-I EREN<

STATES

IENT OF IERCE

ATION

NBS TECHNICAL NOTE 583

Electrochemical

Analysis Section:

Summary of Activities,

July 1970 to June 1971
NATIONAL BUREAU OF STANDARDS

The National Bureau of Standards1 was established by an act of Congress March 3, 1901. The Bureau's overall goal is to strengthen and advance the Nation's science and

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2 Part of the Center for Radiation Research.

3 Located at Boulder, Colorado 80302.

1 Part of the Center for Building Technology.
1&

Electrochemical Analysis Section

Summary of Activities,

July 1970 to June 1971

Richard A. Durst

Electrochemical Analysis Section

Analytical Chemistry Division

Institute for Materials Research

National Bureau of Standards

Washington, D.C. 20234

tf^ 6*>3

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.

'*'*««<* 4

U.S. DEPARTMENT OF COMMERCE

NATIONAL BUREAU OF STANDARDS

Issued February 1973
information which we have struggled to obtain and which we

feel might be of some help to others. Certain areas which

it appears will not be treated fully in regular publications

are considered in some detail here. Other results which are

being written up for publication in the journal literature

are covered in a much more abbreviated form.

At the National Bureau of Standards publications such as these fit logically into the category of a Technical Note.

We plan to issue these summaries for all of our sections.

The following is the seventh annual report on progress of the

Electrochemical Analysis Section:

W. Wayne Meinke, Chief

Analytical Chemistry Division

IV
PREFACE

This is the seventh annual progress report of the

Electrochemical Analysis Section of the Analytical Chemistry

Division. It covers the fiscal year 1971, which began on

July 1, 1970 and ended on June 30, 1971. This report summarizes the total program of the Section, incomplete studies

as well as finished work, and stresses its relationship to

the missions of the Analytical Chemistry Division and the

Institute for Materials Research.

This Section broadly concerns itself with studies of

ionic processes in solution using electroanalytical and

other related techniques. During this year, some redirection

and reemphasis of effort were continued in order to bring the

Section expertise to bear on important analytical problems

in several areas of science, medicine, and technology. The

special interests of the members of the Section lie for the

most part in solution electrochemistry including the competence areas of potentiometry , electrometric titrations,

coulometry, and polarography

.

The Section staff in the past year maintained an overall

scientific effort of about four man-years. The personnel

and their competences are listed in section 8 of this report.

Our most recent staff addition, Dr. Joseph R. Robinson, will

develop a trace analysis competence in the area of anodic

stripping voltammetry to complement the polarographic

analysis competence.

Mrs. E. June Maienthal , who transferred to our Section

this year from the Microchemical Analysis Section, was the

recipient of the Department of Commerce Silver Medal for her

outstanding success in providing novel, sensitive, and

accurate methods for trace and major constituent determinations through polarographic measurement techniques.

Contributions to over 200 Standard Reference Materials

certificates, hundreds of analysis reports, and 15 research

v
publications are indicative of Mrs. Maienthal's productivity

In order to specify the procedures adequately, it has

been necessary in certain instances to identify commercial

materials 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 is necessarily the best available for

the purpose.

The support of the Scientific Apparatus Makers Association (SAMA) for ionic activity studies is gratefully

acknowledged.

The assistance of Mrs. Charlotte Wren and Mrs. Treva

Monti in the preparation of this report is greatly

appreciated.

Richard A. Durst, Chief

Electrochemical Analysis Section

VI
TABLE OF CONTENTS

PAGE

1. INTRODUCTION 2

2. COULOMETRY 4

Introduction 4

Atomic Weight of Zinc . 12

Research 12

Method 13

Results 14

OECD Characterization Exchange Program 18

Single Crystal KC1 19

Gallium Arsenide Stoichiometry 24

Analysis of Standard Reference Materials ...... 29

Tris -hydrochloride 29

Standard Reference KC1 31

Standard Reference NaCl 37

3. POLAROGRAPHY 39

Introduction 39

Trace Analysis 40

Reagent and Environmental Blanks 40

Environmental Analysis 42

Lead in Paint 46

Lead in Industrial Air 47

Copper, Lead, Cadmium and Zinc in a Particulate

Standard Reference Material 47

Iron in 1-ppm Glass 51

vii
TABLE OF CONTENTS (CONT'D)

PAGE

Aluminum, Lead, Bismuth, Tellurium and Titanium

in Special Steels 52

Orchard Leaves 55

Major Constituent Analysis 64

Single Cell Polarography 64

Comparative Polarography 65

pH AND IONIC ACTIVITY STANDARDS 68

Tr is (hydroxymethyl) aminomethane/tris (hydroxymethyl)

aminomethane 'hydrochloride in Aqueous

Solution 68

Comparison of Procedures 72

Borax 73

Future pH Buffer for Clinical Use 75

Ion-Selective Electrodes 75

Equipment

Standards for Sodium, Potassium and Chloride

Activities 77

Solution Standards for Calcium Ion Activity . 77

POTENTIOMETRY 79

Chromatographic Detector for NTA and Other

Complexing Agents Using a Cupric Electrode

Flow-Through Cell 79

Potentiometric Determination of Total Calcium. . . 85

DISSOLVED OXYGEN IN SEAWATER 87

Introduction 87

Experimental 89

Results 90

viii
TABLE OF CONTENTS (CONT'D)

PAGE

Efficiency of the Measuring System 90

Discussion and Summary 91

New Frontiers 92

7. FOREIGN -CURRENCY PROGRAM 93

8. PERSONNEL AND ACTIVITIES 94

Personnel Listing 94

Publications § Manuscripts 94

Talks 96

9. REFERENCES. . . 98

IX
LIST OF FIGURES

FIGURE NO. PAGE

1. Anodic stripping volt amine trie analysis system. 2

2. Coulometric circuit 6

3. A general view of the coulometric facility . . 7

4. A close-up of the coulometric titration cell . 8

5. A typical amperometric end-point 9

6. Comparison of benzoic acid assay by

independent methods 9

7. Comparison of arsenious oxide assay by

independent methods 10

8. Comparison of potassium dichromate assay

by independent methods 11

9. Foundation and versatility of coulometric

measurement 18

10. Differences between individual values and the

corresponding means 23

11. Cathode ray polarograph 39

12. NTA calibration curves 44

13. pH(S) as a function of temperature 70

14. Emf as a function of calcium activity 78

15. Cupric electrode/NTA detector system 80

16. Close-up of the cupric electrode flow-through

cell 81

17. Diagram of flow- through cell and coulometric

cupric ion generator 82

18. Emf response in mV of the cupric ion flowthrough cell 84

19. Hersch cell 89

x
LIST OF TABLES

TABLE NO. PAGE

1. Atomic weight of zinc determined by

coulometry 15

2. Results of coulometric titration of KC1. ... 22

3. Coulometric analysis of GaAs 26

4. Coulometric analysis of GaAs . 26

5. Mass balance for GaAs 27

6. Results of Analysis of Tris -hydrochloride . . . 30

7. Preliminary studies on SRM KC1 32

8. Exposure of KC1 to various humidities 33

9. Final analysis of SRM KC1 35

10. Coulometric determination of halides in

SRM NaCl 38

11. Cu, Pb , Cd, and Zn in acids and distilled

water 40

12. Iron in redistilled acids 41

13. Lead in paint 47

14. Lead in air 48

15. Determination of copper, lead, cadmium, and

zinc in proposed particulate Standard

Reference Material 50

16. Determination of iron in 1-ppm glass 51

17. Aluminum in SRM 1263 and 363 53

18. Aluminum in SRM 1264 53

19. Lead in SRM 1264 53

20. Lead, bismuth and tellurium in SRM 1263

and 363 54

XI
LIST OF TABLES (CONT'D)

PAGE

21. Titanium in SRMs 1262 and 1263 55

22. Titanium in SRM 1264 55

23. Determination of nickel in orchard leaves. . . 56

24. Determination of lead and bismuth in

orchard leaves 58

25. Determination of iron (acid-soluble) in

orchard leaves 59

26. Determination of aluminum (acid-soluble) in

orchard leaves 60

27. Determination of iron (total) in orchard

leaves 62

28. Determination of aluminum (total) in

orchard leaves 63

29. Copper in archaeological specimens 67

30. Average emf values for the standard buffer

containing 0.01667 mol of Tris and 0.0500

mol of Tris-HCl per Kg, from 0° to 50°C ... 71

31. Comparison of extrapolated pH values with

pH determined directly 73

32. Acidity function and emf with varying KC1

molalities 74

33. Total calcium in NBS test solutions as

determined by potentiometric titration. ... 86

34. Cell efficiencies for oxygen determinations. . 91

35. Comparison of dissolved oxygen determined

by the system with literature data 92

XI
ELECTROCHEMICAL ANALYSIS SECTION: SUMMARY OF ACTIVITIES

JULY 1970 to JUNE 1971

Edited by Richard A. Durst

This survey of the activities of the Electrochemical

Analysis Section, Analytical Chemistry Division, covers the

period from July 1970 to June 1971. An attempt is made to

briefly summarize a year's progress on the technical projects

of the Section, to indicate the composition and capabilities

of the unit as a whole, and to stress the Section's role in

the mission of the Institute. Summaries of the work in each

of the Section competences are given. In the area of acidity

measurements, work was completed on the standardization

of tris (hydroxymethyl) aminomethane for use as a biologic pH

buffer material and standard for clinical pH measurements.

High-precision coulometry is used to determine the atomic

weight of zinc, the stoichiometry of gallium arsenide, and

the purity of KC1 and NaCl. Polarography is used to

determine trace elements in a variety of environmental

samples and Standard Reference Materials.

Key words: Acidity; coulometric analysis; electrochemical

analysis; ionic activity; ion-selective

electrodes; pH measurements; polarography; potentiometry; Standard Reference Materials.
1. INTRODUCTION

In last year's report on the activities of the Electrochemical Analysis Section [1], it was noted that the Section's

expertise in the area of electroanalysis was being applied

to a variety of analytical problems. Again this year, the

work reported illustrates the diversity of interesting problems and materials, ranging from environmental samples to a redetermination of the atomic weight of zinc.

A. Facilities

Two additions to the facilities of the Section have

been made this year. The transfer of the polarography competence from the Microchemical Analysis Section brought into

the Section several pieces of equipment, including two

cathode ray polarographs

To supplement the polarographic work, an anodic stripping

voltammetry system was added extending the voltammetric trace

analysis capabilities to even lower concentration levels. The

basic four-cell unit with its associated electronics is extended to eight-cell operation using the equipment shown in

Figure 1. Each cell consists of a three-electrode system

and nitrogen bubbler for deaeration and stirring. By the

use of composite mercury graphite electrodes, trace analyses

can be performed at the sub-ppb level.

Figure 1. Anodic stripping voltammetric analysis system,
B. Activities

The laboratory is now organized into three major groups

with personnel as listed in section 8 of this report. The

groups are (1) potentiometry , (2) coulometry, and (3) voltammetry. The activities of the Section can be broadly divided

into research, SRM certification, and service analyses for

other NBS divisions and government and non-government

agencies

At the present time, automation of the pH and ionic

activity measurement system is in the design stage. This

system will ultimately control the various emf measurement

and cell temperature parameters; perform emf, temperature,

and barometric pressure data acquisition; and evaluate the

pH and ionic activity functions from this data. This system

should be operational by January 1972 and will be described

in detail in next year's report.

NBS Special Publication 314, "Ion-Selective Electrodes"

[2], which was published in January 1970 and reviews the

state of the art of these sensors, has gone into its third

printing after having sold more than 7000 copies in less than

18 months. This indicates the great interest in these sensors

and the value of this monograph to this field.

Richard A. Durst
2. COULOMETRY

"When you can express in numbers

that of which you speak, you have

the beginning of a science. Until

that time your knowledge is meager

and unsatisfactory."

Lord Kelvin

A. Introduction

Today it is not sufficient to express the results of

measurement in numbers . The requirement of today is for

these numbers to be accurate.

Just as the accuracy of time, mass and length measurements throughout the United States depends on the accuracy

of physical standards maintained by NBS, the accuracy of the

chemical measurement depends on the chemical standards which

NBS certifies and disseminates. In contrast to the physical

standards, chemical standards are destroyed in the measurement

process. The result is that chemical standards (though they

are convenient as the medium for the transfer and dissemination) are depleted and periodically must be replenished,

restandardized and reissued. The eminent need of today is

to establish a permanent, nondestructable standard for

chemical measurement of the stoichiometry of materials. In

addition to permanence this standard should fulfill the

requirements of a variety of chemical reactions that are used

in the standardization process. The coulomb fulfills these

criteria . The essence of coulometric analysis, the measurement

system and the consequences of the use of the coulomb will

be briefly discussed as a model for absolute analytical

measurement

.

The coulometric method of analysis involves quantitative

electrochemical conversion of the constituent which is being

determined from some initial state to another well defined
state and the measurement is simply the evaluation of charge

necessary to perform this conversion. Below, two examples

of the coulometric analysis processes are illustrated; a cyclic cathodic process and a unidirectional anodic process :

3 Fe(lll) +3e 3 Fe(ll)

f |

3 Fe(lll) +Cr(lll)« 3 Fe(ll) + Cr(VI)

Ag *Ag+

+ le

i

Ag

+

+ CI" AgCI

In the former case ferric ion is reduced to ferrous at a platinum cathode and the electric current which induces this

reaction is measured in the external circuit. The ferrous

ion thus generated in turn reacts with the hexavalent

chromium, which is the species to be determined, reducing it

to the trivalent state. Thus as long as the hexavalent

chromium is present in the system ferric ion is regenerated.

When all of the unknown has been consumed cycling ceases

and the concentration of ferrous ion begins to increase. This

point can be determined by a number of suitable indicator

systems. In this reaction then one mole of chromium corresponds to three faradays of charge.

The determination of chloride is realized through the

oxidation of silver from the solid phase. The soluble

chloride is precipitated by the reaction product, Ag , into

another solid phase, silver chloride. The measurement again

involves the measurement of charge needed to carry out this

conversion. When all of the soluble chloride, with the

5
exception of the amount furnished by the solubility of AgCl

in solution, has been consumed the concentration of silver

ions in solution increases, and using a suitable indicator

system the completion of reaction can be established.

The general configuration of the coulometric circuit is

shown in Figure 2.

SATURATED WESTON CELL

Figure 2. Coulometric circuit

The circuit consists of a high precision constant current

power supply, an accurate current comparatory system, the

necessary current stabilization resistors, the timing

circuit, the coulometric electrolysis cell and the endpoint

detector system. The general view of the coulometric

facility is shown in Figure 3, and the close-up of the

coulometric cell in Figure 4.

The design of the cell incorporates two significant

features: (1) separation of the anode and cathode compart6
ments in order to prevent the interference of the counter

electrode reaction products with the analytical reactions

conducted in the left hand side of the cell and (2) a provision for returning the unknown, which is invariably lost

during the electrolysis period by diffusion and electromigration, back into the reaction compartment. Other

features visible in the figure are the end-point detector

probe, (glass electrode in this case for acidimetry) and a system for maintaining the inert atmosphere in the reaction

vessel

.

',.„:.

# # #

Iy

Figure 3. A general view of the coulometric facility
Figure 4. A close-up of the coulometric titration cell.

Figure 5 shows the typical amperometric end-point which

one obtains in coulometric measurement. It has been established that in a coulometric titration the precision of a single measurement of 10 parts per million can be obtained.

Thus, the system appears to be in a state of control and we

"can express in numbers" that of which we speak. Let us

examine the data which subjects the coulomb, as the absolute

chemical standard, to a test; the test for accuracy.
u

O

r-<u

5.0

4.0 -

3.0 -

2.0 -

1.0 -

0.5 10 1.5 2.0

^eqOF Fe

++ GENERATED

Figure 5. A typical ampere-metric end-point

Single Crystal Benzoic Acid

Single Crystal KHPhthalate

Benzoic Acid

(Calonmetric

Standard)

Route Assoy, % *, %

1 +3 99.9957 0.0006

2 + 3 99.9953 0.0006

4 99.9963" 0.0004

* Using F = 96,486 70 C mole -

and U S legal volt of 1969 Figure 6. Comparison of benzoic acid assay by independent

methods

.
Standard Reference Material arsenious oxide was compared

by Keith Sappenfield of the Analytical Chemistry Division to

high-purity resublimed iodine via route 2 in Figure 7 and

analyzed in our laboratory coulometr ically via electrogenerated iodine (route 1) . The agreement between these two

independent methods is 5 parts per million.

