Electrochemical Analysis: Studies of Acids, Bases, and Salts by Emf, Conductance, Optical, and Kinetic Methods July 1965 to June 1966
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onal Bureau 01 avauuo*" jibrary, N.W. Bldg NBS 400 ELECTROCHEMICAL ANALYSIS: STUDIES OF ACIDS, BASES, AND SALTS BY EMF, CONDUCTANCE, OPTICAL, AND KINETIC METHODS JULY 1965 TO JUNE 1966 1: I Edited by Roger G. Bates IBSI Hi '.:::.: +** ° F t *oA U.S. DEPARTMENT OF COMMERCE National Bureau of Standards ' *<">cau of THE NATIONAL BUREAU OF STANDARDS The National Bureau of Standards is a principal focal point in the Federal Government for assur- ing maximum application of the physical and engineering sciences to the advancement of technology in industry and commerce. Its responsibilities include development and maintenance of the national standards of measurement, and the provisions of means for making measurements consistent with those standards; determination of physical constants and properties of materials; development of methods for testing materials, mechanisms, and structures, and making such tests as may be neces- sary, particularly for government agencies; cooperation in the establishment of standard practices for incorporation in codes and specifications; advisory service to government agencies on scientific and technical problems; invention and development of devices to serve special needs of the Govern- ment; assistance to industry, business, and consumers in the development and acceptance of com- mercial standards and simplified trade practice recommendations; administration of programs in cooperation with United States business groups and standards organizations for the development of international standards of practice; and maintenance of a clearinghouse for the collection and dissemination of scientific, technical, and engineering information. The scope of the Bureau's activities is suggested in the following listing of its three Institutes and their organizational units. Institute for Basic Standards. Applied Mathematics. Electricity. Metrology. Mechanics. Heat. Atomic Physics. Physical Chemistry. Laboratory Astrophysics.* Radiation Physics. Radio Standards Laboratory:* Radio Standards Physics; Radio Standards Engineering. Office of Standard Reference Data. Institute for Materials Research. Analytical Chemistry. Polymers. Metallurgy. Inorganic Mate- rials. Reactor Radiations. Cryogenics.* Materials Evaluation Laboratory. Office of Standard Refer- ence Materials. Institute for Applied Technology. Building Research. Information Technology. Performance Test Development. Electronic Instrumentation. Textile and Apparel Technology Center. Technical Analysis. Office of Weights and Measures. Office of Engineering Standards. Office of Invention and Innovation. Office of Technical Resources. Clearinghouse for Federal Scientific and Technical Information.** Located at Boulder, Colorado, 80302. ** Located at 5285 Port Royal Road, Springfield, Virginia, 22151. UNITED STATES DEPARTMENT OF COMMERCE • John T. Connor, Secretary NATIONAL BUREAU OF STANDARDS • A. V. Astin, Director NBS TECHNICAL NOTE 400 Issued September 6, 1966 ELECTROCHEMICAL ANALYSIS: STUDIES OF ACIDS, BASES, AND SALTS BY EMF, CONDUCTANCE, OPTICAL, AND KINETIC METHODS JULY 1965 TO JUNE 1966 Edited by Roger G. Bates Electrochemical Analysis Section Analytical Chemistry Division Institute for Materials Research NBS Technical Notes are designed to supplement the Bureau's regular publications program. They provide a means for making available scientific data that are of transient or limited interest. Technical Notes may be listed or referred to in the open literature. For sale by the Superintendent of Documents, U.S. Government Printing Office Washington, D.C., 20402 - Price 55 cents FOREWORD The Analytical Chemistry Division was established as a separate division at the National Bureau of Standards on September 1, 196j>, and became part of the Institute for Materials Research in the February 1, 1964, reorganization. It consists at present of nine sections and about 100 tech- nical personnel encompassing some 45 different analytical competences from activation analysis and atomic absorption to vacuum fusion and X-ray spectroscopy. These competences, and in turn the sections which they comprise, are charged with research at the forefront of analysis as well as aware- ness of the practical sample, be it standard reference material or service analysis. In addition it is their responsibility to inform others of their efforts. Formal publication in scientific periodicals is highly important. In addition, however, it has been our experi- ence that informal, annual summaries of progress describing efforts of the past year can be very valuable in disseminat- ing information. At the National Bureau of Standards such publications fit logically into the category of a