DOCSLIB.ORG

Osmotic Coefficients and Mean Activity Coefficients of Uni-Univalent Electrolytes in Water at 25°C

Total Page：16

File Type：pdf, Size：1020Kb

Download full-text PDF Read full-text
Osmotic Coefficients and Mean Activity Coefficients of Uni-Univalent Electrolytes in Water at 25°C Osmotic Coefficients and Mean Activity Coefficients of Uni-univalent Electrolytes in Water at 25°C Cite as: Journal of Physical and Chemical Reference Data 1, 1047 (1972); https://doi.org/10.1063/1.3253108 Published Online: 29 October 2009 Walter J. Hamer, and Yung-Chi Wu ARTICLES YOU MAY BE INTERESTED IN Mean ionic activity coefficients in aqueous NaCl solutions from molecular dynamics simulations The Journal of Chemical Physics 142, 044507 (2015); https://doi.org/10.1063/1.4906320 Thermodynamic Properties of Aqueous Sodium Chloride Solutions Journal of Physical and Chemical Reference Data 13, 1 (1984); https://doi.org/10.1063/1.555709 Evaluated activity and osmotic coefficients for aqueous solutions: thirty-six uni-bivalent electrolytes Journal of Physical and Chemical Reference Data 10, 671 (1981); https:// doi.org/10.1063/1.555646 Journal of Physical and Chemical Reference Data 1, 1047 (1972); https://doi.org/10.1063/1.3253108 1, 1047 © 1972 The U. S. Secretary of Commerce on behalf of the United States. Osmotic Coefficients and Mean Activity Coefficients of Uni-univalent Electrolytes in Water at 25°C Walter J. Hamer* and Yung-Chi Wu Institute for Basic Standards National Bureau of Standards, Washington, D.C. 20234 This paper gives values for the osmotic coefficients and mean activity coefficents of uni-univalent electrolytes in aqueous solutions at 25 0c. The values are expressed on the molality or weight basis. The data available in the literature have been corrected to the presently accepted scales of atomic weights (1969) and temperature (lPST 1968) and, where necessary, to the absolute electrical units of 1969 and the fundamental constants of 1963. The selected values of osmotic coefficients and mean activity coefficients for individual electrolytes have been made internally consistent thermodynamically. In some cases estimated values are given; in other cases, references only are given when the data are sparse or unsuited to critical evaluation. Values of the osmotic coefficients and mean activity coeffi· cients of 79 compounds are given together with the standard deviation, variance, and normalized standard deviation of their fit to equations which express these quantities as functions of electrolyte concentration. Finally, literature references are given to data on 51 additional uni-univalent electrolytes. Key words: Activity coefficients; osmotic coefficients; p'I{cess Gibbs energy for electrolytes; critically evaluated data. Contents Page Page Introduction ................................................... 1048 3.3 Electromotive Forces (emfs) of Galvanic 1. General Relations for Chemical Potentials, Cells without Liquid Junctions ............... 1052 Activities, and Activity Coefficients ............ 1048 a. Type 1: One Fluid ............................. 1052 2. Theoretical Exprcssions for Activity Coeffi- h. Typc 2: Two Fluids............................ 1052 cients. .. .. .. ... .. .. .. .. 1049 3.4 Emfs of Galvanic Cells with Transference... 1052 3. Determinations of Activity Coefficients ............. 1050 3.5 Diffusion.............................................. 1053 3.1 Vapor-Pressure Lowering and Osmotic 4. Literature Data on Osmotic and Mean Activity Coefficient ......................................... 1050 Coefficients ............................................. 1053 3.2 Isopiestic or Vapor-Pressure 'Equilibra- 5. Evaluation of Data on Osmotic and Mean tion .................................................. 1051 Activity Coefficients.................................. 1055 '6. Compounds................................................ 1058 6.1 Index to Compounds ............................... 1058 *Present address: 3028 Dogwood Street, N.W". Washington, D.C. 20015. 6.2 Compounds Evaluated .... " ....................... 1058 6.3 Compounds Referenced Only ...... ~ ............ 1096 7. Copyright © 1972 by the U.S. Secretary of Commerce on behalf of the United States. This Acknowledgment ......................................... 1097 copyright will be assigned to the American Institute of Physics and the American Chemical 8. References ................................................. 1097 Society. to whom all requests regarding reproduction should be addressed. 