This dissertation has been 64—1312 microfilmed exactly as received WILSON, Larry Eugene, 1935- DETERMINATION OF THE COMPOSITION OF SOLUTIONS OF BINARY HYDROCARBON MIXTURES BY TITRATION WITH WATER. The Ohio State University, Ph.D., 1963 Chemistry, analytical University Microfilms, Inc., Ann Arbor, Michigan DETERMINATION OF THE COMPOSITION OF SOLUTIONS OF BINARY HYDROCARBON MIXTURES BY TITRATION WITH WATER DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of The Ohio State University By LARRY EUGENE WILSON, B.Sc The Ohio State University 1963 Approved by Department of Chemistry ACKNOWLEDGMENT The author wishes to express his sincere appreciation to Dr. Earle B. Caley for his encouragement and guidance throughout the course of this research. ii CONTENTS Page INTRODUCTION . 1 HISTORICAL ........................................... 3 APPARATUS AND CHEMICALS ............................. 17 A p p a r a t u s ................ 17 C h e m i c a l s ....................................... 19 EXPERIMENTAL PROCEDURES ............................. 25 Aromatic Hydrocarbon Mixtures .... .......... 25 Aliphatic Hydrocarbon Mixtures ................... 29 EXPERIMENTAL D A T A ................................... 31 EXPERIMENTAL RESULTS ................................. 138 Precision of Results— Aromatic Mixtures ........ 138 Accuracy of Results— Aromatic Mixtures .......... 1^2 Precision and Accuracy of Results— Aliphatic Mixtures.............................. 150 THEORETICAL CONSIDERATIONS ........................... 15^ SUMMARY ................................................156 BIBLIOGRAPHY ......................................... 158 AUTOBIOGRAPHY ....................................... 160 l i s t o f t a b l e s Table Page I Results of Siggia and Hanna for analysis of acetic acid-carbon tetrachloride-water mixtures.................................. 8 II Results of Jones and Amstell for water content of methanol ................ 9 III Comparison of experimental indices of refraction to theoretical values ........... 23 IV Titration of mesitylene-benzene-etnanol mixtures having a total dilution volume of to.OO mL / ...................... 33 V Titration of mesitylene-benzene-ethanol mixtures having a total dilution volume of 50.00 ml................................. 33 VI Titration of p-cymene-benzene-ethanol mixtures having a total dilution volume of 40.00 ml................................. 38 VII Titration of p-cymene-benzene-ethanol mixtures having a total dilution volume of 50.00 ml................................. 38 VIII Titration of xylene-benzene-ethanol mixtures having a total dilution volume of 4-0.00 ml. 43 IX Titration of xylene-benzene-ethanol mixtures having a total dilution volume of 50.00 ml. 43 X Titration of mesitylene-toluene-ethanol mixtures having a total dilution volume of 40.00 ml......... ........................ 48 XI Titration of mesitylene-toluene-ethanol mixtures having a total dilution volume of 50.00 ml................................. 48 XII Titration of p-cymene-toluene-ethanol mixtures having a total dilution volume of 40.00 ml................................. 53 iv LIST OF TABLES— (Continued) Table Page XIII Titration of p-cymene-toluene-ethanol mixtures having a total dilution volume of 50.00 ml.................................. 53 XIV Titration of mesitylene-benzene-isopropanol mixtures having a total dilution volume of *1-0.00 ml.................................. 58 XV Titration of mesitylene-benzene-isopropanol mixtures having a total dilution volume of 50.00 ml.................................. 58 XVI Titration of p-cymene-benzene-isopropanol mixtures having a total dilution volume of 40.00 ml............... 65 XVII Titration of p-cymene-benzene-isopropanol mixtures having a total dilution volume of 50.00 ml.............. 65 XVIII Titration of xylene-benzene-isopropanol mixtures having a total dilution volume of 40.00 ml.................................. 68 XIX Titration of xylene-benzene-isopropanol mixtures having a total dilution volume of 50.00 ml.................................. 68 XX Titration of mesitylene-toluene-isopropanol mixtures having a total dilution volume of 40.00 ml.................................. 75 XXI Titration of mesitylene-toluene-isopropanol mixtures having a total dilution volume of 50.00 ml.................................. 75 XXII Titration of p-cymene-toluene-isopropanol mixtures having a total dilution volume of 40.00 ml.................................. 78 XXIII Titration of p-cymene-toluene-isopropanol mixtures having a total dilution volume of 50.00 ml. ....................... 