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CHAPTER 15

ELECTROMETRIC METHODS
By W. N. Carson, Jr.*

I n this chapter the electrometric techniques used in the analysis of


atomic energy materials are discussed. The wide diversity of the
methods involved and of their applications requires that some qualifi-
cations be set up to serve as a guide for discussion. This has 'been
done by restricting the methods to be discussed to those in which an
electrochemical phenomenon is involved. The restriction thus excludes
any methods such as photometry, which involves the measurement of
an electrical quantity but which does not involve an electrochemical
phenomenon.
The electrometric methods of analysis are divided into two main
groups in this chapter. The first group comprises the methods in
which measurement of an electrical quantity, such as potential, serves
as the primary measurement of the substance being determined. The
second group comprises the methods in which the measurement of an
electrical quantity serves as a guide to the use of another measure-
ment, such as titration with a standard solution. The second group
also includes those methods in which electricity is used as a reagent
in the analysis, but the quantity of electricity used does not serve as
the measure of the substance being determined.
Material on the theoretical background of the electrochemical phe-
nomena associated with an electrometric method of analysis has been
included to show the unifying principles involved, but this chapter is
not intended to be a complete guide to the complexities of modem
electrochemistry. The emphasis lies on the practical problems
involved in applying electrochemical principles.
Similarly, material on the operating principles of the electrical
equipment used in the methods of analysis has been included. Since
improvements in the electronic and mechanical components used in
the equipment are being made constantly, it would be expected that
any equipment used today would become obsolete relatively quickly.
Hence the emphasis is on principles rather than on details of operation.
The present and potential use of electrometric techniques in automatic
analyzers in the processing of atomic energy materials is also covered
in some detail.

•Advanced Technology Laboratories, General Electric Co., Schenectady, N.Y.


1129
1 1 3 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

15-1 APPARATUS AND GENERAL PRINCIPLES


Electrometric methods for routine analysis are not new, but their
use was limited until the past 10 years or so because the apparatus for
many of the potentially useful methods were inconvenient to use, time-
consuming in operation, and unreliable in the hands of the routine
analyst. The great promise of electrometric techniques has been par-
tially fulfilled by the development of laboratory apparatus which, if
not simple in design, is simple to use and is as reliable as conventional
analytical apparatus and which eliminates many of the tedious and
time-consuming features through automatic control systems and re-
cording components. The great increase in reliability of the apparatus
and the ready adaptation of electrometric techniques to automatic
recording have led to the use of these techniques in automatic process
analyzers.
The reader may find the general references ^"^° useful as sources of
background material on the theoretical and practical aspects of
electrometric analysis methods.
15-1.1 Electrodes
Electrodes are the key elements in electrometric methods of analysis.
I n any electrometric method, two electrodes are required; however, in
many methods only the electrochemical phenomena associated with
one electrode are useful. This electrode is referred to as the "sensi-
tive," or "working," electrode of the pair; the other electrode is the
reference or counter electrode. The sensitive electrodes are discussed
in detail in the sections describing the methods employing them; the
reference electrodes are described below. A distinction is made be-
tween a counter electrode and a reference electrode in that the counter
electrode is used in methods involving electrolysis, whereas the refer-
ence electrode normally is used only to supply a constant potential
reference point for taking measurements. Both a reference and a
counter electrode can be used in an electroanalytical procedure.
The passage of electric current through a solution requires that a
change from electronic to ionic conduction be made at one electrode
and a change in the reverse order at the other. This transfer of
charge is always accompanied by chemical reactions of the oxidation-
reduction type. In the use of a sensitive electrode, the aim is to empha-
size one of the phenomena associated with the oxidation-reduction
reaction occurring at the electrode-solution interface and to minimize
or eliminate all other phenomena. With reference electrodes, on the
other hand, the aim is to design an electrode such that little, if any,
change in the electrode behavior occurs during use. W i t h counter
electrodes, the aim is to provide the second electrode required for
electrolysis. The designer uses the configuration of the electrode, the
ELECTROMETRIC METHODS 1131

materials of construction, and sets the operating conditions he can


control to make the electrode produce the desired response.
Since the reference electrodes used in electrometric analysis are
common to many of the methods, a listing of the types and their char-
acteristics is given here. Associated with these electrodes is the prob-
lem of the junction, or how to connect the reference electrode to the
solution in which the sensitive electrode is immersed. The device used
is called a "salt bridge," and this bridge is one of the major sources of
trouble in electrometric analysis.
(a) Calomel Electrode. The calomel electrode is the most used
reference electrode in electrometric methods of analysis. The cell
reaction

Hg2Cl2(.oiia)+2e^Hg(Hquid)+2C1-

is reversible, and the electrode is not easily polarized. Three types of


calomel electrode are recognized; these usually have the form

Hgciiq),Hg2Cl2(aolid) I KCl(X),Hg2Cl2(8aturated) I K C 1 ( ! F )

where X refers to the concentration of KCl in the electrode solution,


and Y refers to the concentration of KCl in the salt bridge used with
this form. The differences in types lie in the value of X; thus we have
X=0.1N, l.OiV, and saturated (about 4.8iV) giving the one-tenth nor-
mal, normal, and saturated types of calomel electrode. The potentials
of each type of electrode are highly reproducible when made from
properly purified materials; in use the potentials are stable over long
periods of time. The potentials of the calomel and some other elec-
trodes are given in Table 15.1. I n the table all potentials are referred
to the standard hydrogen electrode.
Although the O.IA'^ and l.ON calomel electrodes have lower tempera-
ture coefficients than the saturated electrode and thus have an advan-
tage over the saturated electrode in theoretical electrochemical
investigations, these advantages are outweighed in the routine-analysis
laboratory by the greater convenience of the saturated electrode. This
convenience is a result of the fact that the saturated electrode and the
saturated potassium chloride bridge that is used to connect the calomel
electrodes to the solution can be made as an integral unit. The other
two electrodes require a separate bridge, making them less compact
and more subject to breakage. Maintenance of the saturated electrode
is simpler since loss of water by evaporation cannot change the com-
position of the solution and make-up solution for losses due to flow
out from the bridge need not be analyzed since the saturated condition
can be assured by having an excess of salt present in the storage bottle.
1 1 3 2 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

Table 15.1—REFERENCE-ELECTRODE POTENTIALS*

Calomel typef Potential


Temperature,
° C O.IN l.ON Saturated Ag-AgCl§ Hg-HgjSOil

0 .- . .- .-- - 0 . 2366 0. 6350


6 - -0.2341 0. 6310
10 - 0 . 2314 0. 6270
12 0. 3362 0. 2628 - 0 . 2303 0. 6264
15 . .- . _ 0. 3360 0. 2608 - 0 . 2286 0. 6231
20 0. 3358 0. 2476 -0.2256 0. 6193
25 - 0. 3356 0. 2801 0. 2444 - 0 . 2223 0. 6162
30 0. 3354 0. 2417 -0.2194 0. 6111
35 0. 3363 0. 2391 - 0 . 2190 0. 6070
38 0. 3362 0. 2375 - 0 . 2170 0. 6055
40 - 0 . 2157 0. 6031
45 - - - - 0 . 2121 0. 5990
60 -- - - -0.2084 0. 5949
65 - - - 0 . 2045 0. 5905
60 - 0 . 2006 0. 5866
70 - ... - 0 . 1965
80 -- - 0 . 1878
90 - - -- - 0 . 1787
95 - 0 . 1695
95 - 0 . 1651

•Taken from Bates, Eef. 1, unless otherwise noted.


t Includes salt-bridge junction potential; saturated-KCl dual bridge type tor unsaturated electrode.
t In absolute volts vs. the standard hydrogen electrode.
§ Standard potential.
1 TalJen from Earned and Owen, Kef. 13, standard potential.

The saturated electrode is thus unlikely to have a marked change of


potential due to inadvertent change in potassium chloride concentra-
tion. The larger temperature coefficient of the saturated electrode is
usually not important in its use in electrometric methods of analysis
since the error caused by the change in potential is usually not signifi-
cant compared to the other errors in the analysis. The mechanical
and operating advantages of the saturated type make it the choice
for use in most methods.
The mechanical construction of a saturated calomel electrode varies
for the most part with the nature of the salt bridge incorporated with
it; the electrode structure itself varies depending upon the current
expected to flow through it. Some common designs are described by
Bates; ^ the special designs used in electrometric methods of analysis
will be described in the descriptions of the methods. Hills and Ives ="
and Bates ^ have described in detail the various precautions involved
ELECTROMETRIC METHODS 1133

in making and using the calomel electrode as a precise reference elec-


trode ; for analysis purposes most of these precautions can be relaxed.
Thus, in the preparation of the electrode, unpurified reagent-grade
materials can be used in place of specially purified materials, and the
electrode can be used in contact with air or oxygen. The potentials
of these less carefully made electrodes are not usually the reproducible
potentials and may differ by several millivolts or more from the values
obtained with the best electrodes. However, the potentials are stable
over long periods of time if they are kept uncontaminated with test
solutions. For most electrometric methods, a complete calomel elec-
trode assembly suitable for use without modification of the bridge is
available commercially; for the remaining methods, the calomel elec-
trode assembly used in the commercial assemblies can be removed and
used with the special salt bridge required.
The potassium chloride solutions used in these electrodes tend to
creep up the walls of any containers and to evaporate, leaving a coat-
ing of salt, which is at best unsightly and at worst interferes with the
measurements by shorting out electrode leads. A light coating of
high-melting low-volatility stopcock grease on the affected parts is
recommended to prevent this creep. Vaseline, Apiezon type greases,
and rubber-based greases (e.g., Lubriseal) are satisfactory; silicone-
base greases should be avoided unless it is known that they will not
creep themselves and cover the glassware with a film of grease in
unwanted areas.
(b) Silver-Silver Chloride Electrode. The silver-silver chloride
electrode is an important reference electrode in electrometric methods
in which the solutions contain chloride. In this case the electrode
can be used without a salt bridge; the errors caused by changes in
the reference voltage with small changes in the chloride content of
the solution are negligible compared to the other errors in the methods.
The usefulness of the silver-silver chloride electrode in this applica-
tion is due to the insolubility of silver chloride and the purity of the
electrode reaction in the pH range from below zero to over 13:

AgCl(8oi Id) + e-»Ag(Boi Id) + Cl-

Few anions affect the potential, and many that do can serve in place
of chloride as the electrode anion, thus sulfide, bromide, and cyanide
can be used to give a reference electrode if they are present in solution
in the proper concentration ranges.
The silver chloride electrode can be used in reference-electrode as-
semblies in a manner similar to calomel electrodes; the reproducibility
of the electrode potential is very good when properly purified ma-
terials are used in making up the electrode.
1 1 3 4 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

Three types of silver-silver chloride electrodes, based upon the


method of preparation, are recommended for use where precise
reference-electrode potentials are needed. These are the electrolytic,
thermal-electrolytic, and thermal electrodes. Bates ^ has described the
preparation of the electrolytic electrode by electroplating a layer
of silver on a platinum substrate, washing the deposit carefully to
remove plating-bath impurities, and electrolyzing the electrode in a
chloride solution to convert part of the silver to the chloride. He
describes in detail the preparation of the thermal-electrolytic elec-
trode in which a paste of specially prepared silver oxide in water is
thermally decomposed on a platinum substrate and partially converted
to the chloride by electrolysis. The thermal electrode " is made by
decomposing a paste of silver oxide, silver chlorate (or perchlorate),
and water on the substrate. All the electrode types are highly re-
producible in potential after an initial soaking period.
Less carefully prepared silver-silver chloride electrodes can usually
be used in analysis, particularly for applications where the electrode
is used without a salt bridge. Any uncertainty of the electrode po-
tential in this case is due in large part to the uncertainties in the
chloride concentration; this uncertainty is many times that introduced
by electrode preparation using reagent-grade materials. A particu-
larly useful electrode for titration work is made using pure silver wire
annealed by heating to redness before plating with chloride. Pure
silver wire is readily available from laboratory supply houses.
(c) Other Reference Electrodes. Other electrodes are used occa-
sionally, particularly where the use of chloride salt bridges is not
desirable. The mercurous sulfate electrode, which is similar to the
calomel electrode in construction, can be used with sulfate systems; the
glass electrode is sometimes useful when the acid concentration of the
solution is known or held constant and when its high impedance is
acceptable. Silver sulfate is too soluble to be useful as a reference-
electrode component in most cases where it would otherwise have a
number of advantages.
15-1.2 Salt Bridges
The salt bridge is the component used to provide an ionic-conduction
path between separated parts of electrometric-analysis apparatus.
Salt bridges are used to isolate electrodes from each other when it is
necessary to prevent one electrode reaction or its reaction products
from interfering with the other electrode reaction. They are also used
to preserve the integrity of a standard or reference electrode by pre-
venting contamination of the solution surrounding the electrode; also
the use of a bridge enables the reference or standard electrode to be
ELECTROMETRIC METHODS 1135
used at a different temperature and pressure than the rest of the
apparatus.
The difficulties encountered with salt bridges are such that most
experimenters go to great lengths to avoid their use. Some of these
difficulties are:
1. Uncertainties in the elimination or evaluation of junction poten-
tials of the bridges.
2. Relatively high resistance of the bridges.
3. Mechanical and electrical failures.
4. Contamination of solutions.
Junction potentials arise from differences in the composition of the
two solutions found at the junction of the salt-bridge solutions and the
solution into which the bridge is inserted. The magnitude of this
potential is a complex function of the composition of the bridge solu-
tion, the nonbridge solution, and the method by which the junction
is formed. Theoretical and experimental investigations show that, if
concentrated solutions of certain salts such as potassium chloride are
used as the bridge solution, the junction potentials are often reduced
to a small value that is sufficiently reproducible for most electrometric
methods. Ammonium or potassium nitrate (and other salts if neces-
sary) are also useful in reducing junction potentials and are used
whenever chloride contamination must be avoided. The theoretical
and experimental basis for the use of these salts has been covered in
detail by Bates,^ Chariot,^ and Glasstone.^^
The electrical resistance of electrolytic solutions, even of saturated
salt solutions, is relatively high. This makes the salt bridge a trouble
spot for the designer of electrometric apparatus since the resistance in
the over-all circuit must often be kept as small as possible. The salt
bridges used with reference electrodes can have up to several hundred
thousand ohms impedance, depending upon the measuring equipment
used. The salt bridges used with electrolysis electrodes (electrodes
through which is passed appreciable current) should have resistance
below 100 ohms, preferably less than 10 or so ohms. In electrolysis
circuits the junction potential of the bridge is normally of no concern,
and bridges that are filled with acid or base solutions that have lower
specific resistances than the salt solutions can be employed. The de-
signer uses short bridges of large cross section when the resistance
must be kept low; this is completely analogous to the design of low-
resistance electronic type conductors.
The mechanical failures of salt bridges are the result of mechanical
breakage, the interruption of the solution continuity in the bridge or
junction by solids or gases, and the failure of any artifices used to limit
solution flow from the bridge. Mechanical breakage can be a serious
1 1 3 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