1047 J. Phys. Chem. Ref. Data, VoJ. 1, No.4, 1972 1048 w. J. HAMER AND V-C. WU Introduction This paper gives values for the osmotic coefficients and Here the subscript n' indicates the constancy of all mean activity coefficients of uni~univalent electrolytes components except component a. Thus, the chemical in aqueous solutions at 25°C. The values are expressed potential can be expressed in various ways depending on the molality or weight basis. When the literature gives on what variables are held constant during an experi­ values for both the osmotic coefficients and the mean ment. The last equality is the one generally used in activity coefficients in the same investigation, the in· defining the chemical potential, since experiments temal consistency of the two sets of data has been may be readily designed wherein the temperature checked by iteration using equations which express the and pressure are maintained constant. variation of osmotic coefficients and mean activity As the energy, entropy, enthalpy (heat content), coefficients with molality. The osmotic coefficient, cf>, Helmholtz energy, and Gibbs energy are defined only and the mean activity coefficient, 'Y, are related through by differential equations, we can determine only the excess Gibbs energy, tJ.Gex given by tJ.Gex = differences of these quantities between two states of 2 m RT(1 - cf> + In y), where m is molality, R the gas con­ a system containing the same quantity of matter. It is stant, and T the Kelvin temperatnre. Whp.n only osmotir. therefore customary to tabulate the differences from coefficients or mean activity coefficients are reported some standard state, which is equivalent to an arbi­ in· the literature, the data given were critically evalu~ trary assumption that the various functions are each ated, and the other function was then calculated by the zero in the standard states. For general purposes it is appropriate equation. The theoretical background of customary to assume that the energy, or the enthalpy, of the equations used in analyzing the data is discussed. each· element at some standard temperature, usually The strengths and weaknesses of the various experi­ 25°C, and some standard pressure, usually one atmos~ mental techniques used in determining activity coeffi­ phere, and in its most stable form under these conditions cients are also discussed. is zero. This same standard state may be adopted for the entropy, Helmholtz energy, and Gibbs energy, although 1. General Relarions for Chemical Potentials, the entropy is sometimes taken as zero at a temperature Activities, and Activity Coefficients of 0 K in accordance with the third law of thermo­ dynamics. A knowledge of the individual heat capacities For closed isolated systems to which no matter is and volumcs permits thc calculation of these quantities added or withdrawn, thermodynamics gives: under other conditions. See later for the choice of the standard state for electrolytic solutions. dU = TdS - pdV, (1.1) The same considerations apply to the chemical where U is energy, T the Kelvin temperature (K), S the potential, i.e., only differences from an arbitrarily entropy, P the pressure, and V the volume. For an open selected standard state can be determined. Throughout system to which matter may he added or withdrawn (for this paper the chemical potential is defined in terms of example, addition of a saIt to water or removal .of the partial molal Gibbs energy (fourth equality in equa­ water from a salt solution by evaporation) one has tion 1.6). The difference in chemical potential between two states (compositions) of an ideal solution is given by: dU = TdS - pdV + /LAdnA + ILBdnB ... + J.Lzdnz, ".1-II.~= RT In Pi=RT In Xi (1.7) (1.2) r' rl , " Pi Xi where the n's represent the number of moles of com­ ponent A, B, etc., represented by subscripts and the where i denotes component i, and p and X denote, /L's represent the Gibbs' chemical potential of the respectively, the vapor pressure and mole fraction. If various components. Since from thermodynamic one of the compositions is the pure component with considerations, xi = 1, pi = pi, and lLi JLi, then G = U - TS + pV = Gibbs energy, (1.3) (1.8) H = U + pV = Enthalpy (or heat content), (1.4) where the relative vapor pressure of component i is equal to the mole fraction of component i. For real or A = U - TS = Helmholtz energy, (1.5) non-ideal solutions this equation becomes the chemical potential for component a, for example, lLi= IL~+RT In~= IL,+ RT In ai. (1.9) may be defined in a multiplicity of ways as follows: where at is the activity of component i and defined as the /LA = (au/ana)s,v,n' (aH/ana)s,p,n' relative fugacity, and /L~ is the chemical potential when (aA/ana) T,V ,n' -" (aG/{)na) T,p,n'. (1.6) the aCllv it y i5 unity. J. Phys. Chem. Ref. Data, Vol. 1, No.4, 1972 OSMOTIC AND ACTIVITY COEFFICIENTS 1049 F or solutions of electrolytes the standard state is where Zi is the ionic valence. Henceforth in this paper m chosen so that the ratio of the activity to the concentra­ and y will be used to denote the mean quantities of tion is equal to unity in the limit of c = 0 where the molality and activity coefficient. In this paper which laws of ideal solutions are obeyed. G. N. Lewis [1)1 deals exclusively with uni-univalent electrolytes, v+.
