Louisiana State University LSU Digital Commons LSU Historical Dissertations and Theses Graduate School 1961 Studies on the Extractability of Anions. Apolinar S. Lorica Louisiana State University and Agricultural & Mechanical College Follow this and additional works at: https://digitalcommons.lsu.edu/gradschool_disstheses Recommended Citation Lorica, Apolinar S., "Studies on the Extractability of Anions." (1961). LSU Historical Dissertations and Theses. 674. https://digitalcommons.lsu.edu/gradschool_disstheses/674 This Dissertation is brought to you for free and open access by the Graduate School at LSU Digital Commons. It has been accepted for inclusion in LSU Historical Dissertations and Theses by an authorized administrator of LSU Digital Commons. For more information, please contact [email protected]. This dissertation has been 61—5146 microfilmed exactly as received LORICA, Apolinar S., 1927- STUDIES ON THE EXTRACTABILJTY OF ANIONS. Louisiana State University, Ph.D., 1961 Chem istry, analytic al University Microfilms, Inc., Ann Arbor, Michigan STUDIES ON THE EXTRACTABILITY OF ANIONS A Dissertation Submitted to the Graduate Faculty of the Louisiana State University and Agricultural and Mechanical College in partial fulfillment of the requirements for the degree of Doctor of Philosophy in The Department of Chemistry by Apolinar S • Lorica B.S. Chem., University of the Philippines, 1954 June, 1961 ACKNOWLEDGMENT The author wishes to express his gratitude to Dr. Philip W. West under whose guidance this work was conducted. Discussions with Drs. R. V. Nauman, B. R. Sant, A. K. Mukherji, Alberto Llacer, M. C. Day, and Joel Selbln proved very helpful; they are gratefully acknowledged. This acknowledgment will not be complete without mention of the financial support from the Continental Oil Company and the Standard Oil Company (ESSO), for which the author is very grateful. 11 TABLE OF CONTENTS ACKNOWLEDGMENT............................................................................... il ABSTRACT................................................................................................. I/ll GENERAL CONSIDERATIONS............................................................... 1 EXPERIMENTAL........................................................................................ 13 A. Qualitative Studies ..................................................................... 13 B. Study of a Specific System Extraction of Iodide ............. 28 1. Experimental Procedures .................................................. 29 2. Various Factors Affecting the Extraction of Iodide . 34 3. Sources of Error..................................................................... 39 4. The Hydrogen Ion Concentration ................................... 39 5 . The Cadmium to Iodide Molar R atio ............................. 40 6 . The Initial Concentration of Cadmium Iodide . 41 7. The Effect of Temperature.................................................. 42 8 . Selectivity ............................................................................... 42 DISCUSSION OF RESULTS.................................................................. 44 DEVELOPMENT OF A PROCEDURE FOR THE EXTRACTION METHOD OF IODIDE DETERMINATION......................................... 49 APPENDIX........................................................................................... 52 SELECTED BIBLIOGRAPHY.................................................................. 81 VITA.............................................................................................................. Ill LIST OF TABLES Page I. Extraction of Anions - A Qualitative Survey ....................... 25 II. Effect of Sodium Hydroxide Concentration on the Recovery of Iodide ................................................ 36 III. Effect of Sodium Hydroxide Concentration on the Titration of Iodide ................................................................ 37 IV. Equilibration Time and Percentage Extraction .................... 38 V. Effect of Hydrogen Ion Concentration on the Extraction of Iodide ....................................................................... 39 VI. Effect of Initial Cd/1 Molar Ratio on the Extraction of Io d id e ............................................................................................. 41 VII. Effect of Initial Concentration on the Extraction of Io d id e ............................................................................................. 41 VIII. Effect of Temperature on the Extraction of Iodide .... 42 DC. Gravimetric Standardization of Cadmium Nitrate .............. 52 X. Potassium Iodate Solutions ....................................................... 