BSc Chemistry
4.1 Activity. 4.2 Mean Activity Coefficient. 4.3 Measurement of Activity and activity coefficient. 5. Summary. Page 3. Chemistry. PAPER No. 6: Physical
Activity Coefficients in Electrolyte Solutions
It has been eight decades since activity coefficients came into use in the representation of the solute chemical potential in electrolyte solutions
CHAPTER 1 - INTRODUCTION TO ELECTROCHEMICAL SYSTEMS
Fig 1 provides the dependence of the mean ionic activity coefficient on the ionic strength. The semi-quantitative interpretation of Fig 1 lies in the classical
Debye-Huckel Limiting Law of Activity Coefficients and Its Limitations
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Activity Activity Coefficients
where K is the equilibrium constant and aX is the activity of X and described by the activity coefficient γX and [X]:. aX = γX[X]. W idth tt i ll t i. t l t.
Non-Ideality Through Fugacity and Activity
Fugacity is a direct measure of the chemical potential of a species in a mixture. • Fugacity coefficient of a pure gas or liquid: φpure gas(Tp) = f p.
THE LIQUID-LIQUID EQUILIBRIUM FOR ACTIVITY COEFFICIENT
The method has been appliedto the determination of activity coefficients of hydrocarbon binary systems using water as the solvent. Water is the ideal solvent
3. Activity Coefficients of Aqueous Species 3.1. Introduction
The Davies equation predicts a unit activity coefficient for all neutral solute species. This is known to be inaccurate. In general the activity coefficients
BSc Chemistry
Therefore the individual contributions of the ionic species to the concentration cannot be determined. Thus
Thermodynamics of Liquid Bi-Pb alloys – Experiment vs Modeling
10-Apr-2020 The activities and infinite dilution activity coefficient of Bi-Pb alloys at various temperatures were also calculated by the MIVM. A ...
BSc Chemistry
25: Activity and Mean Activity Coefficient. Subject. Chemistry. Paper No and Title. 6 Physical Chemistry -II (Statistical Thermodynamics
Debye-Huckel Limiting Law of Activity Coefficients and Its Limitations
Hence the activity coefficient is a measure of chemical potential change due to benefits like downloading any PDF document for your personal preview.
THE DETERMINATION OP ACTIVITY COEFFICIENTS AND IONIC
ACTIVITY COEFFICIENTS AND IONIC CONDUCTIVITIES. OP SOME HIGH-CHARGED ELECTROLYTES. IN AQUEOUS SOLUTION AT 25°C. By. Kenneth 0. Groves. A THESIS.
Activity Coefficients in Electrolyte Solutions
activity coefficient depends only on the ion charge and the ionic strength and is independent of the specific ions present.
Activity Activity Coefficients
where K is the equilibrium constant and aX is the activity of X and described by the activity coefficient ?X and [X]:. aX = ?X[X].
No Slide Title
effect of ionic strength on solubility. •calculation of ionic strength. •activity coefficients. •effect of ionic strength and size/charge of ions on activity
CHAPTER 1 - INTRODUCTION TO ELECTROCHEMICAL SYSTEMS
(ii) estimate the mean ionic activity coefficients of electrolytes known as the activity coefficient which has different forms depending upon the.
Individual Activity Coefficients of Ions in Aqueous Solutions
activity coefficient of the ith ion with valence q and I' is the ionic concentration given by with ci in moles per liter.
Chem 35.5 Activity Coefficients
Gravimetric analysis understanding of process
Osmotic Coefficients and Mean Activity Coefficients of Uni-univalent
29-Oct-2009 Finally literature references are given to data on 51 additional uni-univalent electrolytes. Key words: Activity coefficients; osmotic ...
Activity Coefficients
inElectrolyte Solutions
2nd Edition
Editor
Kenneth S. Pitzer, Ph.D.