Load more

Recommended publications
  • Prediction of Osmotic Coefficients by Pair Correlation Function Method" (1991)
    New Jersey Institute of Technology Digital Commons @ NJIT Dissertations Electronic Theses and Dissertations Spring 1-31-1991 Thermodynamics of strong electrolyte solutions : prediction of osmotic coefficientsy b pair correlation function method One Kwon Rim New Jersey Institute of Technology Follow this and additional works at: https://digitalcommons.njit.edu/dissertations Part of the Chemical Engineering Commons Recommended Citation Rim, One Kwon, "Thermodynamics of strong electrolyte solutions : prediction of osmotic coefficients by pair correlation function method" (1991). Dissertations. 1145. https://digitalcommons.njit.edu/dissertations/1145 This Dissertation is brought to you for free and open access by the Electronic Theses and Dissertations at Digital Commons @ NJIT. It has been accepted for inclusion in Dissertations by an authorized administrator of Digital Commons @ NJIT. For more information, please contact [email protected]. Copyright Warning & Restrictions The copyright law of the United States (Title 17, United States Code) governs the making of photocopies or other reproductions of copyrighted material. Under certain conditions specified in the law, libraries and archives are authorized to furnish a photocopy or other reproduction. One of these specified conditions is that the photocopy or reproduction is not to be “used for any purpose other than private study, scholarship, or research.” If a, user makes a request for, or later uses, a photocopy or reproduction for purposes in excess of “fair use” that user may be
    [Show full text]
  • Thermodynamic Properties of 1:1 Salt Aqueous Solutions with the Electrolattice M
    D o s s i e r This paper is a part of the hereunder thematic dossier published in OGST Journal, Vol. 68, No. 2, pp. 187-396 and available online here Cet article fait partie du dossier thématique ci-dessous publié dans la revue OGST, Vol. 68, n°2, pp. 187-396 et téléchargeable ici © Photos: IFPEN, Fotolia, X. DOI: 10.2516/ogst/2012094 DOSSIER Edited by/Sous la direction de : Jean-Charles de Hemptinne InMoTher 2012: Industrial Use of Molecular Thermodynamics InMoTher 2012 : Application industrielle de la thermodynamique moléculaire Oil & Gas Science and Technology – Rev. IFP Energies nouvelles, Vol. 68 (2013), No. 2, pp. 187-396 Copyright © 2013, IFP Energies nouvelles 187 > Editorial électrostatique ab initio X. Rozanska, P. Ungerer, B. Leblanc and M. Yiannourakou 217 > Improving the Modeling of Hydrogen Solubility in Heavy Oil Cuts Using an Augmented Grayson Streed (AGS) Approach 309 > Improving Molecular Simulation Models of Adsorption in Porous Materials: Modélisation améliorée de la solubilité de l’hydrogène dans des Interdependence between Domains coupes lourdes par l’approche de Grayson Streed Augmenté (GSA) Amélioration des modèles d’adsorption dans les milieux poreux R. Torres, J.-C. de Hemptinne and I. Machin par simulation moléculaire : interdépendance entre les domaines J. Puibasset 235 > Improving Group Contribution Methods by Distance Weighting Amélioration de la méthode de contribution du groupe en pondérant 319 > Performance Analysis of Compositional and Modified Black-Oil Models la distance du groupe For a Gas Lift Process A. Zaitseva and V. Alopaeus Analyse des performances de modèles black-oil pour le procédé d’extraction par injection de gaz 249 > Numerical Investigation of an Absorption-Diffusion Cooling Machine Using M.