78 XXIV Titration of mesitylene-benzene-methanol mixtures having a total dilution volume of 50.00 ml..................... 85 v LIST OF TABLES— (Continued) Table Page XXV Titration of raesitylene-benzene-methanol mixtures having a total dilution volume of 60.00 ml. ............ 83 XXVI Titration of p-cymene-benzene-methanol mixtures having a total dilution volume of 50.00 ml.................................. 88 XXVII Titration of p-cymene-benzene-methanol mixtures having a total dilution volume of 60.00 ml. 88 XXVIII Titration of xylene-benzene-methanol mixtures having a total dilution volume of 50*00 ml. 93 XXIX Titration of xylene-benzene-methanol mixtures having a total dilution volume of 60.00 ml. 93 XXX Titration of mesitylene-toluene^methanol mixtures having a total dilution volume of 50.00 ml.......... 98 XXXI Titration of mesitylene-toluene-methanol mixtures having a total dilution volume of 60.00 ml............................... 98 XXXII Titration of p-cymene-toluene-methanol mixtures having a total dilution volume of 50.00 ml. .'.......................... 103 XXXIII Titration of p-cymene-toluene-methanol mixtures having a total dilution volume of 60.00 ml................................... 103 XXXIV Titration of n-decane-n-heptane-isopropanol mixtures having a total dilution volume of 50.00 ml................................ 108 XXXV Titration of n-decane-n-hexane-isopropanol mixtures having a total dilution volume of 50.00 ml................................ 109 XXXVI Titration of n-decane-n-octane-isopropanol mixtures having a total dilution volume of 50.00 ml................................ 109 XXXVII Titration of n-decane-2 methylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml. ....... 112 vi LIST OF TABLES— (Continued) Table Page XXXVIII Titration of n-decane^^,^ trimethylpentane- isopropanol mixtures having a total 1 dilution volume of 50.00 ml.................... 112 XXXIX Titration of n-dodecane-n-decane-isopropanol mixtures having a total dilution volume of 50.00 ml.................................... 115 XL Titration of n-dodecane-n-octane-isopropanol mixtures having a total dilution volume of 50.00 ml.................................... 115 XLI Titration of n-tetradecane-n-decane-isopropanol mixtures having a total dilution volume of 50.00 ml.................................... 116 XLII Titration of n-tetradecane-n-octane-isopropanol mixtures having a total dilution volume of 50.00 m l . ................................. 116 XLIII Titration of n-decane-3 methylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml.................... 119 XLIV Titration of n-decane-2,3 dimethylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml.................... 119 XLV Titration of n-decane-2,3 dimethylbutane- isopropanol mixtures having a total dilution volume of 50.00 ml........... 119 XLVI Titration of n-decane-2,2,3 trimethylbutane- isopropanol mixtures having a total dilution volume of 50.00 ml............................. 122 XLVII Titration of n-decane-3 methylhexane- isopropanol mixtures having a total dilution volume of 50.00 ml............................. 122 XLVIII Titration of n-decane-3 methylheptane- isopropanol mixtures having a total dilution volume of 50.00 ml............................. 123 XLIX Titration of n-decane-2,2 dimethylbutane- isopropanol mixtures having a total dilution volume of 50.00 ml............................. 123 vii LIST OF TABLES— (Continued) Table Page L Titration of n-dodecane-3 methylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml................ 126 LI Titration of n-dodecane-5 methylhexane- isopropanol mixtures having a total dilution volume of 50.00 ml. ....... 126 LII Titration of n-tetradecane-2 methylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml............... 127 LIII Titration of n-tetradecane-3 methylheptane- isopropanol mixtures having a total dilution volume of 50.00 ml............... 127 LIV Titration of n-heptane-2,2,3 trimethylbutane- isopropanol mixtures having a total dilution volume of 50.00 ml............... 130 LV Titration of n-heptane-2,3 dimethylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml............... 130 LVI Titration of 3 methylheptane-2 methylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml............... 131 LVII Titration of 3 methylheptane-2,3 dimethyl- pentane-isopropanol mixtures having a total dilution volume of 50.00 ml......... 131 LVIII Titration of 3 methylhexane-2 methylpentane- isopropanol mixtures having a total dilution volume of 50.00 ml............... 13^ LIX Titration of n-hexane-2,2 dimethylbutane- isopropanol mixtures having a total dilution volume of 50.00 ml................ 13^ LX Titration of n-heptane-n-hexane-isopropanol mixtures having a total dilution