Professor
nesEyileri vo Sueltfiy2 drtKeyfti2 vo SEhtovyrtE .eyPehe2z SEhtovyrtES,S Cyeff .vDE ,Eivr Rrr RyFvy .vfivr NvrcvrPREFACE
The progress toward a second edition of "Activity Coefficients in Electrolyte Solutions" was well advanced by Dr. R. M. Pytkowicz, the editor of the first edition, when he resignedin early 1989 for health reasons. After a substantial hiatus, I was asked to take over the
editorship. Most of the chapters and authors remain as were planned by Dr. Pytkowicz, but a few changes in authorship or coauthorship were necessary and one new chapter (8) was added. 1 am responsible for the present organization of the book but am happy to acknowledgethe role of Dr. Pytkowicz.L2 eKEhMEitvr DvrDeyrtrk iue kereyEh fiEie vo PrvHhecke tr iutf otehc Erc iue vssvyT
iMrtitef ovy EcKErDef Ef Hehh Ef DeyiEtr fseDtotD Dvllerif DvrDeyrtrk svtrif vo svfftFheltfMrceyfiErctrk Eye ktKer tr iue priyvcMDitvrm Ri iutf svtriz p Htfu iv iuErP Ehh vo iue
EMiuvyf ovy iue syvlsi Dvlsheitvr vo iuety DuEsieyf Erc l2 feDyeiEy2z Cekk2 BvMiuEycz ovy EfftfiErDe vr KEytvMf EfseDif vo iutf syv}eDimGerreiu Bm CtigeyActivity Coefficients
inElectrolyte Solutions
2nd Edition
Editor
Kenneth S. Pitzer, Ph.D.
Professor
nesEyileri vo Sueltfiy2 drtKeyfti2 vo SEhtovyrtE .eyPehe2z SEhtovyrtEINTRODU CTIO N
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Section II of Chapter 6. While the title of Chapter 6 is "Activity Coefficients in NaturalWaters," this discussion is comprehensive and not limited to "Natural Waters".'vy f2fielf Htiu htiihe vy rv tvr EffvDtEitvrz fseDtotD trieytvrtD eooeDif Eye fithh ftkrtotDEri
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vkyEsu2 tf DheEy oyvl iue yefMhif syeferiec in various chapters, especially in Chapters 6 and7, The application to aerosols which comprise aqueous electrolytes is less obvious but
important; at low humidity these aerosol solutions become highly concentrated. This isrecognized in Chapter 6.aueye Eye lEr2 FtvhvktDEhh2 tlsvyiEri E"MevMf ohMtcf Hueye DueltDEh iueylvc2rEltDf
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YSuEsiey U vo iue Wfi ectitvrm SuEsiey ( vo iutf ectitvr1 tr iue iyeEileri vo iuety cEiEm prceecz .EMlkEyierWJ uEf sMFhtfuec tr E FtvhvktDEh }vMyrEh E ftlshe DvlsMiey syvkyEl ovy iutf leiuvcm pi feelf syvFEFhe iuEi iue lvye syeDtfe Erc Dvlsheie iyeEilerif cefDytFec tr iutfKvhMle Hthh otrc trDyeEftrk EsshtDEitvr tr FtvhvktDEh f2fielf tr iue reEy oMiMyem'trEhh2z p rvie iuEi tr iue kevhvktDEh EyeE Erc tr erktreeytrk iueye tf kyeEi trieyefi tr
E"MevMf eheDiyvh2ief Ei fithh utkuey ielseyEiMyefz oEy EFvKe (884Sz Erc iutf yErke ye"Mtyef E ctooeyeri iuevyeitDEh EssyvEDu oyvl iuEi Mfec tr iutf FvvPm aueye tf iue suEfe fesEyEitvr vo HEiey Erc Er EssyeDtEFhe fEhi fvhMFthti2 tr iue fieEl suEfem Rhfvz iue DvlsyefftFthti2 vo iue fvhKeri FeDvlef trotrtie Ei tif DytitDEh svtrim auefe EfseDif ye"Mtye iue Mfe vo iue 5ehluvhig ereyk2 yEiuey iuEr iue jtFFf ereyk2 Ef iue FEftD oMrDitvrm Vuthe feKeyEh yefeEyDu DvriytFMitvrf uEKe Feer lEcez HutDu Eye yehEiec iv iutf utkuey ielseyEiMye yErkez lEr2 EfseDif Eye fithh iv Fe trKefitkEiecm pi Hthh Fe Er trieyefitrk otehc Fviu iuevyeitDEhh2 Erc tr EsshtDEitvrf tr iue reEy oMiMyemREFERENCES
1 Robinson. R. A. and Stokes. R. H-, Electrolyte Solutions, revised, Butterworths, London. Isled., 1955;
2nd ed.. revised 1965.Om Harned, H. S. and Owen. B. B., The Physical Chemistry of Electrolyte Solutions, Reinhold Publishing.