Technical Note. In 1966 we plan to issue these summaries for all of our sections. The following is the second annual report on progress of the Electrochemical Analysis Section. W. Wayne Meinke, Chief Analytical Chemistry Division ii PREFACE This is the second in a series of annual progress reports of the Electrochemical Analysis Section of the Analytical Chemistry Division. The report covers the fiscal year 1966, which "began on July 1, 1965, and ended on June 30, 1966. Many of the processes and reactions of analytical interest take place in solutions, and a large fraction of these involve ionized solutes. If the research programs of the Electrochemical Analysis Section were to "be placed in a single broad category, undoubtedly "Solution Electro- chemistry" would "be a. fair choice, with primary emphasis on acid-base phenomena, solvent effects on the behavior of electrolytes, and potentiometry with reversible electrodes. Competence in polarography and coulometry exists elsewhere in the Analytical Chemistry Division] hence, these areas are not a part of the research activity of the Electro- chemical Analysis Section. In line with a uniform policy of the Division, the Section's programs have both research and sample aspects. During the fiscal year Just ending, about 70 percent of the total effort was devoted to re- search, while 20 percent was devoted to programs on Standard Reference Materials and 10 percent to Other-Agency programs. The outstanding event of the present year was the long- awaited move to the excellent new facility at Gaithersburg, Md. The move and the attendant loss of time during re- settlement have inevitably left their mark on the Section's activity* More serious, however, has been a shortage of personnel. Two project leaders, Dr. Robert Gary and Dr. Richard K. Wolford, were chosen as Science and Technology Fellows and were assigned elsewhere in the Department of Commerce for 10 months of the reporting period. iii A third, Dr. Marion M. Davis, retired from the Section on December J51, 1965. On the other hand, Dr. Paul W. Schindler spent nine months in the Section as a guest worker supported by the Swiss National Foundation. The purpose of this report is to summarize the broad program of the Electrochemical Analysis Section and to convey also the manner in which the individual projects contribute to the whole. An attempt is made to set forth in a rather complete way the entire year's activity of the Section and to reveal the ways in which this specialized group contributes to the missions of the Division and Institute of which it is a part. In order to specify adequately the procedures, it has been necessary occasionally to identify commercial materi- als and equipment in this report In no case does such identification imply recommendation or endorsement by the National Bureau of Standards, nor does it imply that the material or equipment identified is necessarily the best available for the purpose. The assistance of Mrs. Rosemary Maddock and Mrs. Marguerite Rauderibush in the preparation of this report is gratefully acknowledged. Roger G. Bates, Chief Electrochemical Analysis Section Washington, D.C. June , 1966 IV TABLE OF CONTENTS PAGE 1. FACILITIES AND EQUIPMENT 1 The Gaithersburg Laboratories ........ 1 Plans and Needs 5 2. MEASUREMENT OF ACIDITY 5 Concepts and Program 5 pH Standards 10 Redetermination of the pH of Potassium Hydrogen Phthalate, Primary pH Standard 10 Method ..... 10 Procedures 11 Results 11 Certification of a New Lot of Potassium Dihydrogen Phosphate ..... 1^ Sodium Hydrogen Succinate, a New Standard Reference Material for pH Measurements . 15 Standard pH Values for 4-Aminopyridine Buffers in 50 Percent Methanol 17 Standards for a pD Scale in Deuterium Oxide. 19 A Scale of Acid Strengths in Benzene 21 Experimental 21 Discussion 22 3. SOLVENT EFFECTS ON ACID-BASE PROCESSES .... 25 Dissociation of Positively-Charged Acids in Methanol-Water Solvents 25 Ammonium Ion 28 Tris (hydroxymethyl )methylammonium Ion 30 Solubility Studies of the Medium Effect ^2 Parameters for the Solvent Effect. 35 Isotope Effects on the Dissociation of Acetic Acid in Water and Deuterium Oxide . 59 v PAGE Acid-Base Behavior in Organic Solvents with Low Dielectric Constants . 45 Spectrophotometry Studies of the Dissociation of Phenols 46 4. EQUILIBRIUM STUDIES OP SYSTEMS OF ANALYTICAL INTEREST 48 Thermodynamics of the Dissociation of Morpholinium Ion in Water ......... 48 Ionization Constant of Deuterium Oxide from 5 to 50 °C 51 Response of the Glass Electrode in Heavy Water 56 5. THERMODYNAMIC STUDIES OF AQUEOUS SOLUTIONS OF MIXED SALTS . 60 6. CONDUCTOMETRIC DETERMINATION OF TRACES OF WATER 63 Objectives and Principle of Method ...... 63 Modification of Apparatus 63 Calibration with Water 68 Analysis of Errors ..... 71 Status of the Project ...... 73 7. KINETIC TECHNIQUES IN TRACE ANALYSIS 74 8.