    [Show full text]
  • CH. 9 Electrolyte Solutions
    CH. 9 Electrolyte Solutions 9.1 Activity Coefficient of a Nonvolatile Solute in Solution and Osmotic Coefficient for the Solvent As shown in Ch. 6, the chemical potential is 0 where i is the chemical potential in the standard state and is a measure of concentration. For a nonvolatile solute, its pure liquid is often not a convenient standard state because a pure nonvolatile solute cannot exist as a liquid. For the dissolved solute, * i is the chemical potential of i in a hypothetical ideal solution at unit concentration (i = 1). In the ideal solution i = 1 for all compositions In real solution, i 1 as i 0 A common misconception: The standard state for the solute is the solute at infinite dilution. () At infinite dilution, the chemical potential of the solute approaches . Thus, the standard state should be at some non-zero concentration. A standard state need not be physically realizable, but it must be well- defined. For convenience, unit concentration i = 1 is used as the standard state. Three composition scales: Molarity (moles of solute per liter of solution, ci) The standard state of the solute is a hypothetical ideal 1-molar solution of i. (c) In real solution, i 1 as ci 0 Molality (moles of solute per kg of solvent, mi) // commonly used for electrolytes // density of solution not needed The standard state is hypothetical ideal 1-molal solution of i. (m) In real solution, i 1 as mi 0 Mole fraction xi Molality is an inconvenient scale for concentrated solution, and the mole fraction is a more convenient scale.
    [Show full text]
  • Friedman's Excess Free Energy and the Mcmillan–Mayer Theory Of
    Pure Appl. Chem., Vol. 85, No. 1, pp. 105–113, 2013. http://dx.doi.org/10.1351/PAC-CON-12-05-08 © 2012 IUPAC, Publication date (Web): 29 December 2012 Friedman’s excess free energy and the McMillan–Mayer theory of solutions: Thermodynamics* Juan Luis Gómez-Estévez Departament de Física Fonamental, Facultat de Física, Universitat de Barcelona, Diagonal 645, E-08028, Barcelona, Spain Abstract: In his version of the theory of multicomponent systems, Friedman used the anal- ogy which exists between the virial expansion for the osmotic pressure obtained from the McMillan–Mayer (MM) theory of solutions in the grand canonical ensemble and the virial expansion for the pressure of a real gas. For the calculation of the thermodynamic properties of the solution, Friedman proposed a definition for the “excess free energy” that is a reminder of the ancient idea for the “osmotic work”. However, the precise meaning to be attached to his free energy is, within other reasons, not well defined because in osmotic equilibrium the solution is not a closed system and for a given process the total amount of solvent in the solu- tion varies. In this paper, an analysis based on thermodynamics is presented in order to obtain the exact and precise definition for Friedman’s excess free energy and its use in the compar- ison with the experimental data. Keywords: excess functions; free energy; Friedman; McMillan–Mayer; osmotic pressure; theory of solutions. INTRODUCTION The McMillan–Mayer (MM) theory of solutions [1–6] is a general theory that was originally formu- lated within the context of the grand canonical ensemble.