Assay, %

99.9873

99.9878

a, %

0.0013

0.0022

Figure 7. Comparison of arsenious oxide assay by independent

methods

Potassium dichromate (Standard Reference Material 136c)

titrated coulometrically in our laboratory via route 1 in

Figure 8, was compared to arsenious oxide by Sappenfield involving a two stage process, route 2 + 3, and analyzed for

impurities (route 4) . The results of these three independent

determinations are again in agreement within 30 parts per

million. Thus, on the basis of these three completely different coulometric reactions there is sufficiently convincing

evidence that the coulomb fulfills two highly important

requirements. Firstly, it unifies chemical measurements

10
through the use of a single standard, the coulomb, and

secondly, this standard is permanent and indestructible

Coulomb

KpCroC 7 M

4 Impurity

SRM 136c ^

Analysis

L V1

As

2 3 SRM 83c

Route Assay, % — V

1

2 + 3

99.9822 99.9852

99.982

0.0007 0.0035 V

4* 0.002

Resu

lo

blimed

Jine

Figure 8

The only significant impurity is 0.018°o H ?

Comparison of potassium dichromate assay by

independent methods.

Accurate coulometric measurement of stoichiometry can

be employed not only for the unification of chemical standard

ization but also in the determination of some important

physical constants.

With the availability of high purity zinc (Standard

Reference Material 682) , the redetermination of the atomic

weight of zinc by the coulometric method posed an unbearable

challenge. In collaboration with Prof. Robert T. Foley of

the American University this challenge was accepted.

To date only a small fraction of the data obtained on

the redetermination of the atomic weight of zinc has been

processed. However, even at this point it is possible to

present a significantly improved value of the atomic weight

of zinc.

11
B . Atomic Weight of Zinc

1 . Research

The nature and experimental detail of some preliminary

investigations will be discussed in future publications.

Nevertheless, it is germane to the subject at hand to outline

the results of these preliminary studies here.

(a) The presence of oxygen (air) in the electrolyte

has a significant effect on the rate of spontaneous corrosion

of zinc. This in turn affects the experimentally determined

electrochemical equivalent and the atomic weight of zinc. For

this reason air was removed from the electrolyte by purging

with nitrogen. A nitrogen atmosphere was maintained in the

coulometer in all final determinations of the electrochemical

equivalent of zinc. In the absence of air the corrosion

current density of zinc amalgam was found to be most sig- -7-2 nificant (1.37 x 10 A cm ).

(b) Commercial grade zincs without any a priori

processing yield a higher electrochemical equivalent (on the

order of 0.01 percent) than the same materials subjected to

vacuum fusion. This could easily be explained by the presence

of gases (notably oxygen) in the commercial material which

are removed under vacuum fusion conditions.

(c) Zinc anodes amalgamated on the surface undergo

electrochemical dissolution without any detectable fall-off

of material in the course of electrolysis.

(d) The difference between the free energies of the

reaction

Zn(Hg) -> Zn

++

+ 2e (U° = +0.799 V) (1)

and the next conceivable reaction

Hg + 20H" -> HgO + H

2 + 2e (U° = +0.098 v) (2)

is sufficiently large that even at current densities as high

as several amperes per square centimeter the former reaction

proceeds at 100.000 percent current efficiency. This was

verified experimentally^ by measurements of the working anode

potentials at different current densities, using first pure

12
mercury anode and then zinc amalgam anodes. Coulometric

experiments conducted at current densities ranging from

10 to 1.0 A cm substantiate this conclusion since no

significant dependence between current density and the

electrochemical equivalent of zinc could be found.

(e) Other parameters investigated include current

(from 10" to 1.0 A), time of electrolysis (from 3 to

4 2 7 x 10"* sec), electrode area (from 0.5 to 10 cm ) , total

4

amount of charge passed through the cell (up to 3 x 10 C)

,

purity of material, and mass of dissolved zinc (up to 10 g)

.

Only the electrode area has a significant effect resulting

from the dissolution of ZnO formed on the surface of the

amalgam during handling of the electrode in air. The

_ 2 magnitude of this effect was evaluated (10.7 ± 1.5 yg cm ) and appropriate correction applied.

2. Method

The approach taken in. this investigation is rather

straightforward in its conception — to determine the mass

of zinc dissolved anodically during the passage of a constant

electrical current through the following electrochemical cell:

Zn(Hg) | ZnCl

2 (3 molal, aq) , NH4

C1 (25 wt %, aq) | Hg (3)

The quantitative reaction which is of specific interest here

is

Zn(Hg) > Zn

++

+ 2e (4)

and the accompanying cathodic reaction is simply the reverse

of reaction (4)

Hg + Zn

++

+ 2e > Zn(Hg) (5)

In such a cell the composition of electrolyte remains unaltered throughout the whole experiment.

The passage of two faradays of charge through the cell

dissolves one mole of zinc from zinc amalgam. The coulometric

circuit enabling passage of charge through the cell within

an accuracy of 0.0002 percent has been described above. A

weighed zinc amalgam anode is suspended at the top of the

coulometer. The mercury pool cathode is located at the

13
bottom of the coulometer. The ground glass flat joint in the

coulometer is provided for insertion of a porous membrane

filter which is used in some experiments to establish the

existence or the absence of any significant fall-off of the

material from the anode in the course of this electrochemical

dissolution. The electrolyte is deaerated and a nitrogen

atmosphere maintained in the coulometer throughout the experiment. Zinc amalgam anodes exhibited no significant material

fall-off.

Zinc anodes are weighed by substitution on a 20-g capacity microbalance . The uncertainity of the mass measurement

process (standard deviation) is 3 x 10 g. The smallest

changes in the mass of Zn anodes roughly equivalent to the

mass of a single weight in the calibrated set of weights

(e.g. 2 g) . After termination of electrolysis, the zinc

anode is carefully removed from the coulometer, washed first

in 0.1 molar NH.C1 solution and then in hot distilled water

and reweighed. Appropriate corrections for the" effects of

buoyancy of air are applied. Thus the charge- to-mass ratio

can be readily computed.

3. Results

The results of experiments with metallic zinc samples

of five different origins are summarized in Table 1. The

first column in the table gives the original number of the

experiment. Material code and the origin of material are

given in columns two and three respectively. The last

column, column four, gives the determined values of the atomic

weight of zinc in each experiment.

The material designated as 1 is high purity zinc

issued by the National Bureau of Standards as Standard

Reference Material (SRM 682) . The material was produced by

Cominco American, Inc. from a special lot of high-grade

electrolytic zinc. It was purified by vacuum distillation,

zone-refining and degasif ication. The overall assessment of

impurities indicates that the material is 99.9999 percent

14
Zn [4] . The material designated as 2 is a special high-grade

metal (99.995 percent Zn) produced by the Electrolytic Zinc

Company of Australasia Ltd. [5]. Materials 3, 4 and 5 were

produced in Peru, Yugoslavia, and Italy respectively.

Table 1. Atomic weight of zinc determined by coulometry.

Experiment

No.

Material

Code

Origin of

Material

Canada

Atomic

Weight of Zinc

139 1 65.3759

140 1 Canada 65.3761

141 1 Canada 65.3782

142 2 Australia 65.3783

143 2 Australia 65.3778

144 3 Peru 65.3786

145 3 Peru 65.3764

146 4 Yugoslavia 65.3761

147 4 Yugoslavia 65.3751

148 5 Italy 65.3784

149 5 Italy 65.3783

150 1 Canada 65.3791

Mean 65.3773,

Pertinent Statistical Data:

Standard deviation of a single determination s = 0.00134

Standard deviation of mean , 0.00039

ts

Two sided 95 percent confidences interval / ^

= + 0.00086

/ n —

for the mean based on 11 degrees of freedom.

15
The calculated values of the atomic weight of zinc in

column four are based on the coulometrically determined

electrochemical equivalent of zinc and adopted value of the

faraday. For the determination of charge consumed in the

electrochemical reaction, the value of electrical current is

based on the NBS ohm and U. S. legal volt of 1969.

Time measurement is based on 100 kHz frequency maintained by NBS. Mass measurements were performed by

substitution using a set of weights calibrated at NBS. The

value of the faraday employed in these calculations is

96486.70 C mole" 1

[6]

The mean value of the atomic weight of zinc based on

coulometric data reported here is 65.37736. A two-sided

95 percent confidence interval for the mean, 0.00086, reflects

adequately the uncertainty in this value due to the random

sources of error. The accuracy of the result, however,

depends not only on the random error of measurement, but

also on the basis which could exist in the various stages on

the measurement process and in the constants which are

employed in calculation of the results.

The assessment of the uncertainties due to all known

sources of possible systematic error (uncertainties in

electrical standards, time, mass and the faraday) indicates

that these sources can contribute as much as 0.002 percent

(0.00131 amu) error. Thus, the sum of the components of

error yields an uncertainty figure of 0.0022 in the atomic

weight of zinc.

It is thus felt that on the basis of this work the atomic

weight of zinc can be assigned the value

65.377 ± 0.003. C6)

All the experimental values reported here lie well within the assigned uncertainty bounds. Further reduction in

the uncertainty of this constant is anticipated when processing of all data is completed. Nevertheless, even the

16
present uncertainty is an order of magnitude smaller than

that of the presently accepted value.

On the basis of data presented here, there appears to be

no significant difference between the values of atomic

weight for materials of different origins even at the 10

percent level of significance. The published results of mass

spectrometric investigations [7] also indicate no significant

differences in the isotopic composition of zinc produced by

electrolytic and chemical reduction processes. To insure that

the value obtained in this research is truly representative

of the terrestrial zinc, an experimental survey of primary

zinc bearing minerals from world-wide sources is now in

progress . This study is conducted on virgin minerals which

have not been subjected to metallurgical processing (other

than flotation) , since this could produce isotope separation

(isotope separation can conceivably occur in such processes

as distillation which is commonly used in purification of

zinc) . The equally challenging problem is the determination of

the stoichiometry of a two component system — gallium

arsenide. Coulometrically the number of moles of each

component is directly determined independently of the atomic

weight of the material and therefore the molar ratio of

gallium to arsenic is directly extractable from the coulometric measurements. The results of this research will be

discussed in a separate section of this report.

It is the aim here to give a varied picture of the

challenging problems of accurate measurement of stoichiometry.

It is attempted to consolidate these ideas as shown in Figure

9. The certification of Standard Reference Materials, the

standardization of research materials such as separated

isotope solutions for calibration of mass spectrometers, the

determination of physical constants, such as the atomic

weights and the faraday, the new area of the measurement of

semiconductor stoichiometry can all be performed using a 17
single standard, the coulomb. The long range goal of the

coulometry program, to place chemical standardization on an

absolute basis, has been achieved. Thus, through coulometry,

the analytical measurement of the chemical composition of

materials is placed on a firm foundation — The International

System of Units (SI), and the standards for this measurement

are the physical standards, maintained by NBS.

ATOMIC WEIGHTS

fARADAY

| P «YS»CAL G0NST*H

TS

/

GiSs

8E HIC0NDUCI(

K

2

Cr2 0, Ml

ASnOj)

ST »miftRD REFtRtWOt

^ MATERIALS

COULOMETRY

SEPARATED ISOTOPt

soL.

! sea water 1 Search iateri*lS

i.

voir

°H|

^BS BASIC STANDARDS

Figure 9. Foundation of versatility of coulometric

measurement

C . OECD Characterization Exchange Program

As part of a chemical characterization exchange program

under the auspices of OECD (Organization for Economic Cooperation and Development) our coulometry laboratory

participated in the determination of chloride in single

crystal KC1 and the determination of the stoichiometry of

single crystal GaAs . In the following pages, the essence and

18
the results of these studies summarized.

1. Single Crystal KC1

Samples of two designations were received from OECD

for analysis: 5.5 and 7.5. Each crystal was removed from

its plastic packaging with a pair of stainless steel

tweezers, placed into a platinum boat without any preliminary

treatment, weighed and delivered into a 12 5 -ml Erlenmeyer

flask by tipping the flask on its side, insertion of the Pt

boat into the flask with tweezers and gentle emptying of the

boat. The Erlenmeyer flasks were previously washed with

fuming sulfuric acid, soaked in distilled water and dried at

110° C in a drying oven. Five milliliters of distilled water

were added to the Erlenmeyer flask (containing the weighed

KC1 sample) by running it gently along the side of the inclined flask. The flask was covered with a small Petri dish.

After dissolution, the KC1 was ready for titration.

a. Method. In one sentence, the method could be

classified as a constant-current coulometric-argentimetric

titration with a biamperometric end-point determination. The

details of procedure are given below.

Basically the method is similar to the one described

earlier [8] with some modifications. The electrolyte was

changed to 20 wt percent HC10,. Coulometric generation of

monovalent silver ion in 20 wt percent perchloric acid has

been investigated in great detail by D. N. Craig et al . [9].

These investigators concluded that the Ag -* Ag + e reaction

proceeds with 100 percent current efficiency for current

2 densities as high as 150 mA/cm . In the titrations reported

2 here the current density was 25 mA/cm for the majority of

the titration. One hundred milliliters of 20 wt percent

perchloric acid were used for each titration. A small

amount {e.g., 20 yeq) of chloride was added to the electrolyte

and pretitrated to saturate it with AgCl. Afterward, 99.9

percent of the calculated amount of silver required for

19
titration were generated at 500 mA. Following pregeneration of silver ion, the sample was introduced into the cell

via a syphon arrangement which is fitted into the flask

containing the dissolved KC1 sample. In this procedure the

sample can be delivered and then electrolyte withdrawn from

the cell back into the Erlenmeyer flask thus rinsing it as many times as desired and yet maintaining virtually constant

volume of electrolyte in the cell.

At this point, the precipitate in the system is permitted to come to equilibrium (about one hour) in the dark.

The titration is then completed at 0.643 mA.

b. Instrumentation. For constant-current coulometric

titrations, three different instrumental facilities are

required for measurements of current, time and end-point

indicator signal.

Current : A Princeton Applied Research constant-current

power supply Model TC602-CR was employed. Its maximum output

is 60V and current rating of 2A. The power supply is

operated in a constant-current mode. The current value is

selected to be such that the IR drop across the standard

resistor equals the voltage of the saturated standard cell.

The standard resistor and standard cells are calibrated at

NBS.

Time : A Beckman Model 3750 Universal EPUT and Timer was

used for measuring the time interval between the start and

the termination of the passage of current through the

coulometric cell.

End-Point Determination : A Sargent Model XXI polarograph

was used for application of the potential (0.05 V) between

two polarizable silver electrodes and for recording the

indicator current.

Mass Measurement : A Mettler Microbalance was used for

weighing. The balance is a constant load type, 20-g capacity

20
The standard deviation of the mass measurement process on

this balance, established over a number of years, is 0.0003

mg. The samples were weighed in a platinum boat by the substitution method. NBS calibrated weights were used for this

purpose. The weight of the samples was corrected to the mass

in vacuum by applying appropriate corrections for the effect

of air buoyancy.

Method of Calibration : The electrical and time measurements were performed against standards calibrated by the

appropriate laboratories of the NBS. The accurate current

measurement was based on the values of a standard resistor

and the voltage of a saturated standard cell. In order to

obtain a statistically larger sample SRM KC1 was analyzed

simultaneously with the samples issued by the OECD. Data

obtained in this manner are useful in establishing whether

or not the measurement process is in the state of control.

c. Standards

Physical Standards : Molecular weight of KC1

Faraday

Volt

Frequency

74.555

96,486.70 C mole

U. S. legal volt of 1969

Frequency standards

maintained by NBS

Reference Material : As indicated earlier, NBS Standard

Reference KC1 was used in conjunction with OECD material

as an independent check on the measurement process. SRM KC1

is a polycrystalline material which requires drying at

500° C to release the entrapped mother liquor.