routine-analysis laboratory problem; it can be avoided through the use


of plastic tubing in the construction of the bridge. Chemically re-
sistant tubing made of materials such as polyethylene, fluorocarbons,
and vinyl chloride formulations are as suitable as glass for most appli-
cations ; the continued use of glass tubing in most bridges must be con-
sidered an anachronism.
The interruption of the solution path by solids or gases often occurs
at the junction, particularly in cases where the junction is a small hole
or a fibrous plug. Changes in the design of the junction and its orien-
tation are the obvious solutions to this problem with both gases and
solids; in general, a large-area junction should be used when solids are
present. The interruption of the solution path by a bubble of gas in
the salt bridge is a common cause of erratic bridge behavior; the salt-
bridge design should be such that bubble traps are eliminated, and
the source of the gas itself should be removed if possible. This
salt-bridge problem is very prevalent in routine analysis if care is not
taken to eliminate it in the design of the apparatus.
Electrical failures are usually associated with mechanical failures;
the most common is the development of a high internal resistance
when the continuity of the solution column is interrupted or partially
blocked by gas bubbles or solid materials. Some bridges, particularly
those filled with a gelled solution, develop a high resistance when a
solid phase develops in the gel. Some bridges, particularly those
filled with concentrated salt solutions, develop a high resistance when
the solution "freezes" to a more or less solid mass of crystalline salts.
Bridges that use a gelled solution of ammonium or potassium nitrate
have been known to ignite and char when miUiampere currents
are passed through them. This is a reaction between the nitrate and
the gelling agent initiated by localized heating at some point in the
solution. This spot is often the site of a small air bubble or salt
crystal imbedded in the gelled solution.
The artifices used to limit the flow of solution from a salt bridge
serve to reduce the frequency with which the bridge-solution reser-
voir must be refilled and to reduce the contamination of the non-
bridge solutions with bridge-solution components. F o r reproducible
and low junction potentials, some flow must be permitted to preserve
the integrity of the junction. I n electrolysis circuits low to zero
flow consistent with low resistance is the aim. The common artifices
in bridge design to limit flow are: to balance the hydraulic heads in-
volved so that no pressure difference exists between the bridge and
other component; to use a gelling agent to immobilize the solution;
to use a plug of fibrous material, fritted glass, porous ceramic, or
porous plastic materials; to use a small orifice or capillary path
through an otherwise sealed end; and to use an ion-permeable mem-
ELECTROMETRIC METHODS 1137

brane. Balancing hydraulic heads is not recommended. The use


of plugs of fibrous materials such as asbestos or glass wool is quite
satisfactory for reference-electrode bridges; large bridges of this
type are hard to make resistant to collapse when subjected to pressure
differences. Glass frit and porous materials are useful; however,
care must be taken to use materials with a relatively high void space
to hold electrolytic solutions or the bridge resistance will be excessive.
Gelling agents such as agar-agar and gelatin are used extensively;
bridges using this artifice usually have limited life and must be re-
placed frequently. These gelling agents are not suitable for elevated-
temperature applications. The use of small orifices or capillary paths
produces a bridge with high resistance and limits application to
reference-electrode bridges. Carson ^* has described the use of a
silica gel bridge for an electrolysis circuit operated at elevated tem-
peratures. The improved version of this bridge uses a coarse glass frit
to hold the gel in place.
Carson, Michelson, and Koyama ^^ have described the use of porous
glass in salt bridges. The glass used is available commercially; it is
the leached, unfired form of Coming Glass Works Vycor glass. The
simplest and most useful bridges are made with short lengths of cane
(rod) attached to glass bridges by a short length of plastic tubing;
porous glass cannot be sealed to other glasses since it is unworkable in
a flame.
The plastic tubing should be clamped or wired tightly to the porous
glass plug to hold the plug in place, although bridges using a semi-
stiff tubing such as Tygon will be mechanically tight without such
clamping. Some bridge-solution salts, such as potassium chloride,
tend to crystallize out between the plastic tubing and the glass parts
unless the plastic tubing is clamped tightly. When such salt solu-
tions are used in the bridge, allowing the bridge to dry out will ruin
the glass plug because the expansion of the salt crystals formed upon
evaporation of the water will shatter the porous glass structure.
The performance of salt bridges made with these plugs is definitely
superior to other salt bridges in terms of low resistance, low rate of
solution flow, and mechanical ruggedness at elevated temperatures
and in the presence of pressure differentials. The junction poten-
tials observed vary with the bridge solution; with saturated potassium
chloride, the bridges have junction potentials of the same order of
magnitude as do bridges using plugs of fibrous materials, gelled solu-
tions, capillary leaks, or small orifices. The flow rates are (for
i4-in.-long plugs y^ in. in diameter) on the order of 1 ml of solution
per month or less, even under pressure differentials as high as 15 psi.
Carson et al.^° also described the use of ion-exchange resin mem-
branes in salt bridges. These bridges show high junction potentials
1 1 3 8 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

and are useful chiefly in electrolysis circuits where a bridge of large


cross section is desired. They possess few advantages otherwise over
the porous glass bridges.
15—1.3 Electrode Reactions
The electrode reaction is the process by which an electric current
creates a chemical change during electrolyses. For use in electro-
metric analysis, the electrode reaction must take place in such a man-
ner that the chemical change and electrical quantities measured are
correlated to each other. This normally requires that the electrode
process be controlled in some fashion to prevent or greatly reduce any
side reactions that would otherwise interfere in the interpretation of
the data. The control of electrode processes requires consideration
of the various aspects of electrode-reaction mechanisms and kinetics.
The primary electrode reaction can be considered to be the result
of three consecutive transfer steps: transfer of the reaction species to
the electrode interface, transfer of electrons at the electrode, and
transfer of the reaction products from the electrode. Other processes,
such as absorption-desorption of a substance on the electrodes and
chemical reaction among the various substances (including the elec-
trode) at the electrode solution interface may also play a part in
the primary electrode reaction. The over-all rate of the electrode
reaction is a function of the kinetics of the various steps; it is usually
possible to alter the rate of any step by altering the conditions at
the electrode-solution interface. Some of the many known means of
varying the rates of various electrode reaction steps are: altering the
rate of mass transfer by stirring, changing the concentration, chang-
ing the primary reaction by changing electrodes or adding reagents,
changing the temperature, and changing the applied voltage.
The two mass-transfer steps are carried out by three principal
modes: diffusion, convection, and migration. Depending upon the
type of electrometric analysis being performed, the first two are the
important modes of mass transfer in electrolysis. The latter is usu-
ally inherently insignificant or is made so by the analysis procedure.
Diffusion is observed whenever the chemical potential (i.e., activity)
of a substance varies from point to point in a solution. The diffu-
sion rate depends upon the temperature, the chemical potential differ-
ences, the nature of the substance diffusing, and, to a great extent,
the path over which diffusion takes place.
Migration is the motion of charged particles in an electric field.
In solution all charged particles carry the electrolysis current in
proportion to their transport number. If the substance being deter-
mined has a small transport number, mass transfer by migration
becomes negligible. This is desirable in most electrometric analyses;
ELECTROMETRIC METHODS 1139

the addition of a large excess of supporting electrolyte to the solution


is often used to accomplish this goal. Salts of the alkali metals,
which do not readily enter the electrode reaction, are frequently used
as the supporting electrolyte; in process work many samples have
sufficient inert electrolyte concentrations to make the addition of a
supporting electrolyte unnecessary.
Convection results from stirring of the solution by mechanical
means; it can also result from differences in density from point to
point in the solution as a result of temperature or concentration
gradients.
Convective mass transfer normally occurs when gases are evolved
during electrolysis. Mechanical stirring generally is used when con-
vection is the desirable mode of mass transfer. In microanalysis
mechanical stirring becomes a major problem since the small volumes
involved are easily splattered and lost.
The basic circuit used in electrolysis is shown in Fig. 15.1. The
power source is connected through a switch to the electrolytic cell.
In the cell one electrode is chosen as the working electrode; the other
electrode then becomes the counter electrode. Depending on the na-
ture of the electrolysis, an ammeter, a voltmeter, or a coulometer may
be used. For the circuit shown in Fig. 15.1, the ammeter and cou-
lometer readings should be corrected for the current flowing through
V; if V were connected between the points designated X, its reading
would have to be corrected for the ohmic drop across A and Q. Usu-
ally, if the reading of J. or ^ is the primary measurement, V will be
connected between the points X so that a correction to the reading is

"^dXD Fig. 15.1—General electrolysis circuit.


P. Power source V. Voltmeter
C. Electrolysis cell A. Ammeter
R. Coimter or reference electrode Q. Coulometer
W. Working electrode

890-4870-^64- -T3
1 1 4 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

not needed; if the reading of V is the primary measurement, then the


connection shown in the figure is better.
The potential of the working electrode when no current is flowing
is given by an expression of the type

^ ' = c o n s t a n t + Z In *• °^^/'^'?j (15.1)


(reduced)
where i^T is a constant depending upon temperature and the nature of
the redox couple controlling the electrode potential, and oxidized and
reduced represent the activities of the oxidized and reduced forms of
the redox couple. This equation is a generalized form of the Nemst
equation:

nF (reduced) ^ '

where E° is the standard potential of the couple and R, T, n, and


F are the gas constant, absolute temperature, number of electrons
involved in the electrode reaction, and Faraday constant, respectively.
The numerical values of the potentials E' and E are measured on dif-
ferent electromotive force scales and hence are not necessarily the
same. The potential of the electrode with respect to the solution is
constant for any given electrode and solution if the electrode reaction
is reversible; it may be constant but is not necessarily so if the elec-
trode reaction is not reversible. A knowledge of this potential would
be very desirable, but unfortunately it is not obtainable since the
measurement of such potential always requires the use of another
electrode and only the difference between the two electrode potentials
can be measured.
The potential of the working electrode when current is flowing
through it assumes a value that is determined by the power-supply
characteristics and the rates of the electrode reactions. It is possible,
with suitable design of controls for the power supply, to conduct
electrolyses in which either the electrode potential (with respect to
a constant potential electrode in the same solution) or the current
flowing in the electrolysis cell can be held constant. These two cases
are the ones most important to electrometric analysis. The third case
that in which neither the potential or the current is held constant,
is of very limited, usefulness in analysis, although it is commonly
encountered in electrolytic processes.
(a) Controlled-potential Electrolyses. In controUed-potential elec-
trolyses, the potential of the working electrode is held constant by the
power supply. The potential is held constant relative to either a
ELECTROMETRIC METHODS 1141
reference electrode or to the counter electrode. In the latter case the
counter electrode used must not change in potential during the
electrolysis.
The current flowing per unit area (current density) of an electrode
during controlled-potential electrcdysis is a function of two sets of
variables: those associated with the electrical circuit and those associ-
ated with the electrode process. The total current in electrolysis is
given by the product of the current density and the area; in some
cases the power-supply characteristics are such that they limit the
total current that can be drawn at the regulated potential, and in
others the area of the electrode is too small for the desired current.
The circuit variables are largely the impedance of the electrolytic
cell, the electrodes, and the power supply and leads. Since, in most
cases, the effects of the circuit variables can be held constant, it is
possible to compensate for them in the design of the apparatus or
to correct for them in the treatment of the data when they affect
the analysis of l^ie sample.
The current-density limitation imposed by an electrode process
step is often the key part of the electrometric technique of analysis.
Thus the limitation of current imposed by the mass-transfer step of
diffusion is the basis of polarography. The process steps that may
limit current density are the rate of mass transfer to or from the
electrode and the rate of electron transfer at the electrode. The
former is a function of the stirring, the diffusion characteristics, and
the concentration of the reacting species; these mass-transfer steps
are normally the current-limiting steps in controlled-potential elec-
trolyses. The rate of electron transfer is a function of the potential
of the electrode vs. the potential given for the couple by Eq. 15.1
and the activation-energy requirements. The potential of the couple
at the electrode is a function of the concentrations in the electrode-
electrolyte interface solution, and, as this potential approaches that
imposed on the electrode, the driving force for the electron-transfer
step decreases to zero and no further electrolysis can occur. This is
the key effect of controlled-potential electrolyses since, by proper
selection of the imposed potential, the potential of a couple in a sam-
ple can be brought to a desired value. The current in controlled-
potential electrolysis is seldom electron-transfer controlled until the
final stages of the electrolysis; up to this point the system is usually
mass-transfer limited, and all the reacting species reaching the elec-
trode interface react before they move away.
For electrolyses in which the aim is to convert a quantity of re-
acting species, the control of the electrode potential is used, usually
to prevent a side reaction that would occur if the electrode potential
1 1 4 2 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