    [Show full text]
  • Section 1: Identification
    RPP-RPT-50703 Rev.01A 8/23/2016 - 10:10 AM 1 of 77 Release Stamp DOCUMENT RELEASE AND CHANGE FORM Prepared For the U.S. Department of Energy, Assistant Secretary for Environmental Management By Washington River Protection Solutions, LLC., PO Box 850, Richland, WA 99352 Contractor For U.S. Department of Energy, Office of River Protection, under Contract DE-AC27-08RV14800 DATE: TRADEMARK DISCLAIMER: Reference herein to any specific commercial product, process, or service by trade name, trademark, manufacturer, or otherwise, does not necessarily constitute or imply its endorsement, recommendation, or favoring by the United States government or any agency thereof or its contractors or subcontractors. Printed in the United States of America. Aug 23, 2016 1. Doc No: RPP-RPT-50703 Rev. 01A 2. Title: Development of a Thermodynamic Model for the Hanford Tank Waste Simulator (HTWOS) 3. Project Number: ☒ N/A 4. Design Verification Required: ☐ Yes ☒ No 5. USQ Number: ☒ N/A 6. PrHA Number Rev. ☒ N/A Clearance Review Restriction Type: public 7. Approvals Title Name Signature Date Checker CREE, LAURA H CREE, LAURA H 08/16/2016 Clearance Review RAYMER, JULIA R RAYMER, JULIA R 08/23/2016 Document Control Approval MANOR, TAMI MANOR, TAMI 08/23/2016 Originator BRITTON, MICHAEL D BRITTON, MICHAEL D 08/16/2016 Quality Assurance DELEON, SOSTEN O DELEON, SOSTEN O 08/16/2016 Responsible Manager CREE, LAURA H CREE, LAURA H 08/16/2016 8. Description of Change and Justification Updated the reduced chemical potential coefficient vlaues for Na2SO4 and Na2SO4·10H2O in Table A.1, as the original values were incorrect.
    [Show full text]
  • 3. Activity Coefficients of Aqueous Species 3.1. Introduction
    3. Activity Coefficients of Aqueous Species 3.1. Introduction The thermodynamic activities (ai) of aqueous solute species are usually defined on the basis of molalities. Thus, they can be described by the product of their molal concentrations (mi) and their γ molal activity coefficients ( i): γ ai = mi i (77) The thermodynamic activity of the water (aw) is always defined on a mole fraction basis. Thus, it can be described analogously by product of the mole fraction of water (xw) and its mole fraction λ activity coefficient ( w): λ aw = xw w (78) It is also possible to describe the thermodynamic activities of aqueous solutes on a mole fraction (x) basis. However, such mole fraction-based activities (ai ) are not the same as the more familiar (m) molality-based activities (ai ), as they are defined with respect to different choices of standard λ states. Mole fraction based activities and activity coefficients ( i), are occasionally applied to aqueous nonelectrolyte species, such as ethanol in water. In geochemistry, the aqueous solutions of interest almost always contain electrolytes, so mole-fraction based activities and activity co- efficients of solute species are little more than theoretical curiosities. In EQ3/6, only molality- (m) based activities and activity coefficients are used for such species, so ai always implies ai . Be- cause of the nature of molality, it is not possible to define the activity and activity coefficient of (x) water on a molal basis; thus, aw always means aw . Solution thermodynamics is a construct designed to approximate reality in terms of deviations from some defined ideal behavior.
    [Show full text]
  • Electrolyte Solutions: Thermodynamics, Crystallization, Separation Methods
    Downloaded from orbit.dtu.dk on: Oct 06, 2021 Electrolyte Solutions: Thermodynamics, Crystallization, Separation methods Thomsen, Kaj Link to article, DOI: 10.11581/dtu:00000073 Publication date: 2009 Document Version Publisher's PDF, also known as Version of record Link back to DTU Orbit Citation (APA): Thomsen, K. (2009). Electrolyte Solutions: Thermodynamics, Crystallization, Separation methods. https://doi.org/10.11581/dtu:00000073 General rights Copyright and moral rights for the publications made accessible in the public portal are retained by the authors and/or other copyright owners and it is a condition of accessing publications that users recognise and abide by the legal requirements associated with these rights. Users may download and print one copy of any publication from the public portal for the purpose of private study or research. You may not further distribute the material or use it for any profit-making activity or commercial gain You may freely distribute the URL identifying the publication in the public portal If you believe that this document breaches copyright please contact us providing details, and we will remove access to the work immediately and investigate your claim. Electrolyte Solutions: Thermodynamics, Crystallization, Separation methods 2009 Kaj Thomsen, Associate Professor, DTU Chemical Engineering, Technical University of Denmark [email protected] 1 List of contents 1 INTRODUCTION ................................................................................................................. 5 2 CONCENTRATION
    [Show full text]
  • Desalination by Salt Replacement and Ultrafiltration