21
Table 2. Results of coulometric titration of KC1.

Titration

Sequence Re

NBS Standard

ference Materials

Assay, %

OECD Single

crystal

Assay, %

OECD

Sample No

1 99.9969

2 99.9952

3 99.9930

4 99.9971

5 99.9979

6 99.9947 5.5

7 99.9961 5.5

8 99.9939 7.5

9 99.9961

10 99.9991

11 99.9988 5.5

12 99.9909

13 99.9985

14 99.9988

15 99.9980

16 99.9960

Average 99.9965 99.9959

Std. deviation

0.0025 0.0022

t S 0.0016 0.0035

/ n

d. Error Analysis. Titrations of KC1 samples issued

by the Office of Standard Reference Materials and OECD were

performed in an experiment which could be viewed as a "process control" experiment. Two different materials were

analyzed in an interdispersed sequence as indicated in the

data table. The standard deviations for each set are nearly

22
the same. The sequential analyses of the differences between

the individual values and the corresponding means are shown

in Figure 10. The data in Table 2 were fitted three ways to

an equation for straight line A = mx + b, by the method of

least squares, where A is (assay - mean assay) and X is the

titration sequence. The first fit included all points, the

second SRM KC1 only the third excluded titration numbers 6,

7, 8, 11 and 12. On the basis of the analysis of these data

there is no evidence to indicate that the measurement process

is not in the state of control (the slope, m, is not significant even at the 10 percent level) . Thus the measurement

process is "in the state of control."

+40

+20

•

-20

-40

O J

O

o

0°a

J

oo

o

o o

J

o

J L J L £L J L 10 12 14 16

TITRATION SEQUENCE

O SRM KCl Q 0ECD KCl

Figure 10. Differences between individual values and the

corresponding means.

In addition to the random error component [standard

deviation) one must also take into account possible sources

of systematic error (due to uncertainties of mass, charge,

23
faraday and molecular weight) . Estimate of the magnitude of

the systematic error is 0.0044 percent. The overall uncertainty (sum of systematic and random error estimates) is

0.0079 percent.

Three comments are in order:

1. It should be stressed that for large samples {e.g.,

11 meq) pregeneration of silver ion is a very important part

of the procedure. Early attempts to deliver the chloride

sample into the cell before generation of the major portion

of silver ion yielded low results. Two factors could be

responsible for this : a) high corrosion current of silver

in the presence of chloride; b) loss of HC1 from strongly

acid (20 percent HC10.) solution by volatilization.

2. KC1 must be predissolved in water (5 ml) since

potassium perchlorate is itself poorly soluble.

3. Before determining the end point, it is advisable to

tap the indicator electrodes in order to remove the silver

chloride precipitate which accumulates on them in the course

of the prolonged equilibration period.

e. Conclusions. Determination of chloride by constant

current coulometric argentimetry can be performed with a precision on the order of 0.0025 percent. In addition to the

random error, the uncertainty in the assay of KC1 must also

include the estimate of possible systematic errors. The

estimate of the total systematic error is 0.0044 percent.

The major part of the systematic error is contributed by the

uncertainties in the atomic weights (0.0027 percent). Thus,

the overall uncertainty in the assay is 0.0079 percent.

2 . Gallium Arsenide Stoichiometry

Samples were removed from their plastic packaging,

placed on a porcelain plate and divided approximately in half

by applying moderate pressure with a steel knife along the

cleavage plane of the crystal. Subsequently each piece was

etched in a platinum crucible using ACS reagent-grade HF

24
washed in distilled water and vacuum dried in a desiccator

as specified in the OECD instructions under deoxygenation

procedure. Each piece was placed into a platinum boat,

weighed and delivered carefully into a previously washed and

dried 125-ml Erlenmeyer flask. Five milliliters of "Suprapure"

nitric acid were delivered into the flask in a hood, the flask

was inclined so that it was virtually horizontal, to prevent

the loss of spray, and left in that position until dissolution of the sample was complete.

a. Method. Since this exercise involved the determination of GaAs stoichiometry obviously t\\ro methods were

used: one for Ga and one for As. Gallium was determined

via an EDTA complexation reaction and back titration of

excess EDTA with zinc. In general, the analytical procedure

of Reilley et al . [10] was adopted. These authors have

already shown that gallium can be determined volumetrically

with precision and accuracy better than 0.05 percent. The

coulometric procedure was developed in our laboratory. The

arsenic determination was based on our earlier work [11]

.

Reilley' s procedure for the determination of gallium

required standard EDTA and standard zinc solutions. Excess

EDTA was added to complex the trivalent gallium (in acetate

buffer solution), heated, and the excess EDTA was back

titrated with standard zinc solution. A small amount of

mercuric EDTA complex was added to the solution to act as a indicator ion, using a mercury indicator electrode.

In our method, EDTA was handled as a solid. It was

standardized coulometrically with electrogenerated Zn and

the end-point was determined amperometrically using a gold

amalgam polarizable electrode, a standard calomel reference

electrode and an applied potential of -1.20 V vs. SCE. This

potential corresponds to the diffusion plateau of the Zn

+ reduction waVe.

b. Results. Two different materials were analyzed:

OECD single crystall GaAs and a commercially available

25
undoped polycrystalline material, which on the basis of impurity analysis was estimated by the manufacturer to be

99.999 percent pure.

The results of analysis are summarized in Tables 3 and

4. Since in the determination of stoichiometry it is the

molar ratio of components which is of interest, the results

are reported as moles of element (Ga or As) per gram of

material

Table 3. Coulometric analysis of GaAs

Polycrystalline Material

Sample No. Ga, mol/g GaAs As, mol/g GaAs Ga/As

1 6.91240 6.01202

2 6.91264 6.91256

3 6.91341 6.91208

Average 6.91282 6.91222

s = 0.00044 0.00029 1.000086

+ 0.000078

Table 4. Coulometric analysis of GaAs

Single Crystal Material (OECD)

As, mol/g GaAs Ga/As

6.91325

6.91283

6.91276

6.91259

6.91286

0.00028 0.999994

Sample No. Ga , mol/g

18 6.91291

21

J_ 6.91324

22 6.91244

24 6.91269

Average 6.91280

s = 0.00035

+ 0.000065

26
c. Discussion. It is quite clear from the data in

the above table that the OECD single crystal material is

stoichiometric within 0.007 percent {i.e., Ga/As = 1.000).

In the polycrys talline material the Ga/As is about 0.01 percent greater than unity. The low value for the concentration

of As appears to be responsible for this, since the concentration of Ga is approximately the same in both materials

.

This polycrystalline material is now under investigation to

determine what element has replaced arsenic in the lattice

(oxygen is one possibility)

.

The situation is quite disturbing when one attempts to

perform mass balance calculations. The results of this

exercise are summarized in Table 5.

Table 5. Mass balance for GaAs

Material Element At Wt of Ga a At Wt of Gab

69.72 69.733

Polycrystalline

material Ga 48.1962 48.2052

As 51.7875 51.7875

99.9837 99.9927

+ 0.0078 + 0078

Single Crystal

Material (OECD) Ga 48 1960 48 2050

As 51 7922 51 7922

99 9882 99 9972

+ 0065 + .0065

'Presently accepted value, C & E News 4_8, 39 (1970)

G. E.

(1935)

b

F. Lundell and J. I. Hoffman, J. Res NBS 15, 409

27
For both materials (disregarding the fact that the

first material appears to be nonstoichiometric) the mass

balance is low by over 0.01 percent. Since the impurity

levels in these materials are such that they cannot possibly

account for this material deficiency, two other alternate

explanations are in order:

(1) Error in the method

(2) Error in the atomic weights

Since all experimental parameters are measured on an

absolute basis, the only other possible way that the measurement method could be in error is if the determination of Ga

and As were biased by the same amount and in the same direction due to unsuspected sources of error. The likelihood

of this is rather remote.

In considering the errors in the atomic weights, arsenic

can be ruled out as a possible suspect (mononuclidic element) . When the report of the IUPAC Commission on Atomic

Weights is examined, one finds that the value 69.72 for the

atomic weight of gallium is based on three independent

determinations: Richards and Craig (1923) 69.713 from

GaCl.,/3 Ag (recalculated on the basis of CI = 35.435;

Au = 107.868); Lundell and Hoffman (1935) 69.7333, from

2 Ga/Ga ? 7

. ratio; and 69.72 value based on the mass spectrometric determination of Ga /Ga ratio by Inghram,

et at. (1948)

Taking the atomic weight of gallium as 69.7333 (Lundell

and Hoffman value) the mass balance is much more satisfactory as shown in the above Table.

Since the atomic weight of arsenic is well known, a more

extensive study of GaAs stoichiometry could produce another

independent value for the atomic weight of gallium on the

basis of combining weight calculations. Further studies of

the direct coulometric determination of the electrochemical

equivalent and the atomic weight of Ga, using high-purity

metal, are now in progress in this laboratory.

28
d. Error Analysis. In addition to the random errors

of measurement there are the following two sources of

possible systematic error: (1) the atomic weight of gallium

is a suspect which might contribute as much as 0.01 percent

error to the assay of GaAs ; (2) other sources (measurement

of current, time , mass and the faraday) amounting to about

0.002 percent.

The coulometric determination of the molar ratio in this

two- component system, however, obviates these sources of the

systematic error and thus only the random error component of

the uncertainty is effective. For single crystal material,

the uncertainty in the Ga/As is only 0.007 percent.

e. Conclusions. Both Ga and As in GaAs can be

determined coulometrically with precision on the order of a few parts in 100,000

.

The method appears promising for the determination of

deviations from 1:1 stoichiometric balance.

The obtained data indicate that the accepted value for

the atomic weight of gallium (69.72) is too low. The Lundell

and Hoffman value (69.733) appears to be more accurate.

Further work is in progress to test this conclusion.

The undoped polycrystalline material appears to be

slightly nonstoichiometric (Ga/As = 1,000086). This material

is still under the investigation to determine what element

replaces As in the lattice.

D. Analysis of Standard Reference Materials

1 . Tr is -hydrochloride

Twelve samples of tris (hydroxymethyl) aminomethane hydrochloride were analyzed for their chloride content. The

analyses were performed on an "as received" basis, i.e., the

material was taken for analysis from sample bottles without

any pretreatment , such as crushing, drying, eto. The accurate

mass of samples was obtained by applying appropriate buoyancy

corrections to the weight in air. The chloride was pre29
cipitated by coulometr ically generated Ag , and the results

of analyses are summarized in the following table.

Table 6. Results of Analysis of Tris-hydrochloride

Sequence of

Analysis

1

2

3

4

5

6

7

8

9

10

11

12

Sample No.

Chloride Assay

% of theoretical

12 99.688

2 99.717

9 99.721

5 99.690

10 99.706

3 99.668

4 99.652

1 99.652

7 99.697

8 99.704

6 99.647

11 99.710

Average

s 99.688

s = 027; / „

= 0.008

The coulometric determinations were shown earlier to be

more than an order of magnitude more precise (0.003 percent)

than the 0.027 percent, the random error estimate of the

above set. On the basis of reasoning that the random error

of a set of determinations is composed of the random error

of measurement component, S , and the random distribution

of impurity in the material [heterogeneity), S, , one can

state that

30
S total " C S h

+ Slh/2

^

inthe case at hand, S. . n = 0.027 percent and S =0.003 ' total r m

percent. Solving the above relationship for S, one can

conclude that heterogeneity of the sample is responsible for

virtually all of the random error.

2 . Standard Reference KC1

a, Preliminary Investigations. The purpose of the

preliminary investigation of the material was to establish:

the suitability of the material to be issued as primary

standard in the form that it was obtained from the manufacturer; the need for such treatment as drying; the drying

conditions; and the effect of relative humidity.

The preliminary investigations were conducted with two

composite samples: Composite I was produced by mixing

together equal weights of KC1 from six bottles (Bottle Numbers

1-6) and Composite II consisted of equal weights of KC1

from the remaining six bottles (Bottle Numbers 7-12).

The results of analysis of the above two composite

samples and the corresponding changes of the conditions are

summarized in Table 7.

From the above data it is quite apparent that the

material in its original state contains nearly 0.1 percent

water (assay on "as received" basis 99.91 percent). As such

it does not meet the requirements for a primary standard,

which must assay 99.98 percent or more. Moreover the occluded water is not distributed uniformly, as evidenced by

the lower precision of the analytical results of untreated

samples in comparison with other data.

Crushing and drying at 130° C apparently releases most

of the occluded mother liquor as indicated by an increase

in the assay of the material (99.97 percent), however not

all of the water is released.

31
Table 7. Preliminary studies on SRM KC1

Treatment

1, None:

"As received"

Composite No. Chloride assay, %

1

1

11

99.915

99.901

99.912

Average 99.909

2. Crushed and dried at

130 °C for 18 hours

1

1

11

11

99.980

99.981

99.982

99.975

Average 99.979

3. Crushed and dried at 1

200 °C for 18 hours 1

11

11

99.997

99.996

99.995

99.995

Average 99.996

4. Uncrushed; dried at

500 °C for 4 hours

99.994

99.990

Average 99.992

32
Crushing and drying at 200° C appears to be highly

satisfactory treatment of the material (assay = 99.996). From

the standpoint of practical use crushing is a process which

could cause contamination of the material, and for that

reason a heat treatment at 500° C in Vycor crucibles without

any crushing was attempted. Pyrex containers cannot be

used for this process. A reaction between Pyrex and KC1

occurs at this temperature. The material processed in this

manner indicate that the material is converted to virtually

stoichiometric KC1 (assay = 99.992 percent). Material tested

in this manner was also checked for decomposition (loss of

KC1 upon heating) by dissolving known amount of material in

deserated distilled water and checking its pH . The pH of

IM solution was very close to 7, indicating no appreciable

decomposition.

The exposure of the material to relative humidities from

"0" (PJ.) to 75 percent for four days indicates that it

does not change significantly from its original state. The

weight changes of KC1 upon exposure to different environments

are shown in Table 8.

Table 8. Exposure of KC1 to various humidities.

Relative humidities

"0" (p

2 o5

) 33%

52%

75%

Percent change weight

(4 day exposure)

-0.006

-0.005

-0.003

+0.002

33
b. Final Determination of Chloride . It was thus

decided that heating of the material at 500 u C for at least

four hours is a satisfactory treatment which insures

virtually complete removal of occluded mother liquor. All

work on final analysis of this material was conducted after

such treatment.

The final analyses of the material were conducted on

twelve samples, each sample representing approximately 8

weight percent of the material in the lot. The results of

analysis are shown in Table 9. Column one represents the

sequence of titrations, column two represents the number

assigned to the sample bottle and column three gives the

assay of material. The assay, 99.9965 percent, is consistent with the value obtained for composite samples (treatment 3 and 4 in Table 7) , with the 95 percent confidence

interval for the mean of 0.0016 percent, based on 11 degrees

of freedom.

It should be pointed out that the assay is computed on

the KC1 basis. Any impurity which is precipitated by silver

is also included in this value {e.g. Br , I , eta.). Moreover, corrections for cations other than potassium should

also be applied. It is for these reasons that another

value, the silver precipitation titer, can be useful:

0.0134124 ± 0.0000011 mol g" 1

. The uncertainty figure represents the sum of the random error estimate (95 percent of

confidence limits) and estimate of the possible systematic

errors. Of all the sources of systematic error the uncertainties in the atomic weights of chlorine and potassium

are by far the largest (total uncertainty 0.004 AMU or

0.005 percent). To reduce the systematic error contributions

due to molecular weight uncertainty and the uncertainty of

the faraday, another useful constant, the electrochemical

equivalent, can be computed for this material. The value of

the electrochemical equivalent for this material is

0. 772724 ± 0. 000019 mg C"

1

. 34
Table 9. Final Analysis of SRM KC1

Titration Sample Assay, wt % sequence No.

1 1 99.9969

2 2 99.9952

3 3 99.9930

4 4 99.9971

5 5 99.9979

9 11 99.9961

10 8 99.9991

12 12 99.9909

13 6 99.9985

14 9 99.9988

15 10 99.9980

16 7 99.9960

99.9965

S = 0.0025

t S

= 0.0016

*In the titration sequence numbers 6, 7, 8, and 11 correspond to titrations of different material (OECD single crystal

KC1) , thus the results are not included in this data table.