were to exceed the set value. I n this case the current limitation im-
posed by the power supply is not critical since the electrode poten-
tial will always be below the set value until the current becomes
mass-transfer controlled. The power supply, when it is operating in
its current-limited region, is unable to supply electrons (or to remove
them if the electrode is an anode) at a high enough rate to maintain
the potential. This is analogous to the effect of a constriction in
a pipe through which gas or liquid flows when the demand for the
liquid or gas is higher at the output end of the line than the possible
flow through the constriction. As electrolysis continues, the concen-
tration of the reacting species decreases to a value at which mass
transfer becomes limiting, and the electrode potential will then come
to the set value.
The current flowing in a constant-potential electrolysis in which the
solution is stirred and in which the current is limited by mass trans-
fer is proportional to the concentration of the reacting species. As
the electrolysis proceeds, the concentration of the reacting species
decreases, and hence the current also decreases. A t any time t when
the current is mass-transfer limited,

where A; is a constant for a given set of electrolysis conditions, i.e.,


stirring rate, electrode area, and applied voltage, and C is the con-
centration of the relative species. Integrating from t=0 and t=t
and setting 0=Co when ^ = 0 ,
C=Coe-^* (15.3)
The current decreases exponentially throughout the electrolysis.
The concentration of reactive species is defined in Eq. 15.3 as the
concentration of reactive species which must be reacted to make the
activity ratio, i.e., oxidized/reduced, assume the correct value to meet
Eq. 15.1. The value of the initial concentration {Co) can be made
any fraction of the total concentration {CT) present by suitable choice
of the electrode potential since the latter sets the value of oxidized/
reduced which will be reached.
The final concentration of the reacting species {CF) never reaches
zero in finite time. Theoretically the concentration will decrease ex-
ponentially in accordance with Eq. 15.3; the time t for stopping the
electrolysis can be selected such that CF is negligible compared to Co.
If CT—CO is also negligible, than the electrolysis can be said to be
complete insofar as any practical significance is concerned. The
completeness of the electrolysis is thus a function of the imposed po-
tential and the time of electrolysis; the proper selection of both can
ELECTROMETRIC METHODS 1143
be made using Eqs. 15.1 and 15.3 when the constants for these equa-
tions are known for the electrolysis.
Although a complete conversion of the reacting species cannot be
achieved in an electrolysis at constant electrode, potential, conversions
of over 99.9 per cent are readily made in many cases. The limit to
the conversion is set by the onset of side reactions that prevent set-
ting the potential at a greater value to increase the fraction converted.
The current in a constant-potential electrolysis theoretically never
reaches zero in finite time but decreases continuously at a slower and
slower rate; practically, the current decreases exponentially to a con-
stant value. This constant final current is known as the residual cur-
rent and is the consequence of side reactions that are not completely
eliminated at the potential imposed on the electrode, the attainment
of a limiting rate owing to the electron-transfer step, the hysteresis
or lack of instantaneous reversibility in the power-supply control sys-
tem, and the presence of electrical leaks, such as the charge and dis-
charge of a condenser formed by the electrode and solution when
certain electrodes or electrolysis cells are used. The value of this
residual current is quite important in electrometric analyses in which
the current flowing is measured or the total quantity of electricity
used is measured. Of the causes, that due to side reactions is usually,
but not always, the largest.
(b) Constant-current Electrolyses. I n constant-current electroly-
ses the electrolysis current is held constant by the power source. I n
the simplest case the electrode reaction is not limiting, i.e., the limit
on the electrolysis current is imposed by the power supply. I n terms
of reaction steps, this means that the mass transport of reacting ma-
terials to the electrode is more than sufficient to maintain the over-all
rate. The electron-transfer step requires that at least a minimum po-
tential, depending upon the nature of the reacting materials, be main-
tained at the electrode-solution interface to provide the driving force
for the step. The electrode reaction that requires the lower potential
will be the one that takes place.
As long as the rate of the reaction with lowest potential is sufficient
to sustain the electrolysis current, other reactions with higher potential
requirements will not occur. However, if the mass-transport step
limits the rate of this lowest potential reaction, the potential of the
electrode will increase until additional electrode reactions with higher
potential requirements can take place.
Electrolysis at constant current is not as selective as electrolysis at
constant potential. However, if the electrode process desired is the
one with the lowest potential requirement in the cell and if the cur-
rent is kept below the limiting mass-transfer rate, then the electroly-
1144 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

sis will proceed only by this reaction. This type of electrolysis is used
extensively in constant-current coulometric titrations.
15—1.4 Direct-measurement Methods
I n these methods the measurement of the electrical quantity serves
as the primary measurement of the analysis.
(a) Potentiometry. I n potentiometric methods the potential de-
veloped by the substance to be determined in a suitable galvanic cell
is Utilized to measure the quantity of the substance present. The rela-
tion between the potential of a galvanic cell and the concentration
of the substance is complex; and only a few systems are known in
which a useful relation for analytical purposes is experimentally
achieved. Although the substances that can be analyzed by potentiom-
eitry are few in number, the need for the determination of one of these,
hydrogen ion, makes this method one of the most commonly used
methods in routine analysis.
(b) Voltammetry. The voltametric methods employ the current-
voltage characteristics of an electrode system which is subjected dur-
ing electrolysis to a limit on current or potential by the kinetics of
one step in the electrode reaction. Of the voltametric methods, the
ones measuring the limited current are known as "amperometric
methods"; no general term has been agreed upon for methods measur-
ing potential.
From a routine-analysis standpoint, direct electrometric methods
based upon voltammetry offer the advantages of being useful for
measuring a variety of substances, of having high sensitivity, of
allowing speed in making the measurements, and of requiring rela-
tively simple, low-cost equipment. The accuracy and precision of the
results is usually poorer than for other methods of analysis but is
often very satisfactory for control purposes or for development work.
(c) Goidometry. Coulometry methods utilize the quantity of elec-
tricity required to chemically change the substance as the measure of
the substance. I n a sense electricity is used as a reagent to effect the
chemical change, and the procedures closely resemble those of vol-
umetric analysis. The basis of the methods consists of the laws of
electrolysis formulated by Faraday in 1834 which relate the quantity
of chemical change associated with passage of electricity through an
electrode-electrolyte system and the quantity of electricity.
Coulometry methods have been particularly useful in micro- and
ultramicro-analysis since the amount of electricity for as little as 10"^
equivalents of chemical change is readily measured with high accuracy
using simple electrical equipment.
(d) Other Methods. Other methods of analysis in which an elec-
trical quantity serves as the measure of the substance to be determined
ELECTROMETRIC METHODS 1145

are po^ible. These methods have not been investigated or developed


to any great extent. The only method falling into this category in
this presentation is the measurement of dielectric constant to analyze
a two-component organic system.
15—1.5 Indicator Methods
In these methods electrometric techniques are employed to indicate
the status of a chemical reaction involving the substance to be meas-
ured. The amount of reagents needed to produce the reaction is
measured by some other means when the "indicator" shows that a
certain state of reaction has been reached. Although it is possible
to convert almost any property of the substance to be analyzed into
an electrical signal by appropriate transducer systems and although
this would allow definition of the transducer systems as electrometric,
only those transducer systems that are based upon electrochemical
phenomena are defined as being electrometric. The remaining trans-
ducer systems form the basis of a number of physical methods of anal-
ysis. Typical of these nonelectrometric methods in which an electrical
signal is measured are the photometric methods based upon measur-
ing the radiation transmitted by a sample with an appropriate radia-
tion detector.

15-2 DIRECT TECHNIQUES


15—2.1 Potentiometry
The use of the potential developed by an electrode as the measure of
the concentration of a substance in solution is theoretically applicable
to a large number of substances. Potentiometry is simple in principle
and employs relatively simple experimental techniques. However,
there are many theoretical and practical limitations to the accuracy
and precision obtainable in relating concentrations to measured poten-
tials. At present the application of direct potentiometry is limited
largely to the determination of pH; a few methods have been described
for the determination of halides in special samples.^"' ^^
This discussion of potentiometry is limited to the determination of
pH; no discussion has been included on the determination of substances
by potentiometry since it is not used routinely in the analytical work
associated with the processing of atomic energy materials. A further
limitation is made in that only procedures involving the glass electrode
have been included; the use of other pH sensitive electrodes is not often
encountered in the analysis of atomic energy materials.
(a) fR Scale. The pH scale can be defined in a number of ways,
none of which are free of arbitrary assumptions or problems of in-
terpretation. From a process-control standpoint, a pH scale can best
be considered as a set of numbers which serves as a practical scale of
1 1 4 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

acidity and alkalinity. A particular p H scale is framed in terms of a


set of operations and calculations. Process-wise, there is little value, if
any, in considering the meaning of p H in terms of solution theory.
This practical p H scale is a consequence of how p H is used in process
control and other applications. Many properties of solutions which
are difficult to measure directly can be correlated with p H ; hence p H
can be used as the measured variable for process control. Among the
properties of solutions in which a p H correlation is often found are:
long-term storability of waste solutions in terms of tank corrosion and
formation of undesirable precipitates; product yields in organic
synthesis, biochemical processes (antibiotics, brewing); rate of reac-
tions in a process; and tendency of a solution to form gels upon cooling.
A common example familiar to most readers is the neutralization
of acid waste solutions before storage to prevent them from damaging
the storage facilities. The cost of neutralizing materials is not trivial,
and it is generally desirable to avoid overneutralization, particularly
for cases in which precipitates may form. The stability under storage
of neutralized waste can be correlated with p H , and the plant opera-
tion can be adjusted to bring the p H of the waste to the correct value.
The waste solution can then be placed in the storage tanks with some
degree of confidence that the storage characteristics of the solution
have been fixed to the desired value in spite of the fact they cannot be
readily measured directly.
The operational definition of the practical p H scale is formulated as
follows:
pB.=pKs+fiT){E-Es) (15.4)

where pHg is the assigned p H of a solution used as a standard refer-


ence point, f{T) is the coefficient relating electrode voltage to the p H
unit which, as is indicated, is a function of temperature, and Es and E
are the voltages of the p H electrode assembly when it is immersed in
the standard solution and in the unknown solution, respectively. Note
that pHs and f{T) need not conform to any solution theory concept
to be useful. A set of standards that define a practical p H scale has
been developed; use of this scale permits intercomparison of p H values
obtained by different groups. This p H scale has been endorsed by
standardizing groups in the United States and Great Britain.^^- ^^
When these standards are used, the factor f{T) is assigned the theo-
retical value wg/2.303 BT, where % is the f araday constant, B is the
gas constant, and T is the absolute temperature. Note that if the two
measured potentials E and Eg are obtained at different temperatures,
there is actually no definition of the p H scale unless the two tempera-
tures are explicitly expressed and the value of T in. f(T) is assigned.
ELECTROMETRIC METHODS 1147
For valid comparisons between pH data obtained by two different
pH measurement systems, it is necessary that the two systems agree on
the assignment of pHs and f{T). The blind assumption of such agree-
ment can lead to disastrous results since the numerical pH value
obtained on a solution in one system may differ by a large amount from
the numerical pH value obtained by the other system on the same solu-
tion. For example, in a study of the difficulties being encountered in
a waste neutralizer that was controlled by a plant pH measurement
system, it was found that the numerical plant pH values differed by
one to two units from the measured laboratory pH values. The waste
solution, neutralized to pH 9.5 to 10.5 according to the plant pH
system, had a laboratory pH value of 7.8 to 8.8. Before the situation
was resolved, the laboratory results were unfortunately confirmed by
the rapid failure of several large circulating pumps due to corrosion
by the improperly neutralized solution. The difficulty arose because
the plant pH control set point was being taken from the laboratory
pH data on the storability of the waste solution. When the plant pH
control set point was moved to the numerical value given by the plant
pH system for properly neutralized waste, the difficulties due to im-
proper neutralization ceased.
It should be noted that the buffers recommended by the National
Bureau of Standards (commercially available) are internally con-
sistent with respect to the value of pH« and f{T). Also the potential
of the hydrogen electrode, and hence of the pH systems correlated to
the hydrogen electrode, is defined only for one temperature. The
changes in potential with changes in temperature cannot be correlated
by resort to nonthermodynamic assumptions.^ In the operation of
conventional electronic pH meters, the temperature compensation sup-
plied applies only to the factor f{T)=n%/2.Z0ZBT and does not
correct for any changes in pH, with temperature.
Other pH scales offer no advantages in so far as process control is
concerned over the practical scale. Difficulties in eliminating the ef-
fects of junction potentials, the change in activity with salt content,
the change in activity and actual stoichiometric concentration with
temperature, and the difference in temperature coefficients of the ref-
erence electrode and the sensitive electrode make it unlikely that any
absolute method will be simpler or less subject to application errors.
In this regard, the determined efforts of manufacturers of pH-meas-
uring equipment and the standardizing groups in making equipment
and standards interchangeable insofar as the practical pH scale is
concerned are noteworthy and are leading to a universal pH scale,
which, if not fundamental, meets all practical needs.
1 1 4 8 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

