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The Determination Op Activity Coefficients and Ionic Conductivities Op Some High-Charged Electrolytes in Aqueous Solution at 25°C

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The Determination Op Activity Coefficients and Ionic Conductivities Op Some High-Charged Electrolytes in Aqueous Solution at 25°C THE DETERMINATION OP ACTIVITY COEFFICIENTS AND IONIC CONDUCTIVITIES OP SOME HIGH-CHARGED ELECTROLYTES IN AQUEOUS SOLUTION AT 25°C By Kenneth 0. Groves A THESIS Submitted to the School for Advanced Graduate Studies of Michigan State University of Agriculture and Applied Science In partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry 1959 ProQuest Number: 10008555 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest ProQuest 10008555 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This work is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 48106- 1346 THE DETERMINATION OP ACTIVITY COEFFICIENTS AND IONIC CONDUCTIVITIES OP SOME HIGH-CHARGED ELECTROLYTES IN AQUEOUS SOLUTION AT 25°C By Kenneth 0. Groves AN ABSTRACT Submitted to the School for Advanced Graduate Studies of Michigan State University of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of DOCTOR OF PHILOSOPHY Department of Chemistry Year 1959 Approved jj- . ACKN ONLEDGIvlENT I would like to give my sincere t?cianks and appreciation to Dr. C. H. Brubaker, Jr., for his guidance and in­ spiration and to Dr. J. L. Dye for his counsel and interest in the work of this thesis. I also would like to express my appreciation to the National Science Foundation who provided financial as­ sistance through the academic year 1958-1959. ABSTRACT Activity coefficients and equivalent conductances have been determined for the electrolytes K^£u(CN)§]•2HgO, p[(Me)4 ^ 4 Mo(CN)8*2B20, Pt{pn)3Cl4*H£>0 and KgPtCCNjq in aqueous solutions at 25°C. The activity coefficients and osmotic coefficients were obtained by isopiestic comparison with aqueous potassium chloride solutions. The values of these coefficients deter­ mined for the first three electrolytes listed above were comparable to those previously found for similar electrolytes of the 1-4, 4-1 charge type. The values found indicate that these electrolytes may be extensively associated in solution. Values of the mean distance of closest approach, 8, have been determined. The numerical values of these para­ meters vary considerably depending upon the method of calcu­ lation. The equivalent conductances were also ascertained in the hope of determining values for a Independent of the iso- piestic method. Such determinations could not be made, how­ ever, since deviations from the limiting conductance equation of Onsager were too great. Because of these deviations, pre­ sent methods of determining limiting ionic conductance values most accurately could not be used. Values for these constants were determined, however, by simple linear extrapolation of equivalent conductance versus c'^i graphs. These derived values are 114.9 ohm"l, 118.2 ohm*"-*-, 90.15 ohm“^, 81.2 ohm“^ for the polyvalent ions Mo(Cil)Q-^, V/(GH)q **^, Pt(pn)^+^ and Pt(GlT)^“^, respectively. Complete evaluation of the conductance behavior of these highly charged species must await further mathematical extensions of the present theory of electrolytic solutions. a LIST OP TABLES Table Page I - Parameters for Equation (57) 89 II - Isopiestic Molalities, Observed and Calculated Osmotic Coefficients of Ft (pnJgCl^HgO ........ 91 III - Smoothed Activity and Osmotic Coefficients at 25°C 95-96 IV - Values for § Determined by the Method of Randall and White .................... 97 V - Valu.es for Limiting Conductance Determined by Linear Extrapolation of A Versus c"”s curves .................................... 103 VI - Parameters of the Empirically Extended Onsager Equation ......................... 106 VII - Ion-Pair Dissociation Constants for 1-4, 4-1 Electrolytes Derived from Bjer,rumls Method .................................... 112 LIST OF FIGURES Figure Title Page 1 Definition of Vectors .............. 31 2 Basic Circuit for Jones Bridge ..... 69 3 Graphical Procedure for Evaluating the Integral (t)/m)dm for Pt(pn)^Cl4 *H2 0 90 4 Graphical Procedure for_xEvaJ.uating the Integral _/*"( 1- (t/mF JdmS1 in the Determination of Y* for the Elec- trolyte K^V(CK)8|*2H20 92 5 Graphical Procedure for gvaly.ating the Integral J ~{ 1 - )dms in the Determination of for the Electrolyte £ N ( M e 4 Mo(CN)g*2 HgO ... 93 6 Graphical Proced.ure for^Evaluating the Integral ^ ( 1 - & /m3 Jdiris in the Determination of ft for the Elec­ trolyte K^PtCCN)^ .......... 94 7 h versus mi for A-KgP'k(ON )4 , B-Pt (pn ) 3 CI4 *H20 C-Kjv (CN )qT* 2H2 0 , D- 0M (Me ) 4 ] 4 M 0 (CN ; q • 2 H^D ......... 