35
Here again the uncertainty figure is the sum of the

95 percent limits of random error (0.0016 percent) and the

estimate of possible sources of systematic error (mass,

electrical and time measurements: 0.0009 percent).

c. Analytical Procedure. After drying the KC1

samples at 500° C for four hours they were placed into a Po^r desiccator and stored there until needed. For each

titration a 2-g sample was weighed out in a Pt boat and delivered into 125-ml Erlenmeyer flask. Five ml of distilled

water were added to the flask and the sample was dissolved.

The titrations were performed by electrogenerated silver

ion. The method was similar to the one described earlier

[12]. The electrolyte was changed to 20 wt percent HC10.,

which was used by Craig and co-workers at the NBS in their

determination of the value of the faraday. Thus the electro

chemical parameters of this system (corrosion current

density, current efficiency, dissolution of silver oxide,

etc.) are well known. Secondly, this electrolyte has lower

specific resistance than the electrolyte used earlier.

Consequently, the power dissipation (heating) in the cell is

reduced accordingly. Following pregeneration at 500 mA of

about 99.95 percent of Ag which is needed to precipitate

all of the chloride in the sample, the sample is delivered

into the cell via a syphon arrangement and permitted to

equilibrate 1 hour in the dark. The titration is finally

completed at 0.6 mA current.

d. Conclusions. The material is homogeneous and

perfectly suitable as a primary standard, provided it is

dried at 500° C for four hours, and can be certified as

99.9965 ± 0.0025 percent based on chloride (halide) assay.

This value is based on 74.555 as the molecular weight of KC1

and 96486.70 C mol" 1 for the faraday.

Based on chloride assay two other useful constants

should be given: silver precipitation titer 0.0134124 ±

36
.0000011 mol g and the electrochemical equivalent

0. 772724 ± 0,000014 mg C"

1

.

3. Standard Reference NaCl

Preliminary evaluation of this lot of NaCl indicated that

this material, as received, does not meet the specifications

for a primary standard. The assay is 99.92 percent (NBS Tech.

Note 505, pp. 65-67). Crushing and drying the material at

200° C improves its assay to 99.99 percent.

The determination of halides in this material was performed by the earlier published method [8]

As in the case of KC1 crushing and drying at 200° C is

a satisfactory treatment for the material. Crushing

however could cause contamination of the material. For that

reason a heat treatment at 500° C without any crushing was

carried out in Vycor crucibles

The results of analyses of samples from eight different

locations in the lot are summarized below (Table 10) in the

sequence in which analyses were performed.

The original design of experiment (as proposed by Dr.

John Mandel, Statistical Consultant, NBS) required duplicate

analysis on each sample, thus enabling separation of variations in the results into two components: (1) those caused

by random errors of the method, and (2) those caused by the

variability of the material in the log (heterogeneity) . Since

in the certification of this material for the purpose at hand

(clinical standard) an uncertainty of 0.01 percent can be

considered negligible, it appears that separation of the two

error components is not warranted. The total error (both

due to the random error component of the method and to the

heterogeneity) is much less than 0.01 percent and one can thus

safely make a statement that the lot is homogenous at the

0.01 percent level.

In summary, halide titrations show that this lot of material conforms to NaCl stoichiometry to the extent of

37
99.9950 ± 0.0035 percent, where the uncertainty figure

represents the 95 percent confidence interval for the mean.

Table 10. Coulometric determination of halides in SRM

NaCl

Sample No Assay as NaCl, %

3C

3A

1A

4D

4B

1C

2B

2D

99.9912

99.9939

99.9946

99.9927

99.9975

100.0002

99.9905

99.9998

Mean

standard deviation

S.D. of the mean

95% confidence

interval for the mean

99.9950

0.0037

0.0013

0.0031

George Marinenko

38
POLAROGRAPHY

A. Introduction

During the past year most of the analytical efforts of

the polarographic laboratory have been devoted to trace

analysis and have been greatly concerned with heavy metals

in environmental samples and Standard Reference Materials.

Considerable effort has also been spent in the analysis of

major constituents, particularly those in copper-base alloys

A few of the more interesting of these activities are described in the following sections of this chapter. The

polarographic facilities have been transferred to the

Electrochemical Analysis Section during the past year and

part of the equipment in the new facilities is shown in

Figure 11.

HjLj5i,L

Figure 11. Cathode ray polarograph

39
B . Trace Analysis

1. Reagent and Environment Blanks

In an effort to increase the quality of the reagents

used in the trace analysis program of the Analytical Chemistry

Division, a number of acids have been redistilled in subboiling quartz stills by Section 310.06 and made available to

other members of the Division. Samples of these acids

weighing from 160 to 290 g as well as a sample of the Division

distilled water were taken for analysis. The samples, which

had been evaporated to dryness in quartz beakers in laminarflow hoods, were treated with 5 drops of nitric acid (purified by 310.06) to destroy residual amounts of organic

material and again evaporated to dryness. One-half ml of

hydrochloric acid was added and the samples were again

evaporated to dryness on low heat. The residues were dissolved in 2.0 ml of 15 percent hydroxylamine hydrochloride,

heated 60 seconds, and measured polarographically . The

results are shown in Table 11.

Table 11. Cu, Pb , Cd, and Zn in acids and distilled water.

Cu, ppb Pb , ppb Cd, ppb Zn, ppb

4 0.4 0.03 0.6

<0.1 <0.5 <0.1 <0.1

<0.1 <0.5 <0.1 <0.1

<0.1 <1 <0.1 <0.1

Iron was also of interest since iron is to be determined

polarographically in lunar samples taken on the Apollo

flights. Additional samples of the acids were evaporated to

dryness and the residues were dissolved in dilute perchloric

acid. Sodium acetate and Solochrome Violet RS were added

and iron was determined polarographically. The results are

given in Table 12.

40

Sample

distilled

H

2

HN0

3

HC1 (6M)

HC10,
Table 12. Iron in redistilled acids

Fe

Sample yg, total ng/g sample

HC1 (9M) 0.62 2.6

HN0

3

0.41 1.4

Since the iron content of the samples to be analyzed

is expected to be about 10 percent, these acids are sufficiently pure for use.

The iron fall-out in the laminar-flow hoods discussed

in last year's annual report [13] was also measured. Some

of the metal in the interior showed corrosion and it was

probable that the iron fallout had increased. An uncovered

50-ml beaker was allowed to stand in the hood 24 hours then

treated with acid and measured polarographically . A value

of 0.55 yg of iron was obtained, which represents about a 10-fold increase from last year.

It was necessary also, in connection with the analyses

of lunar samples, to determine the iron contamination which

would occur if the sample were broken in a diamond mortar.

A piece of a pure quartz container was taken as well as a sample of the same quartz container, crushed to a fine

powder in an agate mortar, after having been first broken

into smaller pieces in an iron mortar. One-gram samples

were dissolved in hydrofluoric acid and fumed to dryness

several times with perchloric acid to remove fluoride. The

residues were dissolved in 1 ml of 9M HC1, transferred to a separatory funnel, diluted to about 10 ml and iron was extracted with cupferron and chloroform. After evaporation of

chloroform and destruction of the organic material by fuming

with nitric and perchloric acids, iron was determined

polarographically as the Solochrome Violet RS complex. Values

of 2.6 ppm of iron were obtained for the uncrushed quartz,

41
and 81.7 ppm for the crushed quartz, showing that considerable

iron contamination arises from the mortar.

2. Environmental Analysis

NTA in water -- The purpose of this project was to

investigate the feasibility of using cathode ray polarography

for the determination of trace amounts of NTA after its

separation from interfering constituents in natural water

and sewage.

A number of polarographic methods for the determination

of NTA have been reported, most of them involving the addition of an excess of metal ion and measuring the reduction

peak of the metal-NTA complex. Daniel and LeBlanc utilized

the addition of excess cadmium ion at a pH of 7-10 to

determine NTA in EDTA by conventional d.c. polarography [14,

15] . Farrow and Hill modified the method somewhat using

standard additions of the Cd-NTA complex and single cell

cathode ray polarography [16] . Haberman determined traces

of NTA in river water and sewage by the addition of excess

indium and measurement of the In-NTA reduction peak [17].

To increase the sensitivity and reduce interferences, he used

both cation and anion exchange column separations . Afghan

and Goulden have developed methods for the determination of

traces of NTA in water by measurement of either the Pb-NTA

complex or the Bi-NTA complex [18, 19]. The method using

the Bi-NTA complex has been adapted by Gahler of the Water

Quality Office, Pacific Northwest Laboratory, Corvallis,

Oregon, for the determination of NTA in seawater [20] and

by the Inland Waters Branch, Department of Energy, Mines and

Resources, Ottawa, Canada, for the determination of NTA in

water [21]

Preliminary studies were conducted involving the lead,

cadmium and bismuth complexes to determine which gave the

best defined polarographic peaks. Indium was not considered

as Afghan [19] reports that very high concentrations of

42
indium are necessary for complete NTA recovery and at a mole ratio of 5:1 of In:NTA, the polarographic peak of the

indium-NTA complex is extremely difficult to measure owing

to its proximity to the indium reduction peak. The Pb-NTA

complex was investigated in 3 different buffer systems : tris

hydrochloride- ammonium hydroxide, glycine- ammonium hydroxide,

and ammonium chloride -ammonium hydroxide around pH 7-8. The

Cd-NTA complex was also measured in an ammonium chlorideammonium hydroxide buffer system at pH about 9. The Bi-NTA

complex was then investigated in NaCl media at pH 2 and

appeared to give the best-defined peaks and the greatest peak

height for a given concentration of NTA.

Aliquots of the supernatant liquid of several solutions

of NTA, which had been equilibrated with river bottom mud

for about a month to give final concentrations of 10 and 20

ppm of NTA, were then analyzed. The river bottom mud

solution contained about 5 percent solids. Values of 5.2

and 10.3 ppm of NTA were obtained showing recoveries of only

about 50 percent. The original NTA solutions used to prepare

the sludge mixtures were then analyzed to determine if the

solution composition had changed. Values of 9.6 and 18.9

ppm were obtained showing good agreement with the 10 and

20 ppm starting compositions.

The recommended procedure for the preparation of the

calibration curves which was essentially that developed by

Afghan and Goulden [18, 19] and recommended by Traversy [21],

utilizing a differential cathode ray polarograph in the subtractive mode of operation is given below. Aliquot 0.0, 1.0,

2.0, 3.0, 4.0, and 5.0 ml of standard NTA solution (10 mg/1)

into 50-ml beakers. Add 5 ml of IN HC1 to the blank. Add

4.5 ml of IN HC1 to each of the other solutions. Add 1 ml

of 1 percent hydroxylamine hydrochloride to each beaker to

reduce iron, then add 0.5 ml of bismuth solution (0.2 mg

Bi/ml in 1M HC1) . Add 25 ml of distilled water to each,

adjust the pH to 2.0 with ammonium hydroxide and dilute the

43
solutions to 50.0 ml in a volumetric flask. Add about 1 ml

of mercury to each polarographic cell and transfer the

solutions to the cells. The blank solution is placed in

the right hand cell position and the sample solutions in the

left hand cell position. Deaerate with nitrogen for 10 min.,

then measure the Bi-NTA polarographic peak at about -0.25V

vs. a mercury pool anode.

Several calibration curves in the region from 0.2 to 1.0

ppm of NTA were then run on different days. The results are

shown in Figure 12.

1 1 1 1

• SET l] — O SET 2 \ DISTILLED H2 A —

A SET 3

J ?

+ TAP WATER ELECTROLYZED 2 HOURS o — STANDARO ADDITION —

A -

o+

• —

A®

®

+

A

•

•

+ -

A -

I

1 1

1

1 1

6 -

5 -

4 -

3 -

0.2 0.4 0.6 NTA, ppm

0.8 1.0

Figure 12 . NTA calibration curves

44
Some tap waters were also measured, but generally

erratic and incomplete NTA recovery was obtained. An interfering peak believed to be copper or ferric ion which had not

been successfully reduced appeared close to the rising

portion of the Bi-NTA peak making reproducible measurement

of the Bi-NTA difficult. Although the solutions were measured

subtractively with a tap water blank in the second cell, it

was not possible to balance out the base lines.

Gahler [20] found that as little as 2 ppm of copper in

water causes very high results. At first this seemed to be

inconsistent with the above findings. Then it was realized

that he was using a low resolution conventional polarograph

which would present the Cu-Bi-NTA peak as a single peak.

The cathode ray polarograph separates the two peaks , but the

Bi-NTA peak follows the interfering peak so closely that a diffusion level plateau from which to measure the base line is

is not reached.

In view of the fact that the chromatographic separation

of NTA might not be feasible, it seemed possible that interfering metal ions could be separated by electrolysis of an

acidified solution of the tap water for several hours at

-0.9V. Preliminary efforts showed this to be feasible. The

results are also given in Figure 12 showing good recovery

except for the 0.4 ppm point.

Although NTA is reported to form complexes with few

metal ions, except bismuth, commonly present in tap water

at pH 2, the possibility exists that incomplete NTA recovery

from tap water could result from its reacting with some other

species in the water. This effect could probably be overcome by a standard addition technique. A set of tap water

samples was taken through the procedure as described above

except 4 ml of additional NTA was added to each solution

including the blank. The results are also shown in Figure

12. It is seen that the recovery is quantitative except

for the 0.2 ppm point.

45
Sufficient instrumental sensitivity is available so that

as little as 0.05 ppm of NTA in the final solution could be

readily determined. Although this is the equivalent of 0.1 ppm

in the original water sample, usually sufficient water sample

is available for preconcentration making possible the determination of even lower levels of NTA.

In conclusion, it appears that the polarographic

determination of NTA as the Bi-NTA complex is a suitable

method. However, if the chromatographic separation of the

NTA is not performed, a pre-electrolysis step and/or the

standard addition technique may be necessary.

C . Lead in Paint

A variety of types of paint was submitted for lead

determinations by the National Commission on Product Safety.

The pigments of the individual samples included lead-base,

titanium-base and others. Approximately 100 mg of the dried

paint samples were slowly ashed in Vycor crucibles to 500° C

and sent for spectrographic analysis which showed no significant amounts of lead present. The filtrates were

evaporated to dryness and diluted with dilute hydrochloric

acid to an appropriate volume in a volumetric flask. Aliquots

were taken and lead was extracted with sodium diethyldithiocarbamate and chloroform. After destruction of organic

material and evaporation to dryness, the residues were dissolved in . IN hydrochloric acid containing ascorbic acid

and measured polarographically . The results are given in

Table 13, as well as values obtained in another laboratory.

Aliquots of samples 2 through 6 were also run directly

with no separations and the results showed good agreement

with those obtained above. The results for samples 2 through 6 were 4.20, 0.37, 0.48, 9.50, and 0.46 percent

lead, respectively.

46
_,ead, Percent

Polarography Atomic absorption

0.11 0.12

4.18 4.6

.34 .40

.48 .54

9.63 9.5

.44 .43

.13 .15

Table 13. Lead in paint

Sample designation

1

2

3

4

5

6

7

D. Lead in Industrial Air

Polarography has again proved to be a very helpful

technique in the monitoring of the safety of a lead-glass

preparation process (13) . The NBS Glass Section collected

a number of particulate samples on Metricil filters at

various steps of the process. The maximum permissible limit

3 of lead exposure is set at 0.2 mg/m /8-hr day/5-day week.

3 The samples were collected at the rate of 0.035 m /min and

3 from 0.017 to 41 m of air was sampled.

The papers were wet-ashed with nitric, hydrochloric and

perchloric acids. After evaporation to dryness, the residues

were dissolved in . IN hydrochloric acid and the lead reduction peak measured polarographically . The results are

shown in Table 14 and are blank corrected. Only one sample,

#789, was above the permissible limit.

E. Copper, Lead, Cadmium and Zinc in a Particulate Standard

Reference Material.