(b) Electrodes. The electrodes used in pH-measuring systems are


used in a galvanic cell of the type
pH-sensitive electrode||solution X|reference electrode
Note that the junction potential of the salt bridge between the ref-
erence electrode and solution X is not eliminated. This bridge is
usually a saturated potassium chloride bridge, and the reference elec-
trode is usually a calomel electrode. The operational definition of
p H includes the junction potential of the reference electrode in any
voltage measurements.
The hydrogen electrode is the standard electrode for determination
of p H values, but it is inconvenient for routine use. Other electrodes
that are more convenient to use experimentally, such as the quinhy-
drone electrode, the antimony electrode, and glass electrodes, closely
approximate the response of a hydrogen electrode to changes in p H
over a part of the p H scale; hence they can be used in place of the
hydrogen electrode within the limits of their range. The performance
of these electrodes is always measured in terms of the equivalent
hydrogen-electrode system. The hydrogen electrode has been studied
for many years, and the reader is referred to B a t e s ' for a more com-
plete discussion.
The hydrogen electrode, quinhydrone electrode, and antimony elec-
trode are pH-sensitive electrodes that function by virtue of an oxida-
tion-reduction reaction occurring at the electrode-solution interface.
This has been described more fully by Bates and others; what is of
concern in this discussion is that this electrode reaction is usually
sensitive to the presence of other oxidation-reduction reaction systems
present in the solution. I n such solutions, the error in the p H value
determined from the voltage of the electrode can be quite large. The
presence of other materials in solution can also affect the p H response;
this is given in more detail by Bates.^
The glass electrode differs from the other pH-sensitive electrodes in
that its response is due to a mechanism other than an oxidation-reduc-
tion reaction.*' ^* This difference in mechanism is due to the fact that
the glass electrode is a membrane system; the voltage of the electrode
is a composite voltage of a reference electrode and the potential
developed across a glass membrane; for example, H g , HgoCU (soud)
HgaCls (saturated) HCl (fixed N) |glass membrane|test solution. The
mercury-mercurous chloride internal electrode and the internal solu-
tion of the glass electrode are used to make electrical contact with the
membrane. The mercury-mercurous chloride electrode is commonly
used as the internal electrode, but other electrodes are also used. The
potential of the internal electrode and of the glass membrane-internal
solution interface is constant; any changes in the potential of the glass
ELECTROMETRIC METHODS 1149

membrane-test solution interface will change the over-all potential of


the glass electrode by an equal amount. The value of the internal
potential is not critical so long as it is kept constant.
If a solution of the same molar concentration of hydrochloric acid
as is used in the internal solution is used as the test solution, the
potential difference across the glass membrane would theoretically
be zero. This is not often the case; a small potential is usually found.
This potential is known as the "asymmetry potential"; its existence
is one of the reasons glass-electrode p H systems must be standardized
periodically by buffer solutions of known p H . The asymmetry
potential of an electrode tends to change with time; the rate of change
is dependent upon the history of the electrode. Thus, when a new p H
electrode that has been stored dry for some time after its preparation
is wetted, the p H response is developed within a few minutes; the
asymmetry potential of the electrode, however, may not stabilize to a
low rate of drift for days. The drift rate of a stabilized electrode is
usually small enough to be neglected in p H work if the electrode-pH
meter system is standardized every day or two.
The p H response of a glass electrode is not altered upon exposure
to the beta-gamma radiation fluxes as found in atomic energy material
process streams. Carson and Michelson ^ found that all the common
electrodes used in electrometric methods of analysis were essentially
unaffected by the presence of beta, gamma, or alpha radiation
although, in the case of glass electrodes, the glass was darkened to
the point of opacity.
The p H response of most glass electrodes is imperfect at both ends
of the p H scale. The errors in highly acid solutions are not as tech-
nically important as the errors caused by a partial sodium-ion re-
sponse at high p H since the latter type solutions are more often
encountered, particularly in waste treatment. Special-purpose glass
electrodes, made using a pH-sensitive glass that uses lithium ions to
replace most of the sodium ions present in the general purpose p H -
sensitive glass, are available for use in such cases. A description of
commercially available p H electrodes and their properties has been
given in Bates.^
(c) Measurement of pH. The measurement of p H with a glass
electrode varies somewhat with the p H meter-glass electrode system
used. The manufacturer's manual should be followed with respect
to the time the p H meter must be warmed up for use, the internal
zeroing of the p H meter scale or reference circuits, and the specific
standardization procedure to be followed. For laboratory instru-
ments, the general standardizing procedure is:
Allow the pH meter to warm up for the required period, and perform
any zero adjustments required. Place the glass and reference electrodes
1 1 5 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

in the buffer solution used for standardization. Adjust the manual


temperature control to correspond to the temperature of the buffer;
alternatively, if automatic temperature compensation is used, allow time
for the detecting element, which should be immersed in the buffer along-
side the glass electrode, to come to equilibrium. Adjust the standardiza-
tion control until the pH meter reads exactly the known pH of the buffer.
Remove the buffer solution, rinse the electrodes carefully, using, if possi-
ble, a portion of the unknown solution as the last rinse. Place the
electrodes in the unknown solution, and read the pH.
Several points in the procedure should be noted: (1) If the glass
electrode has been dry and has not been used for some time, it may
show a drift in potential until it gets back into equilibrium with water.
A dry electrode can be used after a few minutes soak if the standardi-
zation is checked frequently until it is apparent that the electrode is
equilibrated. This will be shown during standardization by the lack
of the need to adjust the standardization control when the electrodes
are placed in the buffer solution. (2) The buffer solution used should
be within a few pH units of the unknown for highest accuracy. This
technique minimizes the errors that may be present in the pH meter
scale. (3) The temperature of the unknown must be the same as the
buffer or it must be the same for the series of measurements with a
constant buffer temperature used. This technique is required to
allow definition of the pH scale and thus to allow reliable correlations
of pH values with solution properties. (4) The pH values measured
should be corrected for any sodium-ion error as necessary to give the
correlation needed. With solutions above O.IM in total ionic content,
the pH of the solution cannot be readily correlated in a simple fashion
with the hydrogen-ion activity.^^
Plant pH-measurement systems are standardized in much the same
manner as the laboratory instruments, i.e., the electrodes are immersed
periodically in a buffer solution and the meter is adjusted. Some
precautions are required to prevent process upset: (1) The process
controller must be "locked out" before any standardization actions are
initiated. In automatic control systems the lockout should be made
automatically as part of the initiation of the standardization proce-
dure. (2) The pH cell, should be rinsed before standardizing. For
installations in which the sampling operation cannot be checked by
visual observation (i.e., to see if solution is flowing into the cell),
a rinse of markedly different pH should be used to produce a large
displacement of the pH meter reading. This will check the rinsing,
as well as assure that flow through the cell is taking place. (3) The
temperature of the buffer should be within the range allowed by the
particularly defined pH scale being used. (4) If the process can be
upset or altered by material from the usual standardizing buffer solu-
tion getting from the pH cell into the process solution, a procedure that
ELECTROMETRIC METHODS 1151

guards against possible plumbing or operator failures is to use process


solutions for the rinse and standard pH solutions. Synthetic process
solutions or a batch of actual process solution can be used. The rinses
need not be analyzed; the pH of the solution that is to be the standard
is carefully measured in the laboratory, with precautions being taken
to avoid errors in scale assignment, changes in pH of the solution dur-
ing the measurements, etc. The stock is then used as the standard
solution in the standardization procedure. Care must be taken to
avoid unknown changes in this solution during storage by carbon
dioxide absorption if the solution is alkaline.
Hahn and Koyama '* have described a pH cell used in plants process-
ing essential materials which takes into consideration the radiation
hazard associated with such processes. Michelson and Carson ^' de-
scribed an earlier version.
(d) pH meters. The pH meter used with glass electrodes was one
of the first applications of electronics in the routine-analysis labora-
tory. Without such meters the glass electrode would still be a labora-
tory curiosity. The development of the electronic pH meter has been
described in detail by Ewing,®' ^° Bates,^ and others. Although the
electronics circuitry and components vary with different manufac-
turers, two general types of instrument are distinguishable: the direct-
reading type and the deflection, or comparison, type. The direct-
reading type allows continuous recording or indication of the p H ; the
accuracy and precision obtainable are less than that obtainable with
a deflection type. For routine analysis and process-control purposes,
a direct-reading instrument has ample accuracy and is the most con-
venient type for use. The'deflection type uses the sensitive electronic
circuit to indicate a null; the voltage comparison is made with a bridge
circuit.
The modem electronic pH meter is one of the most versatile instru-
ments available for use in the analysis laboratory. Miiller'' has re-
viewed the varied uses to which a pH meter has been put which are
of interest to analytical chemists. An additional use not mentioned
by him is the use of a pH meter as an amplifier for simple filter
photometers. All these uses depend in a large part upon the fact
that the input impedance of a pH meter is 10^' to 10^° ohms; this
enables its use with inputs having a large internal impedance of their
own.
(e) Direct Potentiometric Determination of Hydrogen-iSn Con-
centration. This technique has been developed by Jones, Eider, and
Hendrickson '* for solutions containing uranium, thorium, or alumi-
num nitrates. The pH of nearly neutral solutions of uranyl, thorium,
or aluminum nitrate is a sensitive indicator of the free-acid content
of these solutions. Hence a measurement of the pH of a solution
1152 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

containing one of these ions can form the basis of a free-acid deter-
mination if the concentration of this ion is known.
The apparatus described by Jones et al.^'' is a Beckmen model H-2
pH meter with a Beckman number 270 calomel reference electrode and
a number 290 glass electrode. Since the composition of the standard
buffers is not given in the paper, the calibration curves cannot be used
without checking several points to establish the identity of the pH
scales used. A more modem pH meter and other models of glass
and calomel electrodes can be used; here again the pH-scale identity
must be determined. The pH meter-electrode pair was standardized
at pH 7, using the asymmetry (standardization) control. The.elec-
trodes were then placed in a pH 2 buffer, and the meter reading was
adjusted to conform by adjustment of the temperature control. This
procedure adjusts the meter scale to conform with the Nemst equation.
A third standard buffer solution with a p H value close to the pH
value of the samples is used as a check on the setting. For control-
analysis purposes, the direct-reading pH meters are less subject to
operator error than the potentiometric types, offsetting a possible ad-
vantage the latter would otherwise have for this determination.
The calibration curves are made by taking a series of pH measure-
ments on standard solutions containing known amounts of uranium
(or thorium or aluminum) and free acid. The preparation of uranyl
nitrate, thorium nitrate, or aluminum nitrate free of acid or basic
impurities is difficult; the best procedure appears to be to make up
several solutions of relatively high acid or base content which can be
accurately titrated using large samples and to mix them in the
stoichiometric ratios necessary to obtain solutions of the desired final
acid concentration. Several standard solutions made up in this man-
ner can be used to check the free-acid content of the salts used to make
up other standard solutions.
The procedure is to rinse the electrodes carefully with distilled
water; dry them with absorbent paper or cotton, taking care not to
scratch the glass-electrode bulb; and immerse them in the sample
or diluted sample. If possible, rinsing them with the sample before
making the measurement is a good technique. The range of the
method is —0.2M* to -\-0.2M free acid. Samples falling outside this
range should be diluted with standard base or standard acid to bring
them into the correct acid range. The acid value found must be
corrected for the dilution and added base or acid. For highly radio-
active solutions the small samples permitted can be diluted 10- or 100-