53 XI. Effect of Sodium Hydroxide Concentration on the Titration of Iodide: A. B lan k ............................................................................................ 54 B. 0.1 N Sodium Hydroxide ................................................... 55 C. IN Sodium Hydroxide .......................................................... 56 D. 10% and 2% Sodium Hydroxide ....................................... 57 XII. Effect of Sodium Hydroxide Concentration on the Recovery of Iodide: A. 0.1 N Sodium Hydroxide ................................................... 58 B. IN Sodium Hydroxide ......................................................... 59 lv Page C . 10% and 2% Sodium H y d ro x id e ....................................... 60 XIII. Recovery of Iodide with 1 N NaOH: A. 20 mis. of 1 N NaOH ................................................. 61 B. 40 mis. of 1 N NaOH ................................................ 61 C. 60 mis. of 1 N NaOH . ........................................... 62 XIV. Effect of Hydrogen Ion Concentration on the Extraction of Iodide: A. pH - 0 .3 ................................................................................. 63 B. pH - 0 .6 ................................................................................ 64 C . pH - 1 ........................................................................................ 65 D . pH - 2 .......................................................................................... 6 6 E. pH - 3 ........................................................................................... 67 F. pH - 6 ........................................................................................... 6 8 XV. Effect of CdA Ratio on the Extraction of Iodide: A. Cd/l - 1/1 ............................................................................... 69 B. Cd/l = 2 / 1 .................. 70 C . Cd/l = 4 / 1 ............................................................................... 71 XVI. Effect of Initial Concentration of Cdl 2 on th e Extraction of Iodide ; A. 0.001 M Cadmium Iodide ............................................. 72 B. 0.003 M Cadmium Iodide ............................................. 73 C. 0.006 M Cadmium Iodide .............................................. 74 D. 0.01 M Cadmium Iodide .............................................. 75 E. 0.03 M Cadmium Iodide ..................................................... 76 F. 0.1 M Cadmium Iodide ..................................................... 77 v Page XVII. Effect of Temperature on the Extraction of Iodide: A. 2 5 ° C ........................................................................................... 78 B. 4 0 ° C ........................................................................................... 79 Graph No* I: Spectrophotometric Calibration Curve for Cadmium ....................................................................... 80 vl ABSTRACT The extractabillty of fourteen anions has been Investigated. The procedure used In the preliminary qualitative survey was to add a slight excess of certain cations to the solution of the anion In order to form weak electrolytes or lon-associatlon complexes that were extractable. The three types of solvents used for the subsequent extractions were an ether (diethyl ether), a ketone (methyl lsobutyl ketone), and an ester (ethyl acetate). The following anions were extracted well by one or more of the solvents: chloride, bromide, iodide, thlocyanate, cyanide, and nitrate. Fluoride was only slightly extracted. Spot tests also showed extraction of the following anions by diethyl ether: borate, oxalate, orthophosphate, thlosulfate, sulfite, nitrite, and ferrocyanide. The extraction of iodide with cadmium as coordinating cation was chosen for detailed study. Extraction efficiency decreased with dilu­ tion of the cadmium iodide solution, but down to 0.006 M, it was still appreciable. Such factors as temperature, pH of the aqueous phase, and the initial cadmium to iodide mole ratio had only a slight effect. A 1:1 mixture of tributyl phosphate and methyl lsobutyl ketone was used for the immiscible solvent. The existence of the following extractable species has been postulated: (2H+, C dlJ, (H+, Cdlp, Cdl2, (Cdl+, OH"), and (Cdl+ , NO 3 ). An experimental procedure for the determination of iodide by the extraction technique was developed. vii I. GENERAL CONSIDERATIONS Until recent times only the organic chemist* engaged in Isolating a reaction product in high purity* used solvent extraction as a basic tool. The insolubility of Inorganic compounds in organic solvents* the limited number of available solvents* and what Conant called "our slavish devotion to water" probably blocked serious consideration of the use of solvents in Inorganic analysis. There were early isolated Instances*