In the consideration of methods appropriate for the

analysis of a proposed particulate Standard Reference Material, cathode ray polarography seemed to offer many

advantages. Owing to the selectivity of the method, a variety of elements may be determined concurrently. The

sensitivities obtainable are such that less than 0.1 yg of

47
the element in question can be determined, making the use of

small samples possible. Previous experience in this laboratory in the polarographic determination of iron, copper,

lead and cadmium in particulate material collected on

Millipore filters and in dust fall-out has proved the useful

ness and reliability of the technique [13]

Table 14. Lead in air

Sample ? designation Pb , micrograms Sample size, m

781

782

783

784

785

786

787

788

789

790

791

792

793

Although the work described was done with no chemical

separations, it appeared that more accurate results, such

as would be required for SRM's, could be obtained by the use

of some separations. Also other supporting electrolytes

which might give improved peak definition could be investigated. Comparisons of oxalic acid, EDTA-sodium acetate,

and hydroxylamine hydrochloride supporting electrolytes showed

that the latter gave the best-defined peaks for the amounts

and ratios of copper, lead, cadmium and zinc probably present

48

3.8 13.65

0.13 .035

9.5 33.25

8.9 .052

.75 .087

.49 5.25

2.9 15.61

4.9 17.75

22.9 .070

.20 .017

3.2 41.3

2.9 11.9

.09 blank paper
in the sample.

Separation of the copper, lead, cadmium and zinc could

probably be accomplished by extractions with either dithizone

or sodium diethyldithiocarbamate and chloroform. Preliminary

attempts at dithizone extraction were unsuccessful, possibly

because of the interference of large amounts of iron. Large

amounts of iron would also interfere with the extraction by

carbamate so it was decided to remove the bulk of the iron

by extraction with isobutyl acetate prior to the carbamate

extraction [22] . The conditions used for the extraction of

copper, lead, cadmium, and zinc with carbamate were as given

by Bode [23]. Complete recoveries were obtained to within

about ±5%. The possible interference of residual amounts

of iron or manganese could be eliminated by brief, gentle

heating of the hydroxylamine hydrochloride supporting

electrolyte, reducing the iron and manganese to their noninterfering lower valence states

.

Some problems were experienced in the acid dissolution of

the particulate sample. After repeated fumings with nitric

and perchloric acids, several small black particles remained

undissolved. The procedure used is given below.

Duplicate 100-mg samples were dissolved and organic

material was oxidized by fuming with nitric and perchloric

acids. The soluble residues were dissolved in hydrochloric

acid and iron was extracted with isobutyl acetate. The

acid layer was evaporated to dryness and the residues dissolved in hydrochloric acid. Ascorbic acid was added to

reduce residual iron. Sodium citrate and ammonium hydroxide

were added to adjust the pH to about 9, and copper, lead,

cadmium and zinc were extracted with sodium diethyldithiocarbamate and chloroform. After evaporation of chloroform

and destruction of organic material by fuming with nitric

and perchloric acids, copper, lead, cadmium and zinc were

determined polarographically in a hydroxylamine hydrochloride

49
supporting electrolyte which had been heated for 2 minutes

at slightly below 100° C.

A blank solution and two reference solutions, one

containing 81 yg of copper, 406 yg of lead, 6.1 yg of cadmium

and 200 yg of zinc, and the other containing 121 yg of

copper, 812 yg of lead, 10 yg of cadmium and 401 yg of zinc,

were also carried through the procedure.

The results obtained by the above procedure are shown

below in Table 15.

Table 15. Determination of copper, lead, cadmium,

and zinc in proposed particulate standard

reference material.

Cu, % Pb, % Cd, % Zn, % 0.0926 0.709 0.00674 0.368

0.0928 0.713 0.00676 0.339

Except for zinc, it is felt that the results show

excellent agreement and are well within the 2-5 percent

measuring error commonly encountered in polarography . The

inconsistency of the zinc results have not been satisfactorily

explained. A possible, but unlikely, explanation could be

that erratic zinc contamination occurred. However, even the

zinc results are still well within the precision generally

encountered in this type of measurement.

Bismuth and thallium could probably have been determined at the same time on the same sample by use of a slightly larger sample weight. A larger sample weight might

also allow accumulation of sufficient weight of the undissolved particles for a semi-qualitative spectrographic

analysis

Iron, aluminum, and probably nickel could also be

50
readily determined on the same sample.

F. Iron in 1-ppm Glass

The analysis of the trace elements in glass standards

was discussed in detail in last year's report [13]. The

possibility existed that the iron value might be slightly

high in the 1-ppm glass owing to the omission of the ammonium

hydroxide precipitation, so six more samples were taken

through the procedure including the ammonium hydroxide

separation. The supporting electrolyte contained 0.2 ml of

1+1 sulfuric acid, 0.5 ml of saturated sodium pyrophosphate

and sufficient ammonium hydroxide to reach a pH of 2. The

solutions were then diluted to 10.0 ml. The oxygen interference in this supporting electrolyte was found to be

somewhat less than with the EDTA or oxalic acid solutions.

Two or three separate measurements were made on portions of

the same solution of each sample and the average of the

results is given in Table 16.

Table 16. Determination of iron in 1-ppm glass.

Sample No.

2 36

40

69

76

114

Average =

s , ppm

c 9- = O , These values are in good agreement with the 13.5 ppm value

obtained earlier.

51

Fe, ppm

13 3

13 8

12 .6

13 .3

13 .7

12 .8

13 .3

.48

3 .6
G. Aluminum, Lead, Bismuth, Tellurium and Titanium in Special

Steels

The work discussed in last year's annual report [13] on

the determination of several trace elements in special steels

has continued with the determination of aluminum, lead,

bismuth, tellurium and titanium in SRM's 1262, 1263, 363,

and 1264.

For the determination of aluminum in 1263 and 363,

duplicate samples of each weighing 0.5 g were dissolved in

dilute hydrochloric acid, filtered and washed with dilute

hydrochloric acid. The filter papers were ignited and the

residues treated with sulfuric and hydrofluoric acids and

evaporated to dryness. The residues were fused with sodium

carbonate, the fusion products dissolved in water, neutralized with hydrochloric acid and added to the main

filtrate. Ten-ml aliquots were transferred to a separatory

funnel. After buffering with acetic acid and sodium acetate,

iron, copper, manganese, etc. were extracted with chloroform

and sodium diethyldithocarbamate . Aluminum was then extracted from the aqueous layer with chloroform and cupferron.

After destruction of organic material, aluminum was measured

polarographically as the Solochrome Violet RS complex. A

value of 0.045 percent aluminum was obtained on SRM 170a,

which was carried through the procedure at the same time.

The certified value is 0.046 percent. The results are given

in Table 17.

Lead in SRM 1264 was separated from the bulk of the

iron by extraction of the iron from 1-g samples with isobutyl

acetate. Lead was then extracted with sodium diethyldithiocarbamate and chloroform. The extracts were evaporated to

dryness, organic material was destroyed with nitric and perchloric acids, and lead was determined polarographically in

a nitric acid-sodium tartrate supporting electrolyte. The

results for six separate determinations are shown in Table

19.

52
Table 17. Aluminum in SRM 1263 and 363.

Sample Designation Al , % Average

1263 (composite 2A + 2C) 0.234, .233 0.234

363 (composite) 0.231, .232 0.232

Aluminum in SRM 1264 was determined as just described except

1/10 aliquots of solutions from four 1-g samples were taken.

The reduction peaks were somewhat ill-defined, owing to

the close proximity of some more easily reduced substance.

If additional determinations are made, an acid-cupf erron extraction will also be made. The results are given in Table II

Table 18. Aluminum in SRM 1264

Sample Designation Al , % 1264 (composite 1A + 1C) 0.0081

.0084

.0084

.0079

Average 0.0082

Table 19. Lead in SRM 1264

Sample Designation Pb

,

1264 (composite 1A + 1C) 0.0190

.0195

.0174

.0189

.0197

.0200

Average .0191

s = 0.0009%

53
Lead and bismuth were determined in SRM 1263 and 363

polarographically on aliquots equivalent to 0.2-g samples

after separation of iron with isobutyl acetate and separation

of lead and bismuth with sodium diethyldithiocarbamate . A

blank equivalent to 2 ppm of lead was obtained. Tellurium

was determined polarographically after precipitation with SOusing selenium carrier. The results are shown in Table 20.

Table 20. Lead, bismuth and tellurium in SRM 1263 and

363.

Sample

Designation

2A + 2C)

Pb, % 0.0016

Bi, % Te, % 1263 (composite 0.00076 0.0022

n 3 3 2

s .0001 .0001 .0003

363 (composite) .0018 .00060 .0023

n 3 3 2

s .0001 .0001 .0001

For the determination of titanium in SRM 1262 and 1263 ) triplicate 0.5-g samples were dissolved in dilute hydrochloric

acid. Ascorbic acid was added to reduce iron to the ferrous

state, titanium was precipitated with cupferron, filtered,

washed, dried, and ignited in platinum at 550° C. The residues were treated with hydrofluoric, perchloric and hydrochloric acids and fumed to perchloric fumes. The solutions

were then transferred to beakers, titanium was precipitated

with ammonium hydroxide, filtered and washed. After destruction of organic material with nitric and perchloric

acids, titanium was determined polarographically in sulfuric

acid-EDTA-sodium acetate supporting electrolyte. The results

are given in Table 21.

54
Table 21. Titanium in SRMs 1262 and 1263

Sample designation

1262 (composite 2A + 2C)

coarse and fines

1263 (composite 2A + 2C)

Ti, I 0.084

049

0.004

002

Titanium in SRM 1264 was determined as just described

except that quadruplicate samples weighing 0.2 g each were

taken. The results are given in Table 22.

Table 22. Titanium in SRM 1264

Sample designation

1264 (composite 1A + 1C)

Ti, % 0.237

.238

.238

.249

Average .240

s = 0.006

H. Orchard Leaves (SRM 1571)

The need for certified botanical standards both in

research and in industrial and field applications is leading

to the development and production of number of new Standard

Reference Materials by the National Bureau of Standards. The

first of these to be produced and certified is an orchard

leaf standard. The determination of a number of important

trace elements by cathode ray polarography was investigated

and found to offer considerable advantages in sensitivity

55
and accuracy over many other techniques . In addition several

elements may be done simultaneously on the same solution.

The methods were developed and applied to the analysis and

certification of nickel, lead, bismuth, copper and iron in

the orchard leaves. Results were also obtained for aluminum

and cadmium which have not yet been certified.

For the determination of nickel, the samples were dried

for 24 hours at 90° C and 1-g portions were taken. Organic

material was oxidized With hydrochloric, nitric, and perchloric acids. The samples were fumed almost to dryness,

diluted with water and transferred to a separatory funnel.

After addition of solutions of sodium citrate, hydroxylamine

hydrochloride, and dimethylglyoxime , and adjustment of the

pH with ammonium hydroxide, the nickel dimethylglyoxime

complex was extracted with chloroform. The chloroform extracts were then evaporated to dryness and organic material

was destroyed by fuming to dryness with nitric and perchloric

acids. The residues were dissolved in dilute sulfuric acid;

pyridine and water were added and the nickel reduction peak

was measured polaro.graphically at about -0.9V vs. a mercury

pool anode. Solutions for the establishment of a calibration

curve were carried through each step of the procedure. The

results are shown in Table 23.

Table 23. Determination of nickel in orchard leaves.

Samp le d ssignation

2

9

10

11

12

15

19

Average

s;, ppm :

Nickel , ppm

1.4

1.5

1.2

1.5

1.3

1.5

1.5

1.4

0.1

56
An average value of 1.2 ppm was obtained by another

technique, isotope-dilution spark-source mass spectrometry.

The nickel was then certified at 1.3 ppm.

For lead and bismuth, one-gram samples of the dried

material were weighed and organic material destroyed as described above for nickel. The residues were treated with

dilute hydrochloric acid and water and iron was reduced with

ascorbic acid. Lead and bismuth were then extracted with

chloroform as the sodium diethyldithiocarbamate complexes from

an ammoniacal solution using sodium tartrate and potassium

cyanide to complex interferences . The chloroform extracts

were evaporated to dryness and the organic material destroyed

as already described. The residues were then dissolved in

dilute nitric acid and a sodium tartrate solution. The lead

and bismuth reduction peaks were then measured at about -0.7

and -0.5V vs. a mercury pool anode, respectively. Solutions

for the establishment of a calibration curve were also

carried through each step of the procedure. The results are

shown in Table 24.

An average value of 43 ppm was obtained by isotope-dilution spark-source mass spectrometry and 45 ppm by photon

activation analysis. In view of the fact that the sample

contained a small amount of siliceous material which could

possibly contain a small amount of lead, unattacked by the

acids used, it was decided to include hydrofluoric acid in

the sample dissolution. The procedure was repeated on the

last four samples with the addition of hydrofluoric acid and

an average value of 44.0 ppm was obtained. Again #15

showed significantly higher values for lead.

57
Table 24. Determination of bismuth and lead in orchard leaves.

Sample

designation Bi, ppm Pb , ppm

2 0.11 44.2

.10 41.8

9 .10 46.3

10 .13 44.2

.15 44.8

11 .11 44.2

12 .11 43.6

.11 44.2

13 .12 43.0

15

19

.09

.10

.09

.10

Average 0.11

s, ppm .02

47 9

47 9

43 .6

44 .2

44 .6

1 .7

For the determination of iron and aluminum, quarter-gram

samples of the dried material were weighed and organic matter

destroyed as described above. The residues were treated with

1 ml of dilute perchloric acid and the solution transferred

to a separatory funnel. Iron was then extracted with chloroform as the cupferron complex. The extracts were evaporated

to dryness and organic material destroyed by evaporation to

dryness with nitric and perchloric acids. Hydrochloric acid

58
was added and the solution evaporated to dryness on low heat.

The residues were then taken into solution with dilute

sulfuric acid and diluted to volume with a sodium acetate-EDTA suppor

supporting electrolyte. The iron reduction peak was

measured at about -0.2V vs. a mercury pool anode. Solutions

for the establishment of a calibration curve were carried

through each step of the procedure. The results on the first

set (not reported) showed a variation of iron content of 195

to 359 ppm which is far more than has previously occurred

through inherent procedure or measurement errors and could

only be ascribed to either gross environmental contamination

or sample inhomogeneity . Subsequent sets of samples by this

same procedure did not show this variation. The results are

shown in Table 25.

Table 25. Determination of iron (acid-soluble) a in

orchard leaves.

Sample

designation Fe, ppm

2

9

10

11

12

13

15

19

Set II

260

257

263

257

257

254

258

262

259

3.0

Average

s , ppm

Pooled Average 262

Pooled s 8.8

Set III

258

282

272

259

255

253

282

267

266

11.7

L HCl-HNO

3

-HC10

4

59
An average value of 278 ppm was obtained by isotopedilution spark-source mass spectrometry.

Aluminum was separated from the aqueous layer remaining

after the iron extraction by addition of cupferron, then

sodium acetate was added to raise the pH to 4.5 to 5,

followed by extraction of the aluminum cupferrate complex

with chloroform. The organic material was destroyed as already described, the residues dissolved in 1 ml of 6N

perchloric acid and 5 ml of 2M sodium acetate. Five ml of

0.1% Solochrome Violet RS were added, and the solutions were

diluted to 50 ml and transferred to polyethylene bottles.

The solutions were heated in a water bath at 55-70° C for

5 minutes, cooled, and the aluminum-Solochrome Violet RS

complex reduction peak was measured at about -0.7V vs. a mercury pool anode. Solutions for the establishment of a calibration curve were carried through each step of the

procedure. The results are shown in Table 26.

Table 26. Determination of aluminum (acid-soluble) a

j.n

orchard leaves.

Sample Al , ppm

Set I Set II Set III

2 226 lost 218

9 226 222 211

10 228 241 224

11 225 223 225

12 220 226 204

13 225 229 222

18 223 226 222

19 230 228 225

Average 225 228 219

s , ppm 3.0 6.3 7.6

Pooled average 224

Pooled s 6.7

aHCl-HNO

3

-HC10

4

60
A small amount of adventitious siliceous residue was

always present after the hydrochloric-nitric-perchloric acid

dissolution of the orchard leaves. It seemed of interest

then to determine the contribution to the total iron and

aluminum content this residue would make if dissolved by

HF and sodium carbonate fusion. The aluminum content of

the silica-like material would undoubtedly be greater than

that of iron, but some iron would also be expected to be

present. The procedures outlined above for iron and aluminum

were followed with the following variations

After sample dissolution and destruction of organic

material, the residues were treated with dilute hydrochloric

acid and the resulting solutions were filtered through

Whatman #42 filter paper and the residues policed into the

papers. The papers were ignited in platinum crucibles and

the residues were evaporated to dryness with hydrofluoric

acid and perchloric acid to remove silicon. The remaining

residues were fused in sodium carbonate, the fusion dissolved in dilute hydrochloric acid, and added to the main

filtrate. Iron and aluminum were then extracted with cupferron and the procedure completed as already described. The

results are shown in Tables 26 and 27. From comparison with

Tables 24 and 25 it is seen that the iron and aluminum

content of siliceous residue is 50 and 123 ppm, respectively.