•A negatire concentration of acid can exist In these solutions because the so-called
"neutral solutions" (free acid = 0) can dlssolye appreciable quantities of the metal oxide
to form stable solutions.
ELECTROMETRIC METHODS 1153

fold before the pH is measured; this gives a larger volume and


permits the use of the standard size pH electrodes. For uranium the
fluctuation in pH with uranyl-ion content has been found to be smaller
than the other errors in the method when the sample is diluted 100-
fold; hence only one calibration curve is necessary. However, the
precision of the dilution method is somewhat less than with the more
concentrated solutions, since a small error in acid concentration is
multiplied by the dilution factor. This is partially offset by the
greater change in pH with acid content at the dilute salt
concentrations.
The precision of the method lies in the range of ± O.OSM to ± O.ObM
free acid for uranium samples. The direct method gives the better
precision. With proper calibration the method could be used for
mixtures of salts, etc., but the necessary calibration work could be-
come very great if a wide range of concentrations were to be
encountered.
15-2.2 Coulometry
The techniques used in coulometric analyses are closely akin to
those used in classical volumetric analyses. In coulometric titra-
tions the standard solution is replaced by an electric current operating
by means of a suitable electrode reaction on the substance to be de-
termined. The buret is replaced by a device or system that gives the
number of coulombs passed through the electrode during the titration.
The detection of the end point, the sampling, and the preparation of
the sample for analysis are the same as for classical volumetric
analysis.
Although Faraday elucidated his laws of electrolysis as early as
1834, coulometry as a general analytical technique is relatively new.
The work of Szebelledy and Somogyi *° in 1938 can be considered the
start of coulometric analysis; the major effort in coulometry has come
since 1948. Evans and Bannister''^ used coulometric principles in
their measurements, but their work did not receive the attention of
analytical chemists until much later. Lingane,^"-*^'^* Furman,'^"^
and Swift ^^ have been the pioneers in the use of coulometry in analy-
sis; they and their students have demonstrated the versatility and
practical usefulness of coulometry in modern analysis. Comprehen-
sive reviews of coulometry have been prepared by DeFord®*''^ and
Ashley.*^ Tutundzic** has proposed the use of the coulomb as the
standard for titrants.
Coulometric techniques help give high precisions and accuracies to
micro- and ultramicrotitrations, help simplify the design and opera-
tion of remotely controlled titration apparatus, and are highly ame-
nable to automation. These advantages are very useful for handling
1 1 5 4 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

radioactive samples and have made coulometry important in the


analysis of atomic energy materials.
(a) General Considerations. Faraday's laws of electrolysis form
the basis of coulometry; these laws can be summarized by the
equation
W=kQw (15.5)
which states the quantity of substance W that is transformed by the
electrode reaction in an electrolysis in which Q coulombs have been
passed. In the equation, ^ is a proportionality constant and w is the
equivalent weight of the substance for the reaction in the same weight
units as TF. The value of h is 1//, where / is the faraday, 96,490
coulombs (chemical scale) per gram equivalent, i.e., 1.0364 X10"° gram
equivalents per coulomb. The usefulness of coulometry in micro-
and ultramicroanalyses lies in the smallness of this proportionality
constant; a large amount of electricity is required for titration of small
amounts of material. Since values of Q as small as 10"* coulombs
can readily be measured with an accuracy and precision greater than
±0.1 per cent, the accurate analysis of 10"® equivalent of a substance
is theoretically feasible. Titrations involving this small an amount
of material are not yet made routinely because of end point detection
difficulties.
The devices used to measure the amount of electricity used in an
electrolysis are known as coulometers. As a class, these devices are
current-time iiftegrators:

«=r^' it (15.6)

where Q is the number of coulombs passed in the time interval t^ — ti,


It is the current in amperes, and t is time in seconds. The earliest
coulometers, some of which are still used, were chemical coulometers.
In these the electric current is used to electrolyze a solution under
conditions such that the chemical change resulting from one or both
of the electrode reactions can be measured by a gravimetric or vol-
umetric procedure. Thus in the silver coulometer the weight of silver
deposited from a silver nitrate solution is determined; in a gas coulom-
eter the volume of hydrogen and oxygen produced in the electrolysis
of a dilute acid solution is measured. Chemical coulometers are the
standard coulometers to which other coulometers are compared; the
silver coulometer is the ultimate reference for electrical quantity and
current. However, application of chemical coulometers in analysis
is limited because they are relatively inconvenient to use and are not
as precise or as accurate in their usual forms for the integration of
ELECTROMETRIC METHODS 1155

the small currents used in micro- and ultramicrocoulometric titrations


as are other types of coulometers. Page and Lingane °° have described
a micro gas coulometer suitable for coulometric titrations. The cou-
lometer is based on the electrodecomposition of hydrazine in an acid
solution to form nitrogen and hydrogen.
If the current employed in a coulometric titration is held rigorously
constant, the integration of Eq. 15.6 leads t o :
Q=kl {t^-A)=kI At (15.7)
i.e., the measurement required is the time lapse At. This method of
measuring the coulombs used in a titration has proven very useful,
and a large number of analytical procedures have been developed
using this form of a coulometer. The precisions and accuracies of
this form of a coulometer can be very high without elaborate or ex-
pensive equipment, particularly for small currents. Eelatively simple
electronically controlled current sources can hold currents constant to
within ± 0.1 to ± 0.01 per cent; time measurements can be made readily
to within plus or minus a few hundredths of a second. Since the start-
ing or stopping of the addition of current in a titration is controlled by
a switch or relay, the use of electric stop watches wired to start and stop
in synchronization with the switching of the titration current has
proven convenient.
Electronic coulometers suitable for the integration of small cur-
rents have been developed and applied to coulometric titrations with
controlled electrode potentials. A wide variety of basic methods for
integrating a current (or more often, a voltage derived from the cur-
rent by passing it through a resistor) are employed. Among these
are the velocity type integrators. I n these the outputs are shaft rota-
tions, or a series of pulses whose rates are proportional to the input
current. A totalizing counter is used to indicate the number of pulses
or revolutions and thus give a digital output proportional to the num-
ber of coulombs. Meites ^ has described a velocity servo system in
which the revolutions of a servomotor shaft are counted. The input
is amplified, and the output is used to drive the motor. A small
tachometer generator on the motor shaft supplies the necessary feed-
back to maintain the linearity of the system.
Meites ^ has also described a coulometer based on the use of a Weston
model 806 integrating relay. This relay consists of a small d-c motor
constrained to oscillatory motion between two contacts and a count-
ing circuit that registers the number of complete cycles of the motor
armature. The net counting rate is proportional t o the potential
drop across an input resistor. The value of this resistor affects the
counting rate above several thousand ohms; a blank counting rate at
690-457 O—64 74
1 1 5 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

zero current is also found. With proper calibration the unit gives
reasonably good integration of 5 /^a to 80 ma currents, but only if
the currents integrated are reasonably constant.
The use of a special low-inertia integrating motor, such as that
manufactured by Electro Methods, Ltd., Stevenage, England, as a
coulometer has been described by Bett, Noch, and Morris,*' Parsons,
Seaman, and Amich,*' Lingane,^^ and Furman and Fenton.'" These
are permanent-magnet d-c motors with low iron losses, low brush
contact resistances, and negligible shaft friction; hence their speed
is proportional to the driving voltage. Their low inertia gives them
a small time constant of less than 10 msec; they give negligible errors
in starting or stopping. The model 913, used by Parsons, has a nom-
inal 24-volt input; its linear range of operation within ±0.5 per cent
is from 5 volts up. The current drain is well below 0.5 ma. The ac-
curacy and precision of these units appears adequate for routine analy-
sis applications where titrations with reasonably constant but not
controlled currents can be used.
There are electronic circuits that enable the conversion of d-c in-
puts into a train of pulses having a frequency proportional to the level
of th d-c input. One such circuit is shown schematically in Fig. 15.2.
The d-c current flowing in the electrolysis cell charges the condenser
up to a voltage Vt known as the triggering voltage for the gating cir-
cuit G, shown in the figure as a block. The trigger of the gating
circuit initiates discharge of the condenser through the gate and
sends a pulse to the output which can be used to drive a counter to
count the number of times the condenser is charged and discharged
in an interval of time. When the condenser is discharged, the gating
circuit resets itself for the next cycle. The principle of the circuit is
straightforward; the quantity Q of electricity (coulombs) held in a

• =0
ELECTROLYSIS CELL

Fig. 15.2-Schematic diagram of a pulse-generating coulometer.

P. Power supply G. Gate


Ci. Integrating condenser N. Counter
ELECTROAIETRIC METHODS 1157

condenser of capacitance C (farads) is proportional to the voltage E


(volts) impressed across the condenser:
Q=CE (15.8)
For a fixed value of G and £", the quantity Q is also constant; in the
circuit the total number of coulombs passed in the electrolysis is found
by multiplying the number of pulses by the number of coulombs per
pulse.
The principal difficulty in using a circuit of this type is devising a
gating circuit that has stable triggering characteristics so that Vt is
the same for all pulses and that discharges the condenser to a constant
voltage level (this may be zero, but not necessarily). A desirable
feature is that the range of the converting circuit be extendable to
zero inputs without loss of linear characteristics in the integration.
Until recently no reported circuit was able to integrate widely vary-
ing values of the d-c input with precisions better than several per cent;
now, however, at least two instruments are available (Vidar Corpora-
tion and Geotechnical Corporation) that give precisions of 0.1 per
cent or better in d-c frequency conversion and give linear conversions
from zero to the maximum voltage input allowed. The instruments
give a large number of pulses per volt input in the lowest ranges;
hence, a count represents a very small quantity of electricity. Cur-
rents are easily converted to voltage inputs by passing them through
a suitable resistor. The two instruments, plus others that may ap-
pear, offer the possibility of a flexible, precise current or voltage in-
tegrator for the electroanalysis laboratory. As of June 1960 no reports
on their use in analysis had been received by the author, probably be-
cause of the newness of the instruments.
Another large class of electronic integrators is based on the pro-
portionality between the charge stored on a condenser and the voltage
of the condenser (Eq. 15.8). In these integrators the voltage devel-
oped across a condenser is the output measured. For the integrations
the output voltage e^ is related to the input current (or with appropri-
ate circuit changes input voltage) by

eo=- {^^ l{t)dt (15.9)

where I{t) is the current flowing as a function of time (in amperes if


C is in farads). For low-level coulometric titrations, the simple
circuit (a) of Fig. 15.3 would theoretically be feasible for integrat-
ing the current. All the current is stored in the condenser; the con-
denser must have a low leakage rate, the power-supply voltage (E)
must be larger than the final read-out voltage (eo) obtained for the
1 1 5 8 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

D-c POWER ELECTROLYSIS


SOURCE CELL eo
E>eo

(a)

ELECTROLYSIS
D-C POWER
CELL
SOURCE
E>e,>e„

(b)
J: i
Fig. 15.3—Condenser-based coulometer circuits, (a) Basic circuit,
(b) Resistance-capacitance integrator.

quantity of electricity used in the titration, and the read-out voltmeter


must draw only a very small current. These requirements can all be
met without much difficulty; the drawback lies in the size and cost
of the high-quality condensers needed to integrate more than a few
microcoulombs. Low-leakage condensers of 1 /if capacitance are rela-
tively large units and are expensive; if the read-out voltage for 1
coulomb is to be 100 volts, then a condenser bank of 10,000 /*f capaci-
tance would be needed. Yet 1 coulomb represents only 10"' equivalents.
Obviously, this simple direct-integration circuit is not very practical,
even though feasible.
The second circuit (b) in Fig. 15.3 shows a modification of the
basic circuit in which only a fraction of the current to be integrated
is used to charge the condenser. The current is split by the resistors,
and the fraction ri/ra is used for charging the condenser. This frac-
tion can be made very small, and the capacitance values needed for
integration of moderate amounts of electricity are kept in the few
microfarad range. A problem arises in that the charging current
is equal to
. _e,—eo
(15.10)
^2

where e, is the potential drop across ri rather than

(15.11)
r2
ELECTROMETRIC METHODS 1159

ELECTROLYSIS I
D-c POWER CELL e.
SOURCE ^

Fig. 15.4—Analog computer integrator.

which is the condition for linear integration of the electrolysis cur-


rent. Assuming the simplest case, where ei=a constant, and perform-
ing the integration indicated in Eq. 15.9, substituting ic (from Eq.
15.10) for I{t) yields
eo=eta-e-'"2C) (15 12)

and, using the value of i'c from Eq. 15.11 for I(t) in Eq. 15.9,

(15.13)
TtC

The difference between these two outputs represents the error of the
integration and is

(15.14)
r2CL f J

which increases rapidly with increase of t/rzC. Thus the second


circuit (b) of Fig. 15.3 can be used only if t is small compared to ^aC.
The circuit shown in Fig. 15.4 overcomes the nonlinearity in the charg-
ing rate introduced by the buildup of potential across the condenser
through the use of an operational amplifier. These amplifiers are
d-c amplifiers with an amplification factor of 10^ or more and are
widely used in analog computers. With appropriate input and feed-
back elements, they can be used to perform a variety of arithmetical
operations, including integration. Soroka'" and Philbrick '^ have
discussed their use in analog computers. The amplifier is shown in
Fig. 15.4 connected for integration using a condenser as the feed-back
element. The potential at point a is

=^-0 (15.15)
where —4 is the amplification factor of the amplifier, which, as noted
above, is very large. The voltage Co is the voltage appearing across
the condenser as before; the condenser is charged at a rate equal to
Ci/rz by the amplifier. Since no significant back emf is developed at
a, the charging rate remains proportional to e<//'2, and the integration
1 1 6 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