101 8 Variation of -A.°! with Concentration for Various Electrolytes in Aqueous Solution at 25°C; A-KgPt(GN)4 , B-K4 EV (CN) d- 2HoO, C-PtTpn)3 CI4 *H2 0 , D- p f ( Me )4j 4 MoTcN)s*2 H 2 0 ....... 105 9 Graphical Evaluation of the Para­ meters in the Empirically Extended Onsager Equation for Various Elec­ trolytes; A-Pt(pn)3 Cl4 *H2 0 , B- Dj(Me)4]4Mo(CN)8*2B2 0, C-K4JS(CHJ§]• SHgO, D-K2 Pt(CN ) 4 ......... 107 TABLE OF CONTENTS Section Page 1 - HISTORY ......................................... 1 I. Isopiestic Method .......................... 1 II. Conductivity Measurement .................. 8 2 - THEORY ............................................. 19 General Thermodynamic Properties of Solutions .. 19 Activity Coefficients by the Method of Lewis and White ........ 23 The Osmotic Coefficient Concept .............. 26 The Debye-Iluckel "Theory .................. 29 General Treatment ........... 30 The Distribution Function ................. 31 Determination of the Potential Function ... 34 Determination of the Work Required to Charge an Ion to a Potential j........... 39 Activity Coefficients by the Method of Smith ... 42 Extension of the Method of Lev/is and White in Dilute Solutions ................ 45 'The Onsager Conductance Equation ............. 45 The Electrophoretic Effect ............ 48 The Equation of Motion ............... 50 Time Rate of Change of the Distribution Function ................. 51 Perturbation of Ionic Atmospheres........... 51 The Asymmetry Effect ......... 55 General Equation for the Conductance of an Electrolyte 3/hich Dissociates into Two Kinds of Ions ........................ 57 3 - APPARATUS AND PROCEDURE ........................ 60 I. Preparation of Compounds .................. 60 A. Preparation of Potassium Tetracyano- platinate (II) ...................... 60 3. Preparation of Tris-(1,2-propylenediamine) platinum (IV)Chloride, Monohydrate .. 61 C. Preparation of Tetramethyl ammonium Octacyanomolybdate Dihydrate ........ 62 D. Preparation of Potassium Octacyano- tungstate Dihydrate ............... 64 II. Isopiestic Measurements ................... 67 III. Conductance Measurements ............... 69 A. The Alternating Current Bridge and Resistance Measurements ............ 69 B. The Conductance Cells ................ 72 C. Platinization of Electrodes ..... 73 D. Constant Temperature Bath ............ 74 E. Preparation of Conductance Water .... 74 F. General Procedure .................. 75 G. Determination of the Densities of Solutions .......................... 78 H. Determination of the Cell Constant ... 79 4 - RESULTS AND DISCUSSION ........................ 61 Treatment of Isopiestic Data ................. 87 Discussion of Isopiestic Measurements ........ 97 Determination of Ionic Conductances ....... 102 Discussion of Conductance Measurements ...... 106 SUMMARY ........................................ 118 LITERATURE CITED .............................. 120 APPENDIX I (Isopiestic Measurements) ......... 124 APPENDIX II (Conductance Measurements) ..... 128 APPENDIX III (Densities of Solutions) ...... 132 1 1 - HISTORY k. Isopiestic Method The method was first utilized by Bousfield (1, 2) as early as 1913. He introduced the procedure as a method for determining vapor pressure data in order to determine the relative degree of hydration of salts with Identical vapor pressures. The method finally adopted after a number of trials of various procedures and apparatus was as follows. Salts or solutions were placed in separate open ves­ sels in a desiccator which was evacuated to facilitate the exchange of vapor between soltitlons and maintained at a uni­ form temperature* Under these conditions equilibrium was reached by the several solutions gaining or losing water un­ til they arrived at the same vapor pressure. The name "iso­ piestic” was given to these solutions at equilibrium. After equilibrium was reached the containers were weighed, and the amount of water taken up by each salt was recorded* A small quantity of water was then placed in a trough between the vessels containing the solutions and the operation was re­ peated. In this way Bousfield was able to obtain a series of data for salts In various degrees of hydration and deter­ mine approximately the vapor pressure of water above which several pure salts and their hydrates began to take up water. The vapor pressure data used as a standard for each equili­ brium concentration was that of the lithium chloride solu­ tion* Since the accuracy of the vapor pressure data obtained by this method must necessarily depend on the degree of ac­ curacy of the vapor pressure data known for
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