These results were qualitatively confirmed by independent

work on the residues by the Spectrochemical Analysis Section.

Again, one set of iron determinations (not reported)

showed extreme variations of from 263 to 333 ppm. These

variations also could only be attributed to gross environmental

contamination or sample inhomogeneity

Cadmium in the orchard leaves was also of special interest. Cadmium is also extracted with sodium diethyldithiocarbamate along with the lead and bismuth; however the peaks

were small and not too well defined but gave approximate

values of 0.1 ppm. Larger samples were taken and cadmium, as

61
well as additional values for copper, lead, and bismuth were

determined as described below.

Table 27. Determination of iron (total) 3" in orchard

leaves

Sample designation Ironppm

Set I Set III

2 322 297

9 323 314

10 336 295

11 317 310

12 320 310

13 305 295

15 318 317

19 316 300

Average 320 305

s , ppm 8.7 9.0

Pooled average 312

Pooled s 11.4

L HC1-HN0

3

-HC10

4

-HF, Na

2 C0

3

fusion

62
Table 28. Determination of aluminum (total) in orchard

leaves .

Sample designation

2

9

10

11

12

13

15

19

Al , ppm

Set II

359

340

340

340

345

341

346

350

Set III

344

349

341

348

348

350

350

368

Average 345

s , ppm 6 . 7 Pooled average 347

Pooled s 7.5

350

8.0

HC1-HN0

3

-HC10

4

-HF, Na

2 C0

3

£usion

63
Duplicate 5-g samples were dissolved and organic

material destroyed by fuming to dryness with nitric and perchloric acids. The residues were dissolved in hydrochloric

acid, and iron was extracted with isobutyl acetate. The

acid layer was evaporated to dryness, dissolved in 1 ml of

hydrochloric acid and water and residual iron was reduced

with ascorbic acid. Cadmium, copper, lead, and bismuth were

then extracted from a buffered solution with sodium

diethyldithiocarbamate and chloroform. After evaporation to

dryness and destruction of organic material, cadmium, copper,

lead and bismuth were measured polarographically in a hydro - xylamine hydrochloride supporting electrolyte. Values of

0.108 and 0.098 ppm of cadmium were obtained, which gave an

average of 0.103 ppm. Average values obtained at the same

time for the other elements are: Bi, 0.11 ppm; Cu , 11.5 ppm;

Pb , 44.5 ppm. These values are in good agreement with those

already submitted by polarography for lead and bismuth and

with the 12 ppm value for copper obtained by isotope-dilution

spark-source mass spectrometry.

I . Major Constituent Analysis

Cathode ray polarography has also been very useful for

the rapid determination of major constituents. In cases

where errors of ± 2% are permissible, single cell polarography

has sufficed; where greater accuracies are needed, double

cell comparative methods have been used [24]

1 . Single Cell Polarography

Duplicate solutions of a low-melting alloy, probably of

the Woods' metal type, were submitted for determination of

lead, bismuth, and cadmium. Tin had already been determined

by another technique in portions of the solution. For lead

and cadmium, aliquots of the solution equivalent to 100 mg

of sample were evaporated to dryness with hydrobromic and

perchloric acids. The residues were dissolved in 2 ml of

hydrochloric acid, diluted to 250 ml with water and measured

64
polarographically. Values of 25.3 percent lead and 8.9

percent cadmium were obtained. Bismuth was determined on

aliquots equivalent to 20 mg of sample in a nitric acidsodium tartrate supporting electrolyte. An average value of

43.8 percent was obtained. Smaller samples could have been

used with equal convenience.

A segment of metal tube was submitted for a rapid copper

and zinc analysis to determine if the composition was consistent with Admiralty Brass specifications. The sample was

dissolved in dilute nitric acid and taken to dryness. The

residue was dissolved in 20 ml of hydrochloric acid, 40 ml

of pyridine was added and the solution was diluted to 2 liters. Copper and zinc were then determined polarographically and found to be 71 percent and 27 percent,

respectively.

A sample of a portion of a bronze statue was submitted

for polarographic analysis of copper, lead and zinc. This

was readily done on 50-mg samples by a method similar to

that just described after removal of tin. All three

elements could be determined concurrently. Values of 90

percent copper, 2.6 percent lead and 2.3 percent zinc were

obtained, and the bulk of the remainder was assumed to be

tin.

2 . Comparative Polarography

Some work in the Corrosion Section of the Metallurgy

Division required that the zinc composition of a magnesiumzinc crystalline mixture be known to 0.1 percent. This was

readily accomplished by the comparative polarographic method

after dissolution of the sample and measurement in a dilute

hydrochloric acid supporting electrolyte. The reference

standard solutions were prepared from melting-point zinc,

SRM 43e. Duplicate results of 84.16 percent and 84.08

percent were obtained giving an average of 84.12 percent zinc

with a standard deviation of 0.06 percent.

The comparative polarographic technique recently enabled

65
us to participate in a program on the comparative analysis

of archaeological materials. The objectives of the program

were to find how well analyses by different laboratories

using different methods compare and whether standards made

from archaeological specimens are needed or if synthetic

standards would suffice. The Freer Gallery contributed the

two pieces to be studied. One was a fragment of a Shang

Dynasty (1766-1122 B.C.) bronze ku , a ceremonial vessel, and

the other a Luristan spear point. The samples were prepared

from these two bronzes in the form of chips and were sent

out to the cooperating analysis in 500-mg portions. The

first polarographic determinations were to be of copper,

requiring only a few mg of sample. The samples as received

were very heterogeneous; therefore a much larger sample was

taken, hopefully to minimize the inhomogeneity

The samples, in a small glass vial, were mixed by

rotating rapidly for about 5 minutes, then 100 -mg portions

were tapped into a weighing pan and weighed. The samples

were dissolved in 20 ml of dilute HC1 and 1 ml of HNCu and

evaporated to dryness several times with perchloric acid,

hydrobromic acid, and bromine added to remove tin. The

residues were dissolved in 10 ml of hydrochloric acid, 20 ml

of pyridine was added and the solutions were diluted to 1

liter. The reference standard solutions were prepared from

melting-point copper, SRM 45d, and taken through the procedure along with the samples. Copper was then measured

comparatively on several portions of the solutions and the

values obtained are shown in Table 29.

These results are in good agreement with the general

average of the results turned in so far by the cooperating

analysts

66
Table 29. Copper in archaeological specimens.

Sample Cu, % ku 81.06

81.11

81.10

spear point 95.61

95.56

E. June Maienthal

Average

81 .09

81 .09

81 .09

95 .59

95 .59

67
4. pH AND IONIC ACTIVITY STANDARDS

A. Tris (hydroxymethyl) aminomethane/tris (hydroxymethyl)

aminome thane '"hydrochloride in Aqueous Solution

A new buffer has been added as a standard for the pH(S)

scale based upon previous investigations of suitability.

The buffer tris (hydroxymethyl) aminomethane/tris (hydroxymethyl)

aminomethane • hydrochloride(tris/tris •HCl) in a ratio of 1:3

was chosen as a new Standard Reference Material for use

primarily in the field of biological pH measurements. The

tris molality chosen was 0.01667 molal and the tris*HCl is

then 0.0500 molal. This new reference buffer has several

advantages over reference buffers previously available. For

example, the tris buffer will not complex ionic species, such

as calcium and magnesium, present in body fluids. This

compatibility with biologic systems has been a primary

consideration in the selection of this buffer material. Other

considerations have included the desirability of matching

the pH of the tris buffer solution as closely as possible

with the blood acidity range while choosing a buffer having

a sufficient buffer capacity. Another advantage of the new

buffer : s the temperature coefficient ( -0 . 026pH/°C) which

more closely approximates that of whole blood (-0 . 015pH/°C)

and plasma (-0.01pH/°C) [25] than does the phosphate buffer

(-0.0015pH/°C)

Measurements of the potential of the cell without liquid

junction

Pt;H

2 (g) ) tris -HCl (0.0500m), tris (0.01667m) | AgCljAg

were made at 5° C intervals from to 50° C. The buffer

solutions were prepared by dissolving the crystalline salts

in carbon dioxide-free water.

68
The acidity function p(aHy ri ) was derived from the

measured emf of the cell according to the equation

r

-^ E-E° (1) piaH

y Cl J ' £ + log m

cl

where E° is the standard emf of the cell [26] and k is (RT

In 10)/F. Conventional paH values for each buffer solution

were computed by the equation

pa

H

= P(aH

Y cl ) + log yc1 (2)

where the single ion activity coefficient for the chloride

ion was evaluated by the Bates -Guggenheim convention [27]:

i A/ I ( _> lo § YC1

=

1 + 1.5 /I (3)

where A is the Debye-Hiickel limiting slope and I the total

ionic strength. The total ionic strength is calculated by

the equation

I = 1/2 £ m.Z 2 11 (4) K J where m.11and Z. are the molality/ and charge6 of each ionic

species and the summation is made for all the ionic species

present in the solution. In this system the only ionic

species present is tris*HCl, therefore the value of I is

0.05 m. This procedure is similar to that used in the assignment of pH(S) values to the NBS standard buffer solutions

comprising the National pH scale [28].

The tris and tris*HCl were obtained from the Sigma

Chemical Company of St. Louis, Missouri. The salts were

coulometrically assayed and the tris was found to be of

99.99 ± 0.02 mole percent purity after drying in a vacuum

69
oven at 70 °C for 2 4 hours. Coulometric assay of the tris*

HC1 as received was 99.96 ± 0.05 mole percent. The tris*HCl

material should not be heated above 40 °C due to the risk of

decomposition. Further, it is recommended that reference

electrodes containing linen-fiber junctions not be used with

this buffer. Such junctions produce large liquid- junction

potentials, drift, and long equilibrium times [29].

The emf values for six determinations, corrected to a hydrogen partial pressure of 1 atmosphere, are shown in

Table 30. The corresponding pH(S) values are illustrated as

a function of temperature in Figure 13.

i i

i r

Figure 13. pH(S) as a function of temperature

70
Table 30. Average emf values for the standard buffer

containing 0.01667 mol of Tris and 0.0500 mol of

Tris-HCl per Kg, from 0° to 50°C.

Temp, °C

5

10

15

20

25

30

35

40

45

50

Av . emf , mV'

770.68

768.70

766.62

764.47

762.21

759.87

757.46

754.98

752.38

749.73

746.95

Average of six emf determinations at each temperature

71
The pH(S) is described as a function of temperature by

the equation

pH(S) = -12.4746 + 3833. 17/T + 0.0336811T - . 065 5x10

5 T

2 (5

where T is the temperature in kelvins. The standard

deviation of this fit is 0.0005 pH unit.

The maximum difference in emf was 0.09 mV for the six

measurements. Such a difference corresponds to less than

0.002 pH units. The values tabulated apply only to the lots

specified on the SRM certificate. The materials are available as SRM 922 and SRM 923, for preparation of the standard

buffer solution.

B . Comparison of Procedures

As matter of interest in determining the suitability

of the extrapolation to obtain p(aH

y rl )° for buffer solutions

which in turn allows calculation of the conventional pH(S)

the emf of the tris buffer was measured with varied amounts

of KC1. The same procedure described [28] was followed.

The added concentrations of KC1 were 0.015, 0.010 and

0.005 m, and these were used in the extrapolation. In the

calculation of log Ypn from equation 3, the total ionic

strength was calculated for the solution containing no

added KC1 , i.e. 3 the extrapolated solution composition in

which the tris*HCl alone contributed to the ionic strength

(I = 0.05m)

The encouraging results are shown in Table 31. One

should note that the last column is the actual difference

given to four decimal places . This average difference is

seen to be less than 0.001 pH unit, or somewhat less than

the actual experimental error involved in the measurement

of the emf.

72
Table 31. Comparison of extrapolated pH values with

pH determined directly.

(°C)

5 10

15

20

25

30

35

40

45

50

pH(S) (from

extrapolation

procedure with

added chloride)

8.472

8.303

8.142

7.988

7.841

7.699 ( 7.564

7.433^

7.308

7.187

7.071

1

7

1

pH(S) (without

extrapolation

,

no added

chloride)

8.471

8.303

8.142

7.91

7.840.

7.698,

7.563

7.432

7.307

7.186

7.069,

1

2

1

7

ApH

OvOOO,

0.000

0.000

0.000

0.001.

0.001 ( 0.001^

0.000

0.000,

0.000

( 0.001

7

C .

" Borax

Preliminary measurements for the certification of

SRM 187b, borax (Na

2 B

4 ?

• 10H

2 O) buffer were discussed in the

preceding NBS Technical Note 543 [1] . An example of the

data obtained is given in Table 32 which shows emf and

p(apjYC-j) at various KC1 molalities for 25 °C.

73
Table 32. Acidity function and emf with varying KC1

molalities.

Emf (corrected

m KC1 to 1 atm H

2

) p ^ a H

Y Cl') 0.015 0.87717 9.2438

.015 17 .2438

.015 12 .2429

.015 06 .2419

0.010 0.88762 9.2422

.010 59 .2438

.010 54 .2430

.010 53 .2428

0.005 0.90530 9.2422

.005 42 .2442

.005 33 .2427

.005 19 .2403

From the data in Table 32, the limiting acidity function

PC a uYfi) 1S obtained by extrapolation to zero chloride concentration. Then pH(S) is calculated from the relationship

pH(S) = paR= P( a H

T CL

)° " log YC1 C 6)

using equation to obtain log Yp-i • The pH(S) for the 0.01 m borax buffer solution as a function of temperature is given by

pH(S) = 5723.31 - 38.1774/T + 0.032942T - 1.2906xl0 4

T

2 (7)

where T is the temperature in kelvins. The standard deviation of pH(S) from this equation is 0.0002 pH unit.

74
D. Future pH Buffer for Clinical Use

As previously reported [1] , electrochemical studies of

five buffer systems have been made in isotonic saline. This

medium, 0.16 m NaCl in water, was chosen for some of its

characteristics which match those of blood, namely, its osmotic pressure and ionic strength.

In conjunction with the certification of the tris/tris*

HC1 in water, the determination of pH(S) for this same

buffer in isotonic saline is now underway. This new buffer

will consist of tris (0.01667 m) , tris-HCl (0.0500 m) and

enough NaCl to produce a total ionic strength of 0.16 m. The

new ampouled standard will be available in solution form,

designed specif icially for the calibration of clinical pH

meters .

E. Ion-Selective Electrodes

The details of the procedure employed to obtain the

required single ion activities of unassociated chlorides

for certification of Standard Reference Materials has been

presented [1, 30], In brief, the Stokes -Robinson hydration

theory [31] is used to evaluate the hydration number of the

cation assuming that the chloride ion is not hydrated [32]

If the cation is hydrated with h molecules of water and m'

is its molality in moles per kilogram of unbound water, then

m

1 - 0.018hm (8)

The activity of chloride ion is the same on the two scales

my

r

-, - = m'y',-. Then

In yTM+ = In Ya4 + - h In a - In (1 - 0.018hm) (9) 'M 'M w

v j \ j

75
In Y^+ = In £jjH

- In [1 - . 018 (2)m'

(10)

where £nH is the electrostatic contribution expressed as an

activity coefficient on the mole fraction scale, and it

follows that

In ym

+ - In fDH

- h In aw

- In [1 - . 018 (2 -h)m] (1])

With the definition of the osmotic coefficient <f> -In a

A - W

0.018vm (1%

the expressions of the activity coefficients become

lo g TM

+ = log Y+ + 0.00782 hmcj) (1$

and

log y c1

- = log Y+-- 0.00782hm(}) (14)

Using the same procedure one derives the equations

applicable to an unassociated salt MC1

2

»

lo S TM

++ = 2 log y + + 0.00782hmc() + log [1 + . 018 (3 -h)m] (1$

and

2 log Y€1

- = log Y ±

- 0.00782hm(J) - log [1 + . 018 (3 -h)m] (16)

76
1

Equipment

An interim measuring system has been adopted pending

completion of an automated system. A digital voltmeter, DVM,

accurate to 0.01 mV is being used to directly measure the

potential of most of the electrode systems except those of

very high impedance, such as the glass electrodes. In cases

involving high impedance, the DVM is used to measure the output of a vibrating reed electrometer.