    Desalination by salt replacement and ultrafiltration. Item Type Thesis-Reproduction (electronic); text Authors Muller, Anthony B. Publisher The University of Arizona. Rights Copyright © is held by the author. Digital access to this material is made possible by the University Libraries, University of Arizona. Further transmission, reproduction or presentation (such as public display or performance) of protected items is prohibited except with permission of the author. Download date 06/10/2021 02:24:08 Link to Item http://hdl.handle.net/10150/191593 DESALINATION BY SALT REPLACEMENT AND ULTRAFILTRATION by Anthony Barton Muller A Thesis Submitted to the Faculty of the DEPARTMENT OF HYDROLOGY AND WATER RESOURCES In Partial Fulfillment of the Requirements For the Degree of MASTER OF SCIENCE WITH A MAJOR IN HYDROLOGY In the Graduate College THE UNIVERSITY OF ARIZONA 1974 STATEMENT BY AUTHOR This thesis has been submitted in partial fulfillment of require- ments for an advanced degree at The University of Arizona and is deposited in the University Library to be made available to borrowers under rules of the Library. Brief quotations from this thesis are allowable without special permission, provided that accurate acknowledgment of source is made. Request for permission for extended quotation from or reproduction of this manuscript in whole or in part may be granted by the head of the major department or the Dean of the Graduate College when in his judgment the proposed use of the material is in the interests of scholarship. In all other instances, however, permission must be obtained from the author. SIGN: APPROVAL BY THESIS DIRECTOR This thesis has been approved on the date shown below: D.
    [Show full text]
  • Determination of Osmotic Coefficients of Aqueous Solutions Of
    Indian Journal of Chemistry Vol. 41A, June 2002, pp. 1184-1187 Determination of osmotic coefficients of and can be used from 303 K to temperature below the aqueous solutions of polyhydroxylated freezing point of the solvent. compounds at various temperatures Determination of the osmotic coefficients of the aqueous solutions by VPO has been limited to a few 3 S 6 b papers . Continuing our previous work ,7, the present Zuo-Ning Gao* a. b, Jin-Fu Li a & Xiao-Lin Wen note deals with aqueous solutions of glycol, glycerol, a Department of Chemistry, Ningxia University, Yinchuan 750021, P. R. China sucrose and glucose at various temperatures. b Department of Chemistry, Lanzhou University, Lanzhou Experimental 730001, P. R. China All measurements were carried out on aqueous Received 3 May 2001; revised II December 2001 solutions of different solutes (glycol, glycerol, sucrose and glucose) at 313, 323 and 333 K over the Osmotic coefficients of aqueous solutions of polyhydroxylated compounds such as glycol, glycerol, sucrose and glucose at concentration range of 0.0 - 2.0 mol kg" for glycol various temperatures over the concentration range of 0.0 - 2. 1 and sucrose, 0.0 - 2.1 mol kg" for glycerol and mol kg ·1 and 0.0 - 2.0 mol kg·1 have been determined, glucose, respectively, from which the osmotic respectively. Using a linear least-squares fitting routine, the coefficients were derived, using a knauer vapour osmotic coefficients have been fitted by a simple polynomial pressure osmometer Model 11.0 in combination with equation. It is found th at the relation between the experimental 8 results of th e molal osmotic coefficients <t> and the molal a digital meter and a recorder .
    [Show full text]
  • Physical Chemistry Laboratory I CHEM 445 Experiment 1 Freezing Point Depression of Electrolytes Revised, 01/13/03
    Physical Chemistry Laboratory I CHEM 445 Experiment 1 Freezing Point Depression of Electrolytes Revised, 01/13/03 Colligative properties are properties of solutions that depend on the concentrations of the samples and, to a first approximation, do not depend on the chemical nature of the samples. A colligative property is the difference between a property of a solvent in a solution and the same property of the pure solvent: vapor pressure lowering, boiling point elevation, freezing point depression, and osmotic pressure. We are grateful for the freezing point depression of aqueous solutions of ethylene glycol or propylene glycol in the winter and continually grateful to osmotic pressure for transport of water across membranes. Colligative properties have been used to determine the molecular weights of non-volatile non-electrolytes. Colligative properties can be described reasonably well by a simple model for solutions of non-electrolytes. The “abnormal” colligative properties of electrolyte solutions supported the Arrhenius theory of ionization. Deviations from ideal behavior for electrolyte solutions led to the determination of activity coefficients and the development of the theory of interionic attractions. The equation for the freezing point depression of a solution of a non-electrolyte as a function of molality is a very simple one: ∆TF = KF m (1) The constant KF, the freezing point depression constant, is a property of the solvent only, as given by the following equation, whose derivation is available in many physical chemistry texts1: o 2 MW(Solvent)R()TF KF = (2) 1000∆HF o In equation (2), R is the gas constant in J/K*mol, TF is the freezing point of the solvent (K), ∆HF is the heat of fusion of the solvent in J/mol, and the factor of 1000 is needed to convert from g to o kg of water for molality.
