition of the carcass from in vivo measurements showed R2 lower (R2Chemical compounds from components of the empty body of Nellore cattle can be calculated by the following equations: protein (kg) = 47.92 + 0.18 × SBW - 1.46 × uRF - 30.72 × HH (R2 = 0.94, RMSPE = 1.79); fat (kg) = 11.33 + 0.16 × SBW + 2.09 × uRF - 0.06 × AG (R2 = 0.74, RMSPE = 4.18); water (kg) = - 34.00 + 0.55 × SBW + 0.10 × AG - 2.34 × uRF (R2 = 0.96, RMSPE = 5.47). In conclusion, the coefficients of determination (for determining the chemical composition of the empty body) of the equations derived from in vivo measures were higher than those