The DVM has been equipped with a plug-in unit for

binary-coded decimal (BCD) input-output and is compatible

with the Analytical Division computer. Programs are being

written to aid in the future automation of the measuring

functions involving both ion-selective electrodes and pH

measurement

2

Standards for Sodium, Potassium and Chloride

Activities

A major practical accomplishment in the area of ionselective electrodes during the past year was the certification of and the actual issuance of NaCl and KC1 as

Standard Reference Materials 2201 and 2202 respectively.

The values of the ionic activities for these lots of

materials have appeared in the previous Technical Note 543

[1].

3. Solution Standards for Calcium Ion Activity

The reference materials for the calcium ion activity

standards will be made available in ampouled solution form.

Solutions will be prepared by dissolving the presently available calcium carbonate (SRM 915) in a slight excess of

purified hydrochloric acid.

Solutions of calcium chloride have been prepared

from the SRM using this procedure. About 5 grams of calcium

carbonate were dissolved in an excess of 1 molal HC1 obtained

from constant boiling HC1. The solution of about 200 ml was

evaporated to dryness in a 500 ml Erlenmeyer flask. The

77
CaCl ? was redissolved in a small amount of H^O and again

evaporated to dryness. A weighed amount of H~0 was added to

the weighed flask to obtain a solution 0.1 molal in CaCl ?

. The distilled water was purged with pure nitrogen to remove

dissolved carbon dioxide.

Other solutions were prepared by serial dilutions

of 25 ml to 250 ml in volumetric flasks. The molalities used

were 10

_1

, 10" 2, 10

-3

, and 10~ 4 The emf as a function of

activity at 25° C is illustrated in figure 14 for a typical

commercially available calcium-selective electrode. The

observed response slope is 31 mV compared to the theoretical

Nernstian slope of 29.6 mV. Further work is in progress to

elucidate the behavior of calcium-selective electrodes in

these solutions.

lna Ca 2+

Figure 14. Emf as a function of calcium activity

B. R. Staples
5. POTENT I OMETRY

A. Chromatographic Detector for NTA and Other Complexing

Agents using a Cupric Electrode Flow-Through Cell

An electrochemical detector based on the cupric ionselective electrode has been developed for the determination

of complexing agents, such as NTA, EDTA, etc., after separation by ion-exchange chromatography. This detector was

developed independently of the separation methods, and the

evaluation of its response to NTA in the final system must

await completion of the chromatographic method.

The detector system, shown in figures 15 and 16 and

diagrammed in figure 17, is based on the response of a cupric

ion-selective electrode to electrochemically generated cupric

ion in a continuous, flow-through cell arrangement. In

principle, the detector system operates in this way: (1)

cupric ion is generated coulometrically at constant rate

upstream from the detector, i.e., between the chromatographic

column and the detector; (2) the rate of generation is continuously variable to obtain optimum response at the detector

depending upon the concentration of the complexing agents;

(3) the detector assembly, described in detail below, produces a constant emf output until the cupric ion level is

perturbed by complexation with NTA or other ligand; (4) since

the electrode only responds to the uncomplexed cupric ions , the magnitude of the emf change can be related to the degree

of complexation and consequently to the amount of complexing

agent present.

The detector assembly consists of a flow chamber machined

from Teflon into which are mounted the cupric ion-selective

electrode and a reference electrode designed for use in flow

assemblies. The indicator electrode is held securely in

place by the aluminum holder attached to the Teflon assembly

as shown in figures 15, 16, and 17. This holder permits

the electrode to be seated tightly against the flow chamber

79
lip, thus preventing solution leakage around the electrode

tip. The cupric ion indicator electrode is mounted 60°

from the vertical to avoid bubble entrapment in the flow

chamber which could cause spurious electrode response.

Figure 15. Cupric electrode/NTA detector syst em

80
Figure 16. Close-up of the cupric electrode flow-through

cell.
Figure 17. Diagram of flow- through cell and coulometric

cupric ion generator.

a) Sample inlet

b) Teflon assembly for electrochemical generation of

cupric ion

c) Copper wire anode (cupric ion generation)

d) Copper wire cathode

e) Cathode compartment: Cath olyte - 0.01 M KN0 3 , fiber wick junction to sample stream

f) Teflon tubing connection between generator and

detector assemblies

g) Teflon detector assembly

h) Detector cavity - volume: 50 yl

i) Cupric ion-selective electrode

j) Aluminum electrode holder

k) Reference electrode

1) Reference electrode cavity

ml Overflow to waste

82
In order to test the response characteristics of this

system, an electrolyte solution (0.01 M KNO 3 ) was flowed

through the generator and detector assemblies at constant

rate (0.4 ml/min) using a syringe pump (figure 15). A constant current was applied to the coulometric cupric ion

generator. From a knowledge of the flow rate and current,

the concentration of cupric ion generated could be calculated

and a working curve established for the electrode system.

This curve, shown in figure 1 8, is linear from 5 ppm to about

0.2 ppm with a response slope of approximately 21 mV/pCu

(theoretical: 29.5 mV/pCu) . The response time of the

electrode system to achieve a stable emf reading was measured

for step changes in the generator current, i.e. 3 the cupric

ion activity. In general, at the very dilute cupric ion

levels generated (0.1 to 5 ppm), the time required to establish an equilibrium emf was about 3-4 minutes. Calibration

of the electrode system in stirred standard solutions showed

similar behavior, i . e . _, equilibration times of several

minutes and a sub-Nerns tian response slope of approximately

23 mV/pCu. At higher cupric ion concentrations, the

electrode response is faster and more Nernstian.

83
EMF

185

1 I I 1 1

I

180 /

175 /

170 - /

165 / -

160 -

155 -

150 i i . 1

i i i 0.1 0.2 0.5 1.0 2.0 CUPRIC ION CONCENTRATION (ppm)

5.0

Figure 18. Emf response in mV of the cupric ion flowthrough cell.

84
The chromatographic procedure will require the removal

of divalent cations from the complexing ligands, perhaps

using a cation exchanger in the hydrogen ion form, followed

by conversion of the acid-form ligands to their sodium salts

by passage through another cation exchanger in the sodium

form. This procedure would result in a sample of the proper

characteristics to be determined by the cupric ion electrode

detector

B. Potentiometric Determination of Total Calcium

A potentiometric titration method has been developed

for the determination of total calcium in samples provided

as part of the NBS-clinical chemistry interaction exercise.

In anticipation of analyses on actual serum samples, the

procedure developed minimizes potential interferences from

other blood electrolytes, especially magnesium ion.

The method consists of titrating the sample (^10 ml)

with the tetrasodium form of EGTA [Ethyleneglycol bis (2-amino

ethyether) tetraacetic acid] using a calcium ion-selective

electrode as the end-point detector. EGTA was chosen as the

titrant ligand because it selectivity complexes calcium in

the presence of magnesium as demonstrated by Schmid and

Reilley [33]. The Nai+EGTA titrant was prepared according to

the procedure of van ' t Riet and Wynn [34]. The EGTA is dissolved by the addition of an accurately measured volume of

sodium hydroxide solution and adjusted to pH 7. The tetrasodium salt is prepared by the addition of another

identical volume of the NaOH solution.

Since EGTA does not form as strong a complex with

calcium as does EDTA (which also binds magnesium strongly) , the chemical equilibration beyond the end point is rather

slow and results in a somewhat drawn-out sigmoidal titration

curve. For this reason, evaluation of the titration data

was accomplished by a graphical procedure devised by Gran

[35] in which data points before the end point are plotted

85
as an exponential function of the emf vs. milliliters of

titrant and results in a linear extrapolation to the end point

volume

Using this method, three sets of the samples where run

on three separate days. The results of the titrations, which

were performed in a random manner according to exercise

directions, are given in Table 33. The calculated calcium

values, based on the preparation of solutions from standard

reference calcium carbonate (SRM 915), were 8.182 (solutions

2 and 103), 10.391 (solutions 26, 37, and 63), and 11.758

(solutions 42 and 82) . All values are expressed as mg Ca /100 ml of solution.

Table 33.

Total Calcium in NBS Test Solutions as Determined by Potentiom|tric Titration

(Results given as mg Ca /100 ml of solution.)

Solution 2 Solution 103 Solution 42

Set A 8.04 8.36 11.57 11.74

Set B 8.39 8.24 11.99 11.75

Set C 8.15 8.14 11.66 11.81

Average 9.19 8.25 11.74

Pooled

Average 8.22 11.75

Solution 26 Solution 37 Solution 63

Set A

Set B

Set C

Average 10.45 10.43 10.46

Pooled

Average 10.45

Richard A. Durst

86

11.77

10.49 10.42 10.36

10.39 10.41 10.43

10.48 10.47 10.58
6. DISSOLVED OXYGEN IN SEAWATER

A. Introduction

Dissolved oxygen plays a vital role in biological

processes in natural water systems. The measurement of the

amount of oxygen present in these natural waters is of

particular importance in the fields of oceanography and

marine chemistry as well as environmental pollution studies.

The calibration of a wide variety of oxygen-measuring

devices depends on a few absolute measurements. The

National Oceanographic Instrumentation Center (NOIC) of the

National Oceanic and Atmospheric Administration (NOAA) had

a requirement for reference standards and data for calibrating such instruments, and a program to determine dissolved oxygen in a number of saturated solutions of seawater

has been initiated.

The program was designed to determine dissolved oxygen

in seawater samples saturated with each of five different

gas mixtures of varying oxygen content. The mixtures prepared are of the following compositions of oxygen in

nitrogen: 0, 4, 8, 12, 16, and 20.94 mole-percent oxygen.

The determinations were to cover five temperatures: 0, 10,

20, 30 and 40 °C.

Many methods have been employed to measure dissolved

oxygen in aqueous systems. There are few absolute methods

available; the most widely known being the Winkler method

[36]. The Winkler titration method is tedious, cumbersome

and time-consuming. The Winkler (1888) method and numerous

modifications still remain the most accurate procedure for

routine use. The method depends upon the reaction of dissolved oxygen with freshly precipitated manganese hydroxide.

A concentrated solution of manganous chloride or sulfate

is added to the water sample and an excess of a solution of

sodium hydroxide and potassium iodide introduced. The precipitated manganese hydroxide is allowed to settle and is

87
then dissolved by acid. Iodine is liberated and titrated

with standard thiosulfate using starch as the indicator.

The reactions are as follows

Mn(OH)

2 + 1/2

2

-> MnO(OH)

2

MnO :0H)

2 + 4H

+

+ 3.1 "

-* Mn

2+

+ I~ + 3H

2

I + 2S

2

0" -> 31 + S

4

0"

Even at the lowest extreme of concentrations of dissolved

oxygen {e.g. 1 ppb) , the assumption always made is that the

oxidation and reduction of the manganese precipitate is

quantitative under the imposed conditions.

A number of physical methods based on coulometric,

gasometric, polarographic , or amperometric principles are

also in use for determining dissolved oxygen. Most of these

methods require standardization. In 1952, Hersch [37] demonstrated the applicability of galvanic cells for the

determination of low concentrations of oxygen in gas-flow

systems. The Hersch cell contains an alkali hydroxide

electrolyte with a lead anode and an inert cathode of silver

or platinum. The half-cell reactions

1/2

2 + H2 + 2e~ > 2 OH" (cathode)

Pb + 40H" -2e~ -> PbO^ + 2H

2 (anode)

produce a flow of current when oxygen is present. A few

modifications have appeared in the literature [38, 39, 40].

Recently, Ives, et al . [41] have developed a technique

to measure absolute values of oxygen in inert gases over the

range of 1 to 1,000 ppm oxygen. The method involves a flow
of the gas through a series of galvanic cells similar to

Hersch cells. The current outputs of the cells allows

calculation of the absolute concentration of oxygen. These

same cells were used to attempt a determination of the total

amount of oxygen swept out of gas -saturated solutions by a stream of high purity nitrogen, which then passed through

the cells

B . Experimental

The cells and procedure have been described in detail

[41, 42] and only a few modifications were made for the

present purpose. Since the amount of oxygen present is

proportional to the integrated current, the voltage produced

by the galvanic cell was measured across a standard 20-ohm

resistor, then a voltage-to-frequency converter was used to

accumulate counts on an electronic counter- timer . The apparatus is illustrated in Figure 19. The cells are shown

to the left of the picture with the standard resistor in the

foreground. To the right is the V-to-F converter and counter

A U-shaped apparatus with a double rubber septum injection port was used to receive the sample. The purging of

the sample was accomplished with nitrogen bubbling through

the medium porosity glass frit in the U-tube.

Figure 19. Hersch cell.

89
C . Results

1. Efficiency of the Measuring System . To determine

the efficiency of the measuring system a coulometric analyzer

was used to electrolyze distilled water containing Na

2 S04

. The theoretical number of counts was obtained by generating

a known number of microequivalents directly to the counting

system, across a 20.0-ohm resistor. For example, at 6.43 ma,

10.00 meq registered 19.384 x 10 counts (100 mV scale) and

1.000 yeq registered 1.9375 x 10 counts. Then the percentage

recovery of oxygen could be calculated from the current obtained (counts) after purging of the electrolyzed solution

with nitrogen. Efficiencies of the system thus determined

are given in Table 34.

The efficiency of the counting system by direct generation was found to be 100.4 percent as calculated below.

The 100 mV scale and 20.0-ohm resistor gives a current of

V lOOmV

1 = R

= 2M = 5 ma

The rate of counting is 10 counts s and hence for a

5 ma current, there are 0.2 x 10 counts s ma (counts

mC )• Converting this to 5 x 10 mC count"-'' or 5 x 10

mC count , the yeq recovered may be obtained by

f\ - 7 - 1 19.384 x 10 counts x 5 x 10 uC count 1A n , ^y1 = 10.04 yeq

96487 yC yeq

The output of the coulometric analyzer was shown to be

100 percent by measuring the voltage drop across a 10.0-ohm

standard resistor in series with the electrolysis cell. The

emf was 6.435 ± 0.001 mV which gave a current of 0.643 ma,

the nominal rating of the coulometric analyzer.

90
Table 34. Cell efficiencies for oxygen determinations.

Percent

yeq recovery

10 88.0

10 - 81.1

10 78.3

(electrode surfaces cleaned

and new electrolyte added)

10 45.8

1 54.2

10 75.7

5 63.6

10.5 74.3

2 70.2

2 81.9

5 71.0

2 . Discussion and Summary

As observed in Table "

1 , erratic and unpredictable

results were obtained for numerous determinations. Cleaning

and preparing fresh cells as indicated brought little

improvement

.

With a slow flow rate (~2 cc min ) , a second cell in

series showed no change in potential, indicating that all

the 0~ was being consumed in the first cell, and that there

were no leaks of ? into the system.

A steady-state generation of 0- (and H~) by electrolysis

using platinum electrodes gave about 95-98 percent efficiency

indicating that the method was satisfactory as a flow system

but apparently not as a disolete sample method.

Actual samples of air-saturated distilled water were

used to estimate the reproducibility of the method. Using

Mancy ' s [4 5] values for 0- solubility (1.00 yeq ml ) the

results can be compared in Table Z -for selected sample sizes.

91
Table 35. Comparison of dissolved oxygen determined

by the system with literature data.

ml distilled

H

2

yeq ml 1

recoversid

62

0. 53

47

0. 56

0. 44

10

10

5

5

5

5 0.46

10 0.41

10 0.43

10 0.38

10 0.42

air-sat'd. H

2 contains 1V00 yeq ml of?