R
-AW-
BALLAST
RESISTOR
ELECTROLYSIS
CELL
D-C POWER
SOURCE

<2>
AMMETER

Fig. 15.5—Basic constant-current source.

is linear over the range of the amplifier output. Booman et alP and
Kelly et al!'^ have described the use of this type coulometer in con-
troUed-potential electrolysis. Precisions of ±0.01 per cent in integra-
tion are reported.
Constant-current power supplies for coulometric titrations have
been described by a number of investigators.*^' '*"^'' The current
needed in a titration can be estimated from the sample size and desired
length of titration:

*= looor (1^-1^)
where i is the titration current in milliamperes, / is the faraday
(96,490 coulombs per equivalent), 8 is the sample volume in micro-
liters, N is the normality of the substance to be determined, and t is
the titration time in seconds. Titration times between 5 and 10 min
are desirable; hence, for sample sizes below 100 /il and 1 ^ concentra-
tion, the current will be less than 20 ma. F o r the highly radioactive
solutions often encountered in atomic reactor material analyses, the
currents range from a fraction of a milliampere to 20 ma.
Figure 15.5 shows the basic circuit of a constant-current supply.
A source of .d-c potential ( 5 ) , such as a battery, is connected in series
with a ballast resistor {B), the titration cell, and the ammeter. I n
the analysis that follows, B includes the internal resistance of B and
the ammeter. The voltage drop across the cell is composed of the
back emf, e, and the potential drop across the cell resistance (^Xr),
where i is the titration current and r is the cell resistance. The condi-
tion for absolutely constant current is that changes in 5 , B, e, and r
cause zero change in i. The purpose of the ballast resistor is to make
the internal impedance of the power supply vary large so that changes
in {e+ir)/i are small compared to B. Let us designate by r' the value
of (e+ir)/i; r' is the effective cell resistance. The value of B and B
can be calculated if r, the change in effective cell resistance ( A r ' )
that is to be guarded against, e, and the change in current (A^) that is
allowable are assigned. A typical electrolysis cell used in coulometric
ELECTROMETRIC METHODS 1161
titrations will have an effective resistance in the 500-ohm region, plus
or minus 500 ohms. Hence A / is 1000 ohms. Assigning i the nominal
value of 1 ma and A^ the value of ±0.1 per cent, we have from Ohm's
law:
«•'=-^3^^^=0.000999 amp (low limit) (15.17)

«"=4=0-001001 amp (high limit) (15.18)


Solving for B and B, we have
5=500 volts
5=499,500 ohms
These high values show why constant-current power supplies seldom
use a pure resistance B for the ballast; for microampere currents, how-
ever, a simple circuit composed of a battery for B and good-quality
carbon resistors for B is very suitable. Highly precise current regu-
lation can be obtained without an excessively large battery. A close
approximation of the value of B and B can be computed directly:

^ = ^ (15.19)

where i is in amperes, B in volts, and r and B are in ohms; r is taken


as the maximum cell resistance expected.
For small currents the basic constant-current source can be used
with B a pure resistance; for larger currents, other means for com-
pensating the effective cell resistance changes are used. Two general
schemes are used: one is to use as the ballast a dynamic device with
an impedance that can be changed by an input signal, and the other
is to pass most of the current around the control section in a shunt
circuit and to use the dynamic device to control only a part of the
total current. This latter is the most widely used scheme for con-
stant-current power supplies rated at more than a few milliamperes.
A generalized constant-current power supply is shown in Fig. 15.6.
The d-c voltage supply usually consists of a transformer-rectifier-
filter system operating from the 110- or 220-volt a-c line. The
output voltage is in the range of 200 to 500 volts and can be stabilized
against line transients and drift by appropriate control circuits.
The output current (i) passes in part through the shunt, which is
usually a power resistor, and in part through the control element(s).
The latter may be purely electronic, such as vacuum tubes and transis-
tors, or they may be mechanical, such as servo-driven rheostats. In
1 1 6 2 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

TITRATE

OUTPUT

POWER SHUNTS
D-C VOLTAGE SUPPLY
CONTROL
ELEMENT

CONTROL VOLTAGE
AMPLIFIER REFERENCE

VW-
<2>
AMMETER

Fig. 15.6—Electronically controlled constant-current power supply.


Re. Input resistor Ro. Dummy load
Rm. Precision resistor for current Sw. Switch can be ganged to switch an
measurement electric timer

a few cases the control regulates the output voltage of the voltage
supply, rather than the current.
In Fig. 15.6 the current is shown passing through a dummy load;
this is required in some units to prevent upset of the control system.
The value of this dummy load in most cases is zero ohms; however,
in some cases, particularly with mechanical control elements, the
load is adjusted to approximately the value of the external circuit.
It is important to open the output circuit with the switch as indi-
cated and not merely to shunt the output circuit, even if Bi is zero.
The switch preferably has shorting contacts; it is usually ganged with
the timing control so that the power to the electric stop watch and
the titration current are switched simultaneously. The ammeter
shown is usually supplemented with a precision series resistor Bu; a
precise measurement of the current can then be made using a po-
tentiometer to measure ea=iBM.
The current passes through the input resistor Be, which is usually
a variable resistor that can be adjusted to give a continuous adjust-
ment of i over the current range for a single shunt. This resistor
must have good thermal stability and, preferably, a low temperature
coefficient. A drift in the output current is often caused by a drift
in this resistor. The input signal e is amplified as required and ap-
plied to the control element such that changes in i are nullified. The
control amplifier usually operates by comparison of the input voltage
to a reference voltage; the latter may be a standard cell, a voltage-
regulator tube, a Zener diode, a mercury cell, or another constant-
ELECTROMETRIC METHODS 1163
REFERENCE
ELECTRODE
WORKING
ELECTRODE COUNTER
ELECTRODE
CONTROL
ELEMENT

D-C CURRENT CONTROL


SUPPLY AMPLIFIER

o
REFERENCE
VOLTAGE

COULOMETER

Fig. 15.7—ControUed-electrode-potential power supply.

voltage element. A possible method of adjusting the value of i is to


change the reference potential, holding B/ constant.
When a constant-current supply is used, it should be remembered
that the voltage at any break in the current loop will rise to the value
of the output from the voltage supply, which is at least several
hundred volts. The best technique in the use and selection of switch-
ing methods is to maintain a continuous circuit at all times. Note
that shorting a constant-current source normally does no harm to the
supply. In power supplies with a slow-acting control element, the
unit will be upset momentarily.
Power sources for coulometric titrations using a controlled elec-
trode potential have been described by a number of investigators
(Refs. 47, 72, 73, and 88 to 95). The power sources are essentially
constant-voltage regulators in which the input is the potential between
the working electrode at which the electrode reaction of interest is
taking place and a reference electrode. A generalized circuit is given
in Fig. 15.7. The control circuits are similar to those used in constant-
current sources, except that all the current normally passes through
the control element. Since the potential drop between the reference
electrode and the working electrode is included in the input to the
control, it is desirable that the control amplifier input have a high
impedance to minimize the current flowing between the reference and
working electrodes, thus keeping the potential drop at a minimum.
The d-c current source should have a well-filtered output since any
ripple in the electrolysis circuit will affect the precision of the poten-
tial control at the electrode. The reference voltage is used to set the
potential applied. Because of the large size and expense of low-
voltage high-current control elements, the control system may take
the form in which the line input to the current source is controlled.
This may be done by using a saturable reactor to regulate the input
current to the rectifier circuits, or it may be done by using phase-
1 1 6 4 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

shifted thyratrons or controlled silicon rectifiers in the rectifier


circuits.
(b) Constant-current Coulometry. The need to add a suitable re-
acting species to the electrolytes used in constant-current electrolyses
to ensure 100 per cent current efficiencies with respect to a desired
reaction has led to the use of electrolytically generated reagents as

Table 15.2—ELECTROLYTICALLY GENERATED REAGENTS USED IN


COULOMETRY

References

Atomic
energy
Reagent General material

Acid—Base type:
Acid, H+ 40, 76, 77, 96
Base, OH- 44, 76, 77, 97, 98 99-102
Oxidizing type:
Chlorine, CU 77, 84, 103
Bromine, Bra 40, 49, 75, 77, 84, 93, 104-109 28, 99, 110
Iodine, I2 60,84,85,98, 111
Ceric, Ce(IV) 55, 112 57, 113
Argentic, Ag(II) 114
Manganic, Mn(III) 115, 116
Hypobromite, BrO" 117
Dichromate, CraOf^ 118
Reducing type:
Ferrous, Fe(II) 55, 77, 90, 91, 119, 120 99, 121, 122
Uranic, U(IV) 65
Uranium, U(V) 123
Titanoyl, TiCIII) 124r-126 48, 127
Cuprous, Cu(I) 49, 54, 77, 82, 102, 128
Vanadyl, VO+2 129
Copper, Cu 130
Stannous, Sn+'' 54, 106, 131
Precipitation and complexing:
Ferrocyanide, Fe(CN)6+* 60
Ferricyanide, Fe(CN)6+'' 132
Versene* 133, 134
Mercuric, Hg+2 135-138
Mercurous, Hg2"^ 136, 138, 139
Silver, Ag+ 46, 80, 140-142 122
Miscellaneous:
Hydrogen gas, Hj 132, 143
Karl Fischer Reagent, (I2) - _ - 83, 144
Ferrous versenate 145

•Ethjlenediaminetetraacetate (H000)2 N—OHj—GHz—N(COOH)!.


ELECTROMETRIC METHODS 1165

the basis of constant-current coulometry. In addition to solving the


problem of electrode efficiency, electrolytic generation of reagents
makes possible the use of titrants not used in conventional titrations
because they are unstable in solution or are hard to prepare and
keep as a standard solution. It also makes possible the coulometric
titration of substances such as 8-hydroxyquinoline and aniline, for
which there is no known direct electrode reaction suitable for use
in a coulometric titration.
The use of electrolytically generated reagents in the titration of
materials that can react at an electrode is also common. In these
the titration will proceed, in part, by a direct electrode reaction of the
substance to be determined and, in part, by reaction of the sub-
stance with the generated reagent; this latter is known as the indirect
reaction. An example is the constant-current coulometric titration
of ferrous ion described by Furman et al.°' The sample is added to
a saturated solution of cerous sulfate in dilute sulfuric acid and
electrolyzed at a smooth platinum anode. The cathode is isolated
from the titration compartment by a salt bridge. During the elec-
trolysis ferrous ion is oxidized at the anode, but, as the concentration
of ferrous ion decreases, the potential of the anode rises until cerous
ion is oxidized. Any ceric ion generated reacts with ferrous ion in
the solution, and the concentration of ceric ion remains low until the
end point is reached. The titration is equivalent to a titration in
which a standard ceric solution is used to oxidize the ferrous ion.
Although normally cerous ion cannot be oxidized to ceric ion at
100 per cent current efficiencies to achieve solutions with appreciable
ceric-ion concentration, the oxidation of the first few parts of the
cerous ion present occurs at 100 per cent efficiency. Since the concen-
tration of ceric ion is kept small during most of the titration by
reaction with the substance to be determined, the current efficiencies
found in practice are very close to 100 per cent.
The key to the electrolytic generation of ceric ion is the high over-
voltage required for oxygen evolution from smooth platinum. This
enables oxidation of cerous ion to ceric ion rather than the Oxidation
of water, which should, but does not, occur at the potential used. A
number of reagent systems used in coulometry show behavior similar
to the generation of ceric ion. Table 15.2 lists the reagents that have
been electrolytically regenerated in coulometric titrations. The ref-
erences have been selected to give a representative, but not compre-
hensive, listing. The wide variety of reagents that have been shown
to be generated for use in titrations is noteworthy; the span of re-
agents covers most of the range required for conventional titrations.
The principal reagent not as yet generated which is in widespread use
is thiosulfate. The electrolytic generation of arsenite could prob-
1 1 6 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS
LEAD TO PLATINUM
CATHODE

5-MM GLASS
SLEEVE HELD IN LEAD TO SILVER
PLACE WITH CLAMP- ANODE COIL

•4-DRAM PERFUME VIAL


HELD IN PLACE
WITH CLAMP

STIRRING BAR
TEFLON COVERED

MAGNETIC
STIRRER
COVERED WITH
PLASTIC BAG

Fig. 15.8—Coulometric (color end point) acid cell.

ably be used as a substitute for thiosulfate in iodometry, but this has


not been reported to date. In Table 15.2, titrations used in the analy-
sis of essential reactor materials are indicated; they are described
in the following paragraphs.
(c) Determinations iy Constant-current Coulometry. Constant-
current coulometric methods for the analysis of essential reactor ma-
terials have been reported for the determination of acid, uranium, and
plutonium in process streams. Coulometric methods have not sup-
planted conventional volumetric techniques in the analysis of non-
radioactive solutions or in the analysis of process raw materials such
as nitric acid, although coulometric methods can readily be adapted to
such analyses.
(1) Determination of Acid. On a routine basis, the coulometric
titration of acid in radioactive samples is used extensively. The pro-
cedures use the cell and electrode system shown in Fig. 15.8. The
electrode reactions are:
Cathode (platinum) H+"l-e"-»l^ H2
H2O4"6-^1/2 H 2 + O H '
Anode (silver) Ag"i-Br"-»AgBr+e"
ELECTROMETRIC METHODS 1167

