0 RN L-4343 UC-4 - Chemistry Contract No. W-7405-eng-26 ANALYTICAL CHEMISTRY DIVI SI ON ANNUAL PROGRESS REPORT For Period Ending September 30, 1968 M. T. Kelley, Director J. C. White, Associate Director Compiled and Edited by Helen P. Raaen DECEMBER 1968 OAK RIDGE NATIONAL LABORATORY Oak Ridge, Tennessee operated by UNION CARBIDE CORPORATION for the U. S. ATOMIC ENERGY COMMISSION LEGAL NOTICE This report nas prepared as an account of Government sponsored work. Neither the United States. nor the Commission. nor any person acting on behalf of the Commlsslon: A. Makes any warranty or representation. expressed or implied. with respect to the accu- racy, completeness, or usefulness of the idarmation contained in this report. or that the use of any information, apparatus, method, or process disclosed In this report may not infringe privately owned rights: or B. 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Reports previously issued in this series are as follows: ORNL-686 Period Ending March 3 1, 1950 OWL-788 Period Ending June 30, 1950 ORNL-867 Period Ending October 10, 1950 ORNL-955 Period Ending January 10,1951 ORNL-1088 Period Ending March 26, 1951 OWL-1113 Period Ending June 26, 195 1 ORNL-1129 Period Ending September 10, 1951 ORNL-1233 Period Ending December 26, 1951 ORNL-1276 Period Ending March 26, 1952 ORNL- 136 1 Period Ending June 26, 1952 ORNL- 1423 Period Ending September 26, 1952 ORNL-1474 Period Ending January 10,1953 ORNL-1547 Period Ending April 20, 1953 ORNL-1639 Period Ending October 20, 1953 ORNL-1717 Period Ending April 20, 1954 OWL-1788 Period Ending October 20, 1954 ORNL-1880 Period Ending April 20, 1955 0RNL- 19 73 Period Ending October 20, 1955 ORNL-2070 Period Ending April 20, 1956 ORNL-2218 Period Ending December 3 1, 1956 ORNL-2453 Period Ending December 3 1, 1957 ORNL-2662 Period Ending December 3 1, 1958 ORNL-2866 Period Ending December 3 1, 1959 ORNL-3060 Period Ending December 3 1, 1960 ORNL-3243 Period Ending December 3 1, 196 1 ORNL-3397 Period Ending December 3 1, 1962 ORNL-3537 Period Ending November 15, 1963 ORNL-375 0 Period Ending November 15, 1964 ORNL-388 9 Period Ending November 15, 1965 ORNL-4039 Period Ending October 3 1, 1966 ORNL-4196 Period Ending October 3 1, 1967 Preface The general mission of the Analytical Chemistry Division is to provide complete analytical support for the many research programs at ORNL. This support comprises research in analytical chemistry, development of new and improved methods for analysis, and a chemical analysis service that employs a wide variety of analytical techniques. The great diversity in the research programs at ORNL is likewise reflected in a similar diversity in the activities of the Division. The research and development efforts within the Division are oriented toward providing the most suitable analytical techniques for the analyses that the Division is called upon to perform. Efforts are made constantly to provide more precise and more rapid analyses by employing the most advanced instrumentation available and by using automated or semiautomated procedures. Efforts are being made to use electronic data acquisition and processing equipment wherever possible. Considerable progress has been made in this regard this year in that three small dedicated computers have been acquired and commitments have been made for the acquisition of two more such devices. Initially, these will be used primarily for acquisition of data in digital form, but at least one of these will be used to explore the feasibility of computer-controlled analytical instrumentation. It is gratifying to note that the preeminence of the work of the Division in the field of analytical instrumentation has been recognized by the announcement that Dale J. Fisher, Croup Leader of the Analytical Instrumentation Group, will be the recipient of the 1969 ACS Award in Chemical Instrumentation sponsored by the Sargent-Welch Scientific Company. The Division is continuing major research and development programs with the objectives of providing chemical analyses for the MSRE and for bioengineering programs. Efforts in analytical biochemistry continue to occupy a major place in the program of the Division with constant exploration being made of areas that would constitute a logical expansion of present work in this field. This emphasis is in recognition of the increasing importance of biology and biochemistry in the research efforts of ORNL and of the entire scientific community. ... 111 8' . Contents ... PREFACE .................................................................. 111 SUMMARY .................................................................. xiii PART A . ANALYTICAL RESEARCH 1. ANALYTICAL INSTRUMENTATION ............................................ 1 J 1.1 Solid-state Controlled-Potential Coulometric Titrator .............................. 1 1.2 Modifications to the High-Sensitivity Controlled-Potential Coulometric Titrator (ORNL Model Q-2564) ............................................ 2 1.3 Instrumentation for the High-Radiation-Level Analytical Laboratory (HRLAL) ............. 2 1.3.a New Titrant-Delivery Unit and Elevator ................................... 2 1.3.b New ORNL Model Q-1348C Pipetter ..................................... 2 1.4 Apparatus for Precise Control of Mercury Flow Rate of Dropping-Mercury Electrodes (D.M.E.’s) ................................................... 2 1.5 Electrical and Electrochemical Tests of Performance of Polarographs .................... 2 1.6 A Controlled-Potential and Derivative DC Polarograph - Advantages of Kapid and Derivative DC Polarography ............................................ 3 1.7 Polarography of Zirconium in Acetonitrile and Dimethyl Sulfoxide ..................... 3 1.8 Polarographic Survey of Biochemicals ......................................... 4 1.9 ORNL Model Q-2792 Controlled-Potential DC Polarograph and ORNL Model Q-2942 Polarographic Drop-Time Controller ......................................... 5 1.10 Design of Time-Averaging and Time-Derivative Circuits for DC Polarographs ............... 5 1.1 1 Instrument for End-Point Detection in Bipotentiometric Titrations ..................... 5 1.1 2 Controlled-Potential Controlled-Current Cyclic Voltammeter ......................... 6 1.1 3 Derivative Circuits for Use with the Controlled-Potential Controlled-Current Cyclic Voltammeter .................................................... 6 1. 14 On the Separation of Half-Wave Potentials Required for Resolution of Simple, Reversible, Overlapping Waves in Stationary-Electrode Voltammetry ................... 7 1.1 5 Modification of Dual Set-Point Voltage Comparator (ORNL Model Q-2950) ............... 7 1.16 Integrator Module ...................................................... 7 - 1.17 Model IX Flame Spectrophotometer .......................................... 7 1.1 8 Use of Statistical Techniques in Flame Photometry ................................ 7 1.1 9 Instrumentation for Analytical Biochemistry .................................... 7 V vi 1.20 Computer-Assisted Analytical Chemistry ....................................... 8 Q 1.21 Analytical Applications of a Digital Instrument Computer System ...................... 8 1.21.a Capabilities ..................................................... 8 1.21 .b Planned Use with Special Interfaces ..................................... 9 . 1.21.c Use as a Laboratory Test Instrument .................................... 9 1.21 .d Use for Digital Polarography .......................................... 9 1.22 Information Packages Submitted to the Division of Technical Information Extension ......... 9 1.23 Cooperative Projects .................................................... 10 2 . ANALYTICAL METHODOLOGY ............................................... 11 2.1 GasChromatography .................................................... 11 2.1.a Instrumentation ................................................... 11 2.1 .0 A Remodeled Laboratory for