New York. 1958.(m Milner, S. R., The vtrial of a mixture of ions. Phil Mag., 23. 551, 1912; 25. 742. 1913,)m Debye, P. and Huckel, E., Zur theorie der electrolyte, I and II. Phys. Z . 24. 185 and 305. 1923.I Plummer, L. N., Parkhurst, D. L., Fleming, G. W., and Dunkle, S. A., A computer program incor
porating Pilzer's equations for calculation of geochemical reactions in brines. U S, Geological Survey,
Water-Resources Investigations Report 88-4153, Reston. VA. 1988. Also, see Chapters 3. 6, and 7.6. Barrie, C. E. and Weare, J. H., The predication of mineral solubilities in natural waters: the Na-K-Mg-
Ca-CKS0,-M.,0 system from zero to high concentration at 25°C. Geochim. Cosmochim. Acta. 44. 981,W6J8m
Um Filippov, V. K., Dmitriev, G. V., and Yakovleva, S. 1.. Use of the Purer method for calculating the
activity of componcnls in mixed solutions of electrolytes according to data on solubility, Doki Akad Nuuk.
SSSR, Ft:. Khim.. 252. 156. 1980; Engl, transl.. 252. 359, 1980; and subsequent papers.J Mu. C. and Lindsay, W, T., Jr., Thermodynamics of sodium chloride solutions at high temperatures. J
Solution Chem.. 1,45. 1972.6m Albert}1, R. A., Standard Gibbs free energy, enthalpy, and entropy changes as a function of pH and pMg
for several reactions involving adenosine phosphates. J. BioI Chem . 244 . 3290. 1969.W8m Phillips, R. C., George. P., and Rutman, R. J., Thermodynamic data for the hydrolysis of adenosine
triphosphate as a TuncUon of pH. Mg-' ion concentration, and ionic strength. J Biol Oirm.. 244, 3330.
1969.11 Goldberg. R. N. and Tewari, Y. B., Thermodynamics of the disproportionation of adenosine 5'-dtphos-
phate to adenosine 5'-tnphosphatc and adenosine 5'-monophosphate. Biophys. Chem., 40. 241, 1991.WO Guyrin, R. W., Gelberg, H. J., and Veech, R. L" Equilibrium constants of the malalc dehydrogenase,
citrate synthase, citrate lyase, and acetyl coenzymc A hydrolysis reactions under physiological conditions.