The electrolyte may contain chloride in place of bromide. The use of


this electrode pair eliminates the salt bridge that is necessary if both
electrodes are inert since, in this case, the anode reaction is
20Hl*y202 + H . O + 2 g
H20^i/202"F2H+-F2e
in effect reversing the cathode reaction. This platinum-silver electrode
pair can be used in solutions containing nitric acid but not in solutions
containing readily reduced ions, such as dichromate or ferric ion.
Anions that react with silver ion to form insoluble precipitates do not
interfere; reducing ions may interfere if they can reduce the silver
salt formed.
The titration vessel shown in Fig. 15.8 is a 4-dram perfume vial;
other small glass or plastic vessels can be used. The use of the per-
fume vial is recommended for routine analyses of radioactive samples
since it is inexpensive enough to be discarded after use, a much less
costly procedure than cleaning a more permanent vessel. A Teflon
or other fluorocarbon vessel is recommended if a permanent vessel is
required. Adsorbed radioactivity can be removed readily from Teflon
by a rinse in dilute nitric acid; whereas a prolonged treatment with
hot dichromic acid would be required to remove the same activity from
glassware. Magnetic stirring is the most convenient stirring method
since it does not require a shaft running through the top of the vessel.
Teflon, or another fluorocarbon plastic, covered stirring bars are the
most economical in the long run since they can be readily decontami-
nated. Covering the stirring motor assembly with a polyethylene bag
such as is used in food preservation will minimize the damage resulting
from a spill of solution or radioactive sample; the control can be op-
erated through the bag. Note that no ventilation of the motor or
control rheostat is possible if the bag is used; the stirrer should not be
left running when not in use, nor should the bag be used if ventilation
is required to keep the motor or rheostat cool.
The determination of acid in the presence of hydrolyzable ions sudi
as uranyl, plutonium, aluminum, iron, etc., requires the use of com-
plexing agents to hold the ion in solution. Fluoride and oxalate have
been the best agents found. I n the absence of hydrolyzable ions and
oxidizing agents such as dichromate and permanganate, the determina-
tion of acid is straightforward. Either colorimetric or potentiometric
end points can be used.
Colorimetric end points are recommended'because of their<"inherent
simplicity and ease of use. The most precise determinations are ob-
tained by having the operator pretitrate the supporting electrolyte to
an end point he can duplicate, adding the sample and titrating back
to the end point. A comparison sample made by titrating a separate
1168 ANALYSIS o r ESSENTIAL NUCLEAR REACTOR MATERIALS

sample of the electrolyte to an end point can also be used to aid in


matching end points. With a little practice, most operators can make
replicate determinations to within a few tenths of a per cent. The
choice of indicator should be made to fit the p H of the end points; it
has been found that even color-blind operators can distinguish the end
point of an indicator that goes from a light color (pink or yellow) to
a dark color (blue) at the end point. Thus thymol blue and bromo-
thyniol blue are good choices when they can be used.
Acid titrations with potentiometric end points are also feasible; a
titration assembly using a glass electrode is shown in Fig. 15.9. The
electrolysis-current field can affect the p H indication of the glass elec-
trode to a large degree, unless precautions are taken to minimize the
field about the glass electrode. A suitable artifice is to use a coil of
silver wire as the generator anode, and place the platinum wire cathode
within this coil. I t is also necessary to us a highly salted stock elec-
trolyte to minimize the solution resistance. The glass electrode and
reference electrode are thus kept out of the generator field set up by the
electrolysis current. An additional problem arises if the p H meter
used cannot be used with grounded electrodes. I n this case the gen-
erator power-supply output must be isolated from ground, and care
must be taken to avoid grounding the titration vessel. The use of a
p H meter that allows a grounded input is recommended. Generally
speaking, potentiometric end points give slower titrations than color-
imetric end points since the end point must be approached more slowly.
The silver bromide deposit on the silver electrode must be removed
periodically. A convenient reagent for this is hydriodic acid (sp. gr.,

BECKMAN - LEAD TO PLATINUM


290-7 CATHODE
GLASS ELECTRODE

- LEAD TO SILVER
ANODE

-15- TO 30-ML SOFT-


GLASS BOTTLE

-STIRRING BAR

Fig. 15.9—Potentiometric acid titration cell.


ELECTROMETRIC METHODS 1169

1.5 to 1.9). Einse the electrodes with water to remove any titration
solution and then with acetone to dry them; then immerse them in 1 to
2 ml of hydriodic acid for a few seconds. The acid can be used a num-
ber of times. Rinse the electrodes free of hydriodic acid with acetone
first, then with water. The hydriodic acid converts silver halide de-
posits to iodide complexes; these are soluble in hydriodic acid and a
number of organic solvents. Dilution with water precipitates silver
iodide.
Procedure {in Ahsence of Hydrolyzable Ions). Add 1 to 2 ml of stock
reagent soluition to the titration vessel, and titrate to an end point. Add
the sample and pipet rinses, and titrate back to the end point. Several
samples, if the volume and radioactivity level are not too large, can be
run in succession. Clean the electrode after each set of determinations.
This method can be used for 0.01 microequivalent of acid up to several
milliequivalents per sample.
The stock electrolyte is 5 per cent sodium or potassium bromide plus
10 per cent sodium sulfate for potentiometric titrations. If pretitratlon
to an end point is used, the stock solution should be made slightly acid
to allow a 20- to 30-sec pretitratlon time. The pretitration procedure
eliminates any blanks in the acid determination due to the presence of
traces of acid or alkali in the water or reagents. Standard deviart:ions
on a single sample of ±0.01 to ±0.2 per cent are obtained routinely,
using both potentiometric and colorimetric end points on 10- to 200-/il
samples.
Procedure {in Presence of Bydrolyeable Ions. Oxalate Oomplexing
Method). This procedure and its modifications have been developed by
Carson'"" and can be used for solutions containing O.OM and up of
uranium and 0.2M and up of free acid. Phosphate, permanganate,
dichromate, and aluminum Interfere. Lower acid concentrations can
be determined if a known spike of acid is added to the sample; this
technique extends the acid range to negative values up to 0.2M.* For
solutions containing at least 0.5M acid, add the sample and the pipet
rinsings to the titration vessel. Add a volume of 25 per cent potassium
oxalate solution equal to five times the product of the uranium molarity
and the sample size in microliters. Stir vigorously until a precipitate
forms; seed with uranyl oxalate crystals if necessary. Add 500 /jl of 5
per cent sodium or potassium bromide solution (to which is added bro-
mothymol blue indicator if a colorimetric end point is used). Mix ajid
then add 100 per cent isopropyl alcohol until the solution is 70 to 80 per
cent alcohol by volume. Titrate at 3 to 5 ma to the end point

•Uranium nitrate solutions at low acidities contain chain polymers of uranyl ion United
through oxygen. I.e., —O—UOr—0—UOa—. These are formed by the hydrolysis of uranyl
salts with the formation of free acid :
2U02 (N03)2-1-H20^1J205 (N03)2-f2HN0,
TJ02(N08)2-fH20-)-U2O5(N03)!r»U3O8(N0a)2-t-2HN0s
and so on. This permits the existence of the so-called "acld^deflcient" solutions in which
the stoichiometric ratio of nitrate ion to uranyl ion is less than 2 ; these solutions can be
made by dissolving uranium trioxide in uranyl nitrate solutions. The designation 0.2if
acid deficient thus means that 0.2M nitric acid must be added to give a stoichiometric
ratio of two nitrate ions per uranyl ion.
1 1 7 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

For solutions containing less than 0.5M acid, use an acid spike to bring
into the range of 0.2Jlf to 0.5M acid if necessary. Add the sample, the
spike, and the pipet rinses to the titration vessel. Add a volume of 2.5
per cent sodium citrate and IM potassium thiocyanate equal to twice the
product of the uranium molarity and the sample volume in microliters.
Stir vigorously for 1 min; then proceed as above.
The citrate and thiocyanate break up the basic uranium complexes to
simple uranyl compounds; oxalate tends to precipitate the basic com-
plexes, giving high results. The alcohol is used to precipitate neutral
oxalates and lessen the pH buffering effect of oxalate ion, thus making
the titration end point sharper. In essence, the procedure converts the
free acid to oxalic acid, which is titrated.
Single-sample standard deviations of ± 0.1 to 2 per cent are obtained
on 10-/J1 samples without spike additions. With spike additions single-
sample deviations of up to ± 7 per cent are obtained, based on the orig-
inal acid content, i.e., total acid less the spike.
Procedure {in Presence of Sydrolyga'ble Ions. Phosphate Precipita-
tion Method). This procedure has been developed by Carson^"^ and is
useful for microsamples containing IM acid and up, phosphate, and less
than 0.5M uranium. Aluminum and oxidizing agents interfere. The
sample is added to 1 to 2 ml of a pretitrated stock electrolyte composed
of O.OOIM disodium phosphate, 5 per cent sodium bromide, and 0.025 per
cent thymol bjue. The uranium precipitates as sodium uranyl phos-
phate, releasing 1 mole of acid:
Na2HP04-|-U02(N03)2-»NaU02P04-f-NaN03-|-HNOa
The titration is carried out at 3 to 10 ma to the blue-green end point. A
correction for the acid released by the uranium must be made; since the

ZERO 10,000 a
ADJUSTMENT

too D

L SN
CHART
DRIVE
.r
pH TITRATION
RECORDER TITRATE)V"5~
SWITCH T CELL

MAGNETIC
STIRRER
CONSTANT
CURRENT
SOURCE

Fig. 15.10—Acid-uranium titration apparatus.


ELECTROMETRIC METHODS 1171
14.0

13.0 -
12.0 - / —
11.0 -
10.0 — / —
f K2U40,3
9.0 — / E N D POINT —

8.0 - / —
70 -
e.o - ' —
6.0 —
yU0^(0H)2
4.0 - ^ END POINT -
3.0 - - ^ • ' ^ I N O T E N D POINT

2.0
_J
1.0 ^

TIME

Fig. 15.11—Covaometric titration of acid and uranium by base generation.

uranium is normally determined anyway, this does not necessarily make


an additional determination necessary. Large samples, in excess of 3 to
5 microequlvalents of uranium, should be avoided since the precipitate
tends to interfere with the titration. Standard deviations of a single
sample of ±0.5 to ±1.5 per cent are obtained on 10-/J1 samples; these
would be subject to an additional precision factor by whatever error is
made in correcting for the uranium content.
Procedure {in Presence of Hydrolyzable Ions. Differential Titration
of Add and Uranium). This procedure has been developed by Carson""
and is useful for samples containing 1.5M and up of acid and l.OM and
up of uranium. The titration determines both the a d d and uranium in
a 10-/il sample added to 2 ml of 5 per cent potassium bromide. Figure
15.10 shows the apparatus used. The titration is conducted at 5 to 6
ma and uses potentiometric end points determined from a plot of pH vs.
time (titrant added). The titration vessel and electrodes of Fig. 15.9
are used. A typical titration curve is shown in Fig. 15.11. The flrst
Inflection is the pH change as the acid is neutralized. The second in-
flection does not always appear; it corresponds to the formation of
UOa (OH)2 (2 moles base to 1 mole uranium). The last inflection occurs
for moles of base to moles of uranium ratio of 2.5 to 1; a yellow pre-
cipitate forms at this point. This corresponds to the formation of potas-
sium tetrauranate, i.e., K2U4O1S. The formation of dluranate or uranate
is not observed; such formations require moles of base to moles of ura-
nium ratios of 3 to 1 and 4 to 1, respectively. The addition of eomplex-
ing agents, such as fluoride or thiocyanate, and other salts (except
phosphate), such as sulfate or chloride, does not affect the stolchiom-
etry. The first uranium inflection is suppressed in solutions containing