D. New Frontiers

Although the method seems to be unsuitable for discreet

solution samples, it has stimulated interest in using a number of other approaches for solving this important problem

Experiments are now underway to investigate the feasibility

of using coulometric determinations in systems such as ferrous sulfate, chromous chloride, and modified Hersch

cells containing large amounts of electrolyte.

The method involving chromous ion and its rapid and

quantitative reaction with Cu looks promising. Other preliminary results on cells containing different metal

electrodes in Ca(OH)

7 solutions as well as KOH solutions,

seem to point to a two-electron reduction of ? as suggested

by G. Marinenko. It is anticipated that publication of

these results will be forthcoming.

B. R. Staples

92
7. FOREIGN -CURRENCY PROGRAM

A research project on the measurement of ionic activities

in multicomponent systems and biologic fluids has been initiated under the direction of Dr. J. Padova of the Soreq

Nuclear Research Center in Yavne , Israel. This project,

funded under Public Law 480, will involve the measurement of

electrolyte activities by two independent techniques

(1) a gravimetric isopiestic method using an improved apparatus developed in Dr. Padova' s laboratory and (2) an

electrometric method using ion-selective electrodes in cells

without liquid junctions.

The isopiestic method is very convenient for deriving

the activity of electrolytes in multicomponent systems from

measurements of the activity of the solvent and calculations

involving the Gibbs-Duhem equation. Ion-selective electrodes

will be used to measure ionic activities directly in cells

without transference and these results will be correlated

with the isopiestic data.

The proposed investigation is aimed at gathering

activity data for ions in solutions of increasing complexity

with an ultimate view to producing standards for ions which

are important in physiological processes. The systems to be

studied will consist of mixed solutions of such ions as sodium, potassium, calcium, magnesium, chloride, bicarbonate,

phosphate, organic acids, and proteins as are found in

biologic fluids.

Richard A. Durst

93
8. PERSONNEL AND ACTIVITIES

A. Personnel Listing

Richard A. Durst, Section Chief

Charlotte P. Wren, Section Secretary

pH and Ionic Activity-

Bert R. Staples

Coulometry-

George Marinenko

Dale Friend (part time)

Polarography-

E. J. Maienthal

Anodic Stripping--

Joseph R. Robinson (EOD 6/14/71)

Potentiometry-

Richard A. Durst

Benjamin T. Duhart (part time)

B

Publications and Manuscripts

1. Bates, R. G., Staples, B. R. , and Robinson, R. A.,

"Ionic Hydration and Single Ion Activities in Unassociated Chlorides at High Ionic Strengths," Anal. Chem.

4_2, 867-71 (1970) .

2. Robinson, R. A., "The Dissociation Constant of m-Nitroanilinium Ion in Water-Tetrahydrofuran Solvents at

25° C," J. Res. NBS 3 74A, 4, 495-97 (1970).

3. Champion, C. E., Marinenko, G., Schmidt, W. E., and

Taylor, J. K., "Determination of Submicrogram Amounts

of Chromium by Coulometric Titrimetry," Anal. Chem.

42, 11, 1210-13 (1970).

4. Cantanzaro, E. J., Champion C. C., Garner, E. L.,

Marinenko, G. , Sappenfield, K. M. , and Shields, W. R.

"Boric Acid -- Isotopic and Assay -- Standard Reference

Material," NBS Special Publication 260-17, U. S.

Government Printing Office, Washington, D. C. 20402,

(1970).

5. Durst, R. A., and Duhart, B. T., "Ion-Selective

Electrode Study of Trace Silver Adsorption on Selected

Surfaces," Anal. Chem. 4_2, 1002 (1970).

94
6. Thun, H. P., Staples, B. R. , and Bates, R. G., "Thermodynamics of Hydrochloric Acid in 80 Weight Percent

2-Methoxyethanol and 20 Weight Percent Water from 10 to

50° C," J. Res. BBS 74A, 641-45 (September -October 1970).

7. Paabo, J., and Bates, R. G. , "Acidic Dissociation of

Diprotonated Piperazine in Methanol-Water Solvents from

10 to 40° C," /. Res. NBS 74A , 667-71 (SeptemberOctober 1970) .

8. Durst, R. A., "Pick an Ion, Any Ion," Ind. Res. 36-9

(1970) .

9. Davis, M. M. , "Bronsted Acid-Base Behavior in Inert

Organic Solvents" in the Chemistry of Nonaqueous Solvents , J. J. Lagowski, Editor, Vol. Ill, Chapter 1, 1-135,

Academic Press, Inc., New York (1970).

10. Durst, R. A., Editor , 'Electrochemical Analysis Section:

Summary of Activities July 1969 to June 1970," U. S.

National Bureau of Standards Technical Note 543, 1-81,

U. S. Government Printing Office, Washington, D. C.

20402, (1970).

11. Bates, R. G., " Measurement of pH" in Handbook of

Biochemistry , Sober , H. A. , Editor , 190 -95 , Chemical

Rubber Co., Cleveland, Ohio (1971).

12. Durst, R. A., "Ion-Selective Electrodes in Science,

Medicine, and Technology," American Scientist 5_9_, 3,

353-61 (1971) .

13. Marinenko, G., and Foley, R. T., "A New Determination of

the Atomic Weight of Zinc," Phys. and Chem. (In press).

14. Durst, R. A., and Staples, B. T., "Tris/Tris -HC1

:

A Standard Buffer for Use in the Physiologic pH Range,"

Clinical Chemistry (In press).

15. Durst, R. A., "Ion-Selective Electrodes," Proceedings

International Conference on Localized Corrosion

(In press)

.

95
C. Talks

1. B. R. Staples, "Dissociation of Protonated Tris(hydroxymethyl) am inome thane in Aqueous Alcohol Solvents,"

160th National Meeting American Chemical Society,

Chicago, Illinois, September 1970.

2. G. Marinenko, "Coulometric Determination of GaAs

Stoichiometry ," Third International Symposium on Gallium

Arsenide and Related Compounds, Aachen, Germany,

October 3-9, 1970.

3. E. J. Maienthal, "Polarographic Analysis," NBS

Activation Analysis Section Seminar, October 5, 1970.

4. R. A. Durst, "Ion-Selective Electrode Potentiometry ,"

NIH/NBS Conference on Meaningful Clinical Analysis

Standardization, Gaithersburg , Maryland, October 9, 1970.

5. R. A. Durst, "Ion-Selective Electrode Monitoring of

Environmental Pollutants," 14th Conference on Analytical

Chemistry in Nuclear Technology, Oak Ridge National

Laboratory, Gatlinburg, Tennessee, October 14, 1970.

6. G. Marinenko, "Coulomb -- The Absolute Chemcial Standard,"

1970 Eastern Analytical Symposium, Statler-Hilton

Hotel, New York City, November 1970.

7. B. R. Staples, "Activity Standards for Ion-Selective

Electrodes," Combined Southeast - Southwest Regional

Meeting, American Chemical Society, New Orleans,

Louisiana, December 1970.

8. R. A. Durst, "Ion-Selective Electrodes - Mechanisms and

New Directions," (Discussion Leader), Gordon Research

Conference on Electrochemistry, Santa Barbara,

California, January 18, 1971.

9. R. A. Durst, "Ion-Selective Electrodes - Theory,

Characteristics, and Methodology," University of

Maryland Seminar, College Park, Maryland, February 19,

1971.

10. R. A. Durst, "Ion-Selective Electrodes," Some Current

Research in IMR, NBS/IMR Conference, Gaithersburg,

Maryland, February 23, 1971.

11. G. Marinenko, "Accurate Measurement of Stoichiometry,"

Some Current Research in IMR, NBS/IMR Conference,

Gaithersburg, Maryland, February 23, 1971.

96
12. G. Marinenko, "Accurate Measurement of Stoichiometry ,"

Bell Telephone Laboratories, March 11, 1971.

13. R. A. Durst, "Ion-Selective Electrodes," Detroit Section

of the American Chemical Society, Detroit, Michigan,

March 16, 1971.

14. R. A. Durst, "Ion-Selective Electrodes," Chemistry

Department Seminar, Renssalaer Polytechnic Institute,

Troy, New York, March 18, 1971.

15. E. J. Mainethal, "Polarographic Analysis of Trace

Elements in Glass," ASTM Committee C-14 and E-2, NBS

,

April 13, 1971.

16. R. A. Durst, "Recent Developments in Ion-Selective

Electrodes and Coulometry," Frontiers in Chemistry

Lecture Series, State University College, New Paltz,

New York, May 6, 1971.

17. R. A. Durst, "Activity Standards for Ion-Selective

Electrodes," Instituto Superiore di Sanita and

C.I.T.C.E. Symposium on the Biological Aspects of

Electrochemistry, Rome, Italy, June 4, 1971.

97
9. REFERENCES

[1] Durst, R. A., Editor, Electrochemical Analysis Section:

Summary of Activities, July 1969 to June 1970, NBS

Technical Note 543, U. S. Government Printing Office,

Washington, D. C. 20402, 81 pages, (1970).

[2] Durst, R. A., Editor, Ion-Selective Electrodes , NBS

Special Publication 314, U. S~! Government Printing

Office, Washington, D. C. 20402, 452 pages (1969).

[3] Bates, R. G., Wichers, E., J. Res NBS 59_, 9 (1957).

[4] This high purity Standard Reference Material, SRM No.

682 is available from the Office of Standard Reference

Materials, National Bureau of Standards, Washington,

D. C. 20234, along with the "Certificate of Analysis"

at a unit price of $90.00.

[5] Gill, A. S., Acting General Superintendent of Electrolytic Zinc Company of Australasia Ltd. , Private

Communication

[6] Taylor, B. N. , Parker, W. H., and Langenberg, D. N.,

Revs. Mod. Rhys. 41_, 375 (1969).

[7] Hess, D. C, Inghram, M. G., and Hayden, R. J., Rhys.

Rev. 7_4, 1531 (1948).

[8] Marinenko, G., Taylor, J. K. , J. Res. NBS 67A , 31 (1963).

[9] Craig, D. N., Hoffman, I. I., Law, C. A., and Hamer,

W. J., J. Res. NBS 6_4A, (Phys . $ Chem.) 381 (1960).

[10] Reilley, C. N. , Schmidt, R. W. , and Lomson, D. W.

Anal. Chem. 30_, 835 (1953) .

[11] Marinenko, G., Taylor, J. K., Anal. Chem. 3_9, 1569 (1967)

[12] Marinenko, G., Taylor, J. K. , J. Res NBS 67A , (Phys. §

Chem.) 31, (1963).

[13] Maienthal, E. J., "Polarographic Analysis" in Microchemical Analysis Section, Summary of Activities, July

1969 to June 1970, NBS Technical Note 545, U. S.

Government Printing Office, Washington, D. C. 20402,

114 pages (1971)

[14] Daniel, R. L., LeBlanc, R. B., Anal. Chem. 31, 1221

(1959) .

98
LeBlanc, R. B., Anal. Chem. 31, 1840 (1959).

Farrow, R. N. P., Hill, A. G. , Analyst 9_0_, 241 (1965).

Haberman, J. P., Anal. Chem. 43_, 63 (1971).

Afghan, B. K. , Goulden, P. D., Journal of Environmental

Science and Technology 3 5_, 601 (1971).

Afghan, B. K. , "Differential Cathode Ray Polarography

for Trace Analysis with Special Reference to NTA and

Its Complexes with Heavy Metals," a talk presented at

the International Symposium on Identification and

Measurement of Environmental Pollutants, Ottawa,

Canada, June 15, 1971.

Gahler, A. R. , private communication.

• Traversy, W. J. , "Methods for Chemical Analysis of

Waters and Waste Waters in Use in Water Quality Division

Laboratories," Inland Waters Branch, Department of

Energy, Mines and Resources, Ottawa, Canada (1971).

Rooney, R. C, Analyst 83, 83 (1958).

Bode, H., Anal. Chem. 144, 165 (1955).

Maienthal, E. J., Taylor, J. K. , Microchim. Acta 1967 , 939.

Rosenthal, T. B., J. Biol. Chem. 173 , 25 (1948).

Bates, R. G. , Bower, V. E., J. Res. NBS 5_3, 283 (1954).

Bates, R. G. , Guggenheim, E. A., Pure Appl. Chem. 1,

163 (1960) . Staples, B. R. , Bates, R. G., J. Res. NBS 73A , 37 (1969),

Westcott, C. C, Johns, T., Appl. Res. Technical Report

No. 542, Beckman Instruments, Inc., Fullerton,

California.

Bates, R. G., Staples, B. R. , and Robins, R. A.,

Anal. Chem. 42_, 867 (1970).

Stokes, R. H. , Robinson, R. A., J. Amer. Chem. Soc. 70 , 1870 (1948).

Glueckauf, E., Trans. Faraday Soc. 51, 1235 (1955).

99
[33] Schmidt, R. W. , Reilley, C. N., Anal. Chem. 29_, 264

(1957)

[34] Van't Riet, B., Wynne, J. E., Anal. Chem. 41_, 158 (1969).

[35] Gran, G. , Acta Chem. Soand. 4_, 559 (1950) ; also Analyst

TJ_, 661 (1952) .

[36] Winkler, L. W. , Bev. dtsah. ohem. Ges . 2_1, 2843 (1888).

[37] Hersch, P., Nature 1_69, 792 (1952).

[38] Hersch, P., Anal. Chem. 32, 1030 (1960).

[39] Waclawik, J., Waszak, S., Chem. Anal. (Warsaw) 8_,

865 (1963).

[40] Keidl, F. A., Ind. Eng. Chem. _5_2_, 491 (1960).

[41] Ives, J. M. , Hughes, E. E., and Taylor, J. K., Anal.

Chem. 40_, 1853 (1968) .

[42] Taylor, J. K. , Editor, Microchemical Analysis Section:

Summary of Activities, July 1967 to June 1968, NBS

Technical Note 455, U. S. Government Printing Office,

Washington, D. C. 20402, 132 pages (1968).

[43] Mancy, K. H. , Editor, Instrumental Analysis for Water

Pollution Control , Ann Arbor Science Publishers, Inc.,

Michigan (1971) .

4 11. S. GOVERNMENT PRINTING OFFICE : 1973—511-323/168

100
yi NBS-U4A (1-71) U.S. DEPT. OF COMM. JIBLIOGRAPHIC DATA

SHEET

1. PUBLICATION OR REPORT NO. NBS TN-583

2, Gov't Accession No.

TITLE AND SUBTITLE

ECTROCHEMICAL ANALYSIS SECTION: SUMMARY OF ACTIVITIES,

jly 1970 to June 1971

3. Recipient's Accession No.

5. Publication Date February 1973

6. Performing Organization Code

\UTHOR(S)

Durst, Richard A

8. Performing Organization

PERFORMING ORGANIZATION NAME AND ADDRESS 10. Project/Task/ Work Unit No.

NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE

WASHINGTON, D.C. 20234

11. Contract/Grant No.

Sponsoring Organization Name and Address

Same as No. 9

13. Type of Report & Period Covered

Final

14. Sponsoring Agency Code

SUPPLEMENTARY NOTES

ABSTRACT (A 200-word or less factual summary of most significant information. If document includes a significant

bibliography or literature survey, mention it here.)

This survey of the activities of the Elec

ection, Analytical Chemistry Division, covers

o June 1971. An attempt is made to briefly s n the technical projects of the Section, to i

nd capabilities of the unit as a whole, and t

ole in the mission of the Institute. Summari

he Section competences are given. In the are

ork was completed on the standardization of t

ethane for use as a biologic pH buffer materi

linical pH measurements. High-precision coul

he atomic weight of zinc, the stoichiometry o he purity of KC1 and NaCl. Polarography is u lements in a variety of environmental samples

laterials

trochemical Analysis

the period from July 1970

ummarize a year's progress

ndicate the composition

o stress the Section's

es of the work in each of

a of acidity measurements,

ris (hydroxyme thy1) amino

al and standard for

ometry is used to determine

f gallium arsenide, and

sed to determine trace

and Standard Reference

KEY WORDS (Alphabetical order, separated by semicolons) Acidity; COulometric analysis; electrotemical analysis; ionic activity; ion-selective electrodes; pH measurements; polarog-

; : Phy; potentiometry ; Standard Reference Materials.

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