    [Show full text]
  • TEMPERATURE EFFECTS on the ACTIVITY COEFFICIENT of the BICARBONATE ION Thesis by Fernando Cadena Cepeda in Partial Fulfillment O
    TEMPERATURE EFFECTS ON THE ACTIVITY COEFFICIENT OF THE BICARBONATE ION Thesis by Fernando Cadena Cepeda In Partial Fulfillment of the Requirements for the Degree of Doctor of Philosophy California Institute of Technology Pasadena, California 1977 (Submitted December 20, 1976) ii ACKNOWLEDGMENTS I would like to acknowledge my fiancee, Stephanie Smith, and thank her for her love and moral encouragement during my studies at Caltech. I would also like to thank her for her excellent typing of this thesis. I am especially grateful for my advisor, Dr. James J. Morgan, for his interest and guidance in the preparation of this work. I would also like to thank the Mexican Commission of Science and Technology, CONACYT, for financing my studies while in the United States. I extend my deep appreciation to my parents, Mr. and Mrs. Raul Cadena, for their constant interest in my well being. I am appreciative for the faculty of Environmental Engineering at Caltech for their excellent teaching. I extend my grateful appreciation to my friends at Lake Avenue Congregational Church for their prayers and moral support. This dissertation is dedicated to Jesus Christ, the only begotten Son of God, "in Whom are hidden all the treasures of wisdom and knowledge." (Colossians 2:3) iii ABSTRACT Natural waters may be chemically studied as mixed electrolyte solutions. Some important equilibrium properties of natural waters are intimately related to the activity-concentration ratios (i.e., activity coefficients) of the ions in solution. An Ion Interaction Model, which is based on Pitzer's (1973) thermodynamic model, is proposed in this dissertation. The proposed model is capable of describing the activity coefficient of ions in mixed electrolyte solutions.
    [Show full text]
  • MKT04050701 Rev0.Qxd
    The Physical Chemistry, Theory and Technique of Freezing Point Determinations Table of Contents Chapter 1 — Physical Chemistry Review 1 1.1 Measuring the concentration of solutions 1 1.2 Comparison of concentrative indices 7 1.3 Osmotic concentration and fluid movement 8 Chapter 2 — Freezing Point Theory & Technique 11 2.1 Definitions 11 2.2 Theory 12 2.3 Thermodynamic Factors 16 2.4 Conclusion 17 1 Physical Chemistry Review 1.1 Measuring the concentration of solutions 1. Definition of a solution: A homogeneous single-phase mixture of solute and solvent, where: a. Solvent = the liquid component. b. Solute = the solid component, or liquid in lesser proportion. Suspensions or colloids are not solutions. The solvent must fully dissolve the solute. 2. Two common expressions of concentration: a. Molarity = grams of solute per liter of solution. b. Molality = grams of solute per kilogram of solvent. fluid volume liter mark displaced by solute molar molal Figure 1: A 1 molal solution is generally more dilute than a 1 molar solution. 1 The Physical Chemistry, Theory and Technique of Freezing Point Determinations 3. Methods of molality measurement... definition of osmolality a. Colligative properties: When one mole of non-ionic solute is added to one kilogram of water, the colligative properties are changed in the following manner and proportion: • freezing point goes down 1.86°C • osmotic pressure goes up 17000mmHg (17000mmHg = 22.4 atmospheres) • boiling point goes up 0.52°C • vapor pressure goes down 0.3mmHg (vapor pressure of pure water = 17mmHg) b. Osmolality: • One mole of non-ionic solute dissolved in a kilogram of water will yield Avogadro's number (6.02 × 1023) of molecules.
    [Show full text]