J Biol. Chem.. 248. 6957, 1973.13 Cohen. C. J., Fozzard, H. A., and Sheu, S.-S., Increase in intracellular sodium ion activity during
stimulation in mammalian cardiac muscle. Circ, Bex , 50, 651. 1982.W) Shorofsky, S. R., Field, M., and Fozzard, H. A" Mechanism of Cl secretion in canine trachea; changes
in intracellular chloride activity with secretion, J Membrane Biol., 81,1. 1984.WI Biber, T. U. I... Drewnowska, K., Baumgarten. C. M.. and Fisher, R. S" Intracellular Cl activity
changes of frog skin. Am. J Physiol., 249. F432. 1985.W;m Gambalc. F., Menini, A., and Rauch, G " Effects of calcium on the gramicidin A single channel in
phosphatidvlserine membranes. Eur. Biophys. J , 14. 369. 1987.17 Kitic, D., Pallia. M. L" Favetto, G. J., and Oiirife, J., Mixed saturated salt solutions as standards for
w ater activity measurements in the microbiological growth range. J. FaodSci.. 53, 578. 1988, and preceding
articles there citedWJ .EMlkEyierz Sm Lmz R syvkyEl ovy DEhDMhEitvr vo EDitKti2 DveootDterif Ei feheDiec DvrDeriyEitvrf Erc
ielseyEiMyefz Comput. Biol. Med., II. 189, 1981.THE EDITOR
Kenneth S. Pitzer was bom in Pomona, California in 1914. He received his B.S. degree from the California Institute of Technology in 1935, his Ph.D. from the University of California, Berkeley in 1937, a D.Sc. from Wesleyan University in 1962, and an LL.D. from the University of California in 1963 and from Mills College in 1969. He was a member of the faculty at Berkeley from 1937 to 1960, serving also as Dean of the College of Chemistry from 1951 to 1960. On leave from the University of California, he was Technical Director of the Maryland Research Laboratory, a World War II entity from 1943 to 1944, and was Director of Research for the U.S. Atomic Energy Commission from 1949 to 1951. In 1961, he became President and Professor of Chemistry at Rice University, serving until 1968 when he became President of Stanford University until 1970. In 1971 he returned to the University of California, Berkeley, as Professor until 1984 and thereafter as Professor Emeritus butwas recalled for continued service.His advisory committee and other part-time service included the General Advisory
Committee to the AEC, 1958 to 1965 (Chairman 1960 to 1962); President's Science Advisory Committee, 1965 to 1968; Commission on Chemical Thermodynamics of the International Union of Pure and Applied Chemistry, 1953 to 1961; NASA Science and Technology Advisory Committee, 1964 to 1965; Trustee, Harvey Mudd College, 1956 to 1961, Mills College, 1958 to 1961, Pitzer College 1966 to the present, Rand Corporation, 1962 to 1972; Member of the Board of Directors, Owens Illinois, Inc., 1967 to 1986; Federal Reserve Bank of Dallas, 1965 to 1968, the American Council on Education, 1967 to 1971; and Member of the Council of the National Academy of Sciences, 1964 to 1967 and 1973 to1976.His research has extended through many areas of physical chemistry and into topics of
importance including inorganic and organic chemistry, chemical engineering, and geochem istry. In addition to work on aqueous electrolytes reflected in this volume, his research has included quantum theory and statistical mechanics as applied to chemical problems ranging from the potential restricting rotation about single bonds, to the bonding in polyatomic carbon molecules, and to the effects of relativity on chemical bonds involving very heavy atoms. In addition to many journal articles and several book chapters, his books include Quantum Chemistry, 1953; Selected Values of Physical and Chemical Properties of Hydro carbons and Related Compounds, with F. D. Rossini and others, 1947, 2nd edition, 1953;Thermodynamics, 2nd edition with L. Brewer, 1961, and a revision of the 1st edition ofG. N. Lewis and M. Randall.
His honors and awards include the National Medal of Science, 1975, the Robert A. Welch Award in Chemistry, 1984, the Alumnus of the Year Award, University of California, Berkeley, 1951, and the Alumni Distinguished Service Award, California Institute of Tech nology, 1966. From the American Chemical Society he received the Award in Pure Chem istry, 1943, in Petroleum Chemistry, 1949, the Gilbert Newton Lewis Medal, 1965, the Priestley Medal, 1969, and the Willard Gibbs Medal, 1976. Other recognitions include many special lectureships, a Guggenheim Fellowship, 1951, and election to the National Academy of Sciences in 1949.CONTRIBUTORS
James N. Butler, Ph.D.
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TABLE OF CONTENTS
Chapter 1
Thermodynamics of Solutions............................................................................................ 1R. H. Stokes
Chapter 2
Introduction to the Statistical Mechanics of Solutions .......29Robert M. Mazo and Chung Yuan MoilChapter 3
Ion Interaction Approach: Theory and Data Correlation .............................75Kenneth S. PitzerChapter 4
Experimental Methods: Potentiometric
.........................................................................155James N. Butler and Rabindra N. Roy
Chapter 5
Experimental Methods; Isopiestic........................................................................ ,209
Joseph A. Rard and Robert F. Platford
Chapter 6
Activity Coefficients in Natural Waters
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