6 9 0 - 4 5 7 O—64 75
1 1 7 2 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

fluoride, thiocyanate, acetate, and other complexing agents. Phosphate


gives a different stoichiometry, as explained above. If the phosphate
molarity is greater than the uranium molarity, all the uranium pre-
cipitates as the alkali uranyl phosphate; if it is less, all the phosphate
precipitates, and the excess uranium precipitates as the tetrauranate.
A similar titration involving aluminum can be made. In this case
the final inflection corresponds to Al2(OH)+ ; a number of inflections
are found between the free-acid one and this.
For 10-/«1 samples the single-sample standard deviation is ± 2 to 3
per cent for uranium and ± 2 to 5 per cent for free acid. Most of the
error is in the determination of the time of titration.
Procedure {Acidmetrio Titration of Phosphate). O&rson and Gile'°
determined phosphate in samples containing uranium by a modification
of the method of Helrich and Rieman.'*" In this procedure the sample
is passed through a short cation ion-exchange resin colunm (Dowex 50
or equivalent) in the acid form to remove uranium and other metals.
The eluate of mixed acids is preneutralized to a methyl red end point,
which corresponds to the neutralization of all the strong acids plus
the first hydrogen of phosphoric acid. The titration is now made at
5 to 8 ma to a thymol blue end point, which corresponds to the neutrali-
zation of the second phosphoric acid hydrogen. For 25-/J1 samples of
0.15 to 0.401^ phosphate containing 0.2M to O.SM uranium, the standard
deviation of a single sample was ± 3 to ± 5 per cent.
(2) Determination of Uranium. The coulometric determinations
of uranium are redox type titrations in which the uranium is titrated
from the U ( I V ) valence state to the U ( V I ) valence state or from the
U ( V I ) valence state to the U ( I V ) valence state. Nitrates, chromium
compounds, tungstates, and molybdates are interferences in the meth-
ods, in addition to other substances, depending upon the method
employed.
Procedure {Electrolytically Generated Ceric Ion Titration). Furman,
Bricker, and Dilts^' developed a procedure in which U(IV) is titrated
with electrolytically generated ceric ion. The titration and the reduc-
tion of the uranium are carried out under a blanket of nitrogen or car-
bon dioxide; a sulfate medium is used. The reagent-generation system
employs a two-compartment cell, with the cathode separated from the
bulk of the solution in a glass tube sealed at the bottom with a glass frit,
which serves as the connecting salt bridge. The anode is a 2- by 2-cm
piece of platinum-irldium foil. The catholyte is 12JVr sulfuric acid, and
the anolyte is the titration medium. The anolyte consists of 5 ml of 5
per cent ferric sulfate, 20 ml of saturated cerous sulfate in 3 ^ sulfuric
acid, and 5 to 10 ml of the sample and the column rinses. The medium
is pretitrated to the end point before the sample or rinses are added.
The indicator system is an amperometric system described by Cooke,
Eeilley, and Furman ^'" and consists of a saturated lead amalgam-lead
sulfate reference electrode and a platinum-wire operating electrode for
the larger uranium samples or a 1-cm square platinum-irldium foil
electrode for the smaller uranium samples. The end point is set such
that the indicator current is zero when the potential of the solution is
1.300 volts vs. the reference electrode.
ELECTROMETRIC METHODS 1173
The uranium sample in 3 ^ sulfuric acid is degassed to free it of oxygen
and is then reduced by passing it through a column of finely divided 26
per cent cadium amalgam. The reduction is quantitative to the (IV)
valence state. Iron and other reducible ions, halldes, and nitrates must
be absent. The eluate is caught in the pretitrated titration medium.
In this, the U(IV) reacts with the ferric ions present to give U(VI)
and ferrous ion.
ir*4-2H20-|-2Fe*'-*U02**-|-4H*-f2Fe**
Theferrous ion is then titrated with the generated ceric ion. Although
the oxidation of U(IV) by ferric ion is slow, the large excess of ferric
ion present makes the rate high enough to i)ermit titration at room tem-
perature. The direct oxidation of the uranium with ceric ion is too slow
to be useful in titration. The reported precision, expressed as the devia-
tion from the accepted value, for 5-mg samples was less than ±0.5 per
cent and for 25 ng samples, ± 9 per cent. A 1- to 2-/(g blank was found.
Procedure {Electrolytically Generated Bromine Titration). This
procedure was developed by Carson ^ and later modified by Carson and
Blouin"" for the titration of uranium in nitrate solutions. The titra-
tion vessel Is a special all-glass system with ports for the various
electrode assemblies, a thermocouple well, and gas and solution inlets.
The generating system is a two-compartment system. The cathode is
a short heavy-gauge platinum wire immersed in dilute sulfuric acid con-
tained in an 8-mm tube sealed at the bottom with a silica gel plug that
serves as the electrolysis circuit salt bridge. The anode is a 4- to 6-in.
length of platinum wire wound in a tight spiral about the cathode com-
partment. The indicator system is the derivative polarographlc system
described by Reilley, Cooke, and Furman; ^*' the electrodes are short
lengths of platinum wire sealed into a lead-glass tube. These electrodes
are polarized with a constant current of 1 ita obtained from a battery
and resistor current supply. The potential across the electrodes is read
using a line-operated pH meter.
The uranium sample, which may contain phosphate, sulfate, fluoride,
perchlorate, iron, oxidizing agents, or reducing agents, is pretreated by
heating it several minutes with an excess of hydrobromic acid (48 per
cent) to remove oxidizing interferences or with a mixture of acid and
free bromine to remove reducing interferences. The sample is trans-
ferred to the titration vessel and swept free of air by a continuous flow
of oxygen-free carbon dioxide or nitrogen; then 5 to 7 ml of electrolyte
are added (3Jlf HBr plus 0.02M Fe). The sample is heated to DO'C
and is reduced by the addition of a small excess of chromous chloride
solution. The excess reductant is titrated at 90°C'With electrolytically
generated bromine. The end point is a sharp increase in indicator po-
tential from below 100 mv to 300 mv or more. The uranium is titrated
to the second end point; the potential rises to 600 to 700 mv during the
titration, then falls rapidly at the end point to below 100 mv.
The direct oxidation of uranium by bromine Is slow, even at the ele-
vated temperature, and the addition of iron is required to prevent loss of
the volatile reagent. The sluggishness of the ferric-U(IV) reaction
gives a number of false end points during the titration. In automatic
titrator terminology this type of behavior is known as an anticipation
of end point. It is desirable since it prevents gross overtitration of the
1 1 7 4 ANALYSIS OF ESSEIWIAL NUCLEAR EEACTOR MATERIALS

sample by cutting off titrant addition until the previous additions of


titrant are reacted. The Indicator behavior is as expected for the revers-
ible chromous-chromic and ferrous-ferric couples and the irreversible
U(IV)-U(VI) couple.
The original procedure used a lead column described by Cooke, Hazel,
and McNabb "° for the preliminary reduction of the uranium. Hydro-
bromlc acid with iron was used in place of the hydrochloric acid called
for in the reference. The titration results using the column were satis-
factory. The change to chromous-ion reduction was made because the
lead column always produced some chromous ion when solutions contain-
ing chromium were analyzed, which required a change in the automatic
titrator to make this preliminary titration. It proved convenient to
use chromous chloride for the reduction and pretitration of all samples
analyzed.
The precision, expressed as the standard deviation of a single result,
was ±0.3 per cent for 7 mg of uranium and ± 6 per cent for 30 iig. A
blank correction was required for samples below 1 mg.
(3) Determination of Plutoniwm. The determination of plutonium
by a redox type titration is based either on the oxidation of plutonium
from the Pu(III) to the Pu(IV) valence state or by the reduction
of the Pu(VI) to the Pu(IV) valence state. The oxidation from the
Pu(IV) to the Pu(VI) valence state is difficult to accomplish quan-
titatively unless an excess of the oxidizing reagent is employed; hence
this redox reaction is not used as the basis for a titration method.
Dreeben ^^^ has described a coulometric titration of plutonium from
the (III) to the (IV) valence state with electrolytically generated
eerie ion as the oxidizing agent. Since the potential of the P u ( I I I ) -
Pu(IV) couple is close to the F e ( I I ) - F e ( I I I ) couple (about 0.70
volts), iron impurities in the sample and reagents constitute a serious
interference in methods using oxidation of Pu(III) to Pu(IV). The
reduction of Pu(VI) to Pu.(IV) is not subject to an iron interference,
although under some conditions chromium and eerie ion interfere.
Procedure (Hanford Constant-current Method). This procedure was
developed by Oarson, Vanderwater, and Gile '^ for the direct determina-
tion of plutonium nitrate samples that might contain iron, chromium,
uranium, fluoride, rare earths, and organic acids. Sulfate interferes
if chromium or cerium is present, although the direct determination is
possible with sulfate present and chromium absent if the pretreatment
step is modified. The method has been tested for 2 /ig to 10 mg of
plutonium-
The pretreatment of the sample to remove interferences and to oxidize
the plutonium to Pu(VI) is carried out in a reaction vessel attached
to the titration vessel by a length of capillary glass tubing. This tub-
ing extends as a center tube in the vessel; it is used to introduce gas for
stirring during the pretreatment and to transfer the sample to the
titration vessel. The pretreatment vessel is fitted with one side tube to
permit addition of sample and reagents and a second tube connected to
the gas exhaust scrubber. During pretreatment a gas stream is used
ELECTROMETRIC METHODS 1175
to stir the sample and reagents added to the pretreatment vessel. This
gas is vented thru the exhaust side arm along with a stream of air
drawn into the vessel through the other side arm. This air sweep is
necessary to prevent diflBculties in adjusting the stirring gas stream.
The titration vessel is all glass, with ports for the addition of electro-
lyte, generator electrodes, and indicator electrodes. Magnetic stirring
is used.
The reagent-generation system uses a divided cell in which the anode
is isolated from the titration by a silica gel salt bridge. The anolyte
is '2N sulfuric acid and the anode is a short heavy platinum-10 per cent
iridium wire. The generator cathode is a 6- to 8-in. length of platinum-
10% iridium wire wound in a coil about the anode compartment. The
two indicating electrodes are platinum-10% iridium wires sealed in a
lead-glass tube; about % in. of the length is exposed. These electrodes
are used in a derivative polarographic type end point system and are
polarized with a 0.1-/ia current.
The titration medium is O.dM ferric ammonium sulfate in 25 per cent
sulfuric-10 per cent orthophosphoric acid. To this stock solution just
before use is added 6.5 g of urea per 100 ml. This solution is pretitrated
to the end point before the sample is added. Potassium dichromate
is added if necessary to give a 50- to 100-sec blank titration. Ferrous
sulfate is used to adjust the siolution if larger blanks are found. The
urea is added to permit generation of ferrous ion in the presence of
nitrate. It acts by breaking the reaction chain found in nitric acid oxi-
dations at the nitrite stage:
( N a ) 2CO -|-2HN02-» 2N2-f COs+SHjG
In the absence of nitric oxide, nitrogen dioxide, and nitrite, cold dilute
nitric acid does not oxidize ferrous ion.
The plutonium sample is placed in the pretreatment reaction vessel,
diluted to 1 to 2 ml with perchloric acid (1-f 1), and oxidized with O.IM
potassium permanganate at 70 to 80 °C. If the sample volume is below
100 fil or below IM in nitrate, 100 /tl of 5 to 6if nitric acid is added with
the sample. The excess i)ermanganate and any manganese dioxide or
dichromate formed are removed by adding an excess of 57 per cent
formaldehyde solution and heating to 90°C. Further heating initiates
the reaction between nitric acid and the excess formaldehyde. The
sample is cooled and pulled into the pretitrated electrolyte solution
through the connecting capillary. A portion of the pretitrated electro-
lyte solution is withdrawn in a clean dry pipet first; this is used to rinse
the reaction vessel.
The excess i)ermianganate and manganese dioxide are destroyed with
hydrochloric acid if the sample contains sulfate, and no nitric acid is
added. This procedure does not reduce Pu(VI) or dichromate; if form-
aldehyde is used in the presence of sulfate, Pu(VI) is reduced along
with dichromate. The reason for this behavior is that Pu(IV) forms
a sulfate complex that increases the Pu(VI) to Pu(IV) oxidation po-
tential to about the same value as the dichromate-chromic couple of 1.3
volts. In the absence of sulfate, the potential of the Pu(VI) to Pu(IV)
couple is about 1 volt.
The indicator potential during titration rises from about 300 mv to
over 700 mv and falls sharply to below 100 mv at the end point. The
1 1 7 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

break is very sharp; a rounding of the break point is found only for
low-current generation. The polarization current is critical; above
0.1 fia. the sensitivity falls drastically. Samples containing 300 /ig or
more of uranium and less than 10 fig of plutonium require a partial
separation of the uranium, which otherwise interferes in the pretreat-
ment by blocking the reaction of nitric acid with formaldehyde. A con-
venient procedure is a coprecipitation of plutonium fluoride on
lanthanum fluoride.
The precision of a variety of sample types, expressed as the standard
deviation of a single result, was ± 3 per cent for 2-/ig samples.
(d) Controlled Electrode Potential GouLometry. The attainment
of 100 per cent current efficiency in an electrolysis can be obtained in
many titrations by using controlled electrode potential electrolyses.
This technique requires the use of a current-time integration system
that will integrate a variable input. The basic power source and
coulometer systems have been described above. Meites '^^ has described
a procedure for determining Q, the number of coulombs needed to
complete a controlled-potential electrolysis, from data obtained in the
early part of the electrolysis. The determination of Q by this method
gives good precision and accuracy and cuts down the required elec-
trolysis time by a factor of 2 to 3. Controlled-potential coulometric
procedures have been gaining in acceptance compared to constant-
current techniques as the precision and accuracy of the coulometers
and electrode controls have increased. The inherent accuracies and
precisions of the most recent apparatus are as good as the better con-
stant-current systems, and the applications of controlled-potential
coulometry should increase.
(e) Determinations of Controlled Electrode Potential Coulometry.
(1) Determination of JJraniwm.
Procedure (Simultaneous Determination of Uranium and Copper).
The original procedure of Farrar, Thomason, and Kelley^" has been
revised by Shults and Thomason "^ to allow for varying ratios of uranium
and copper in the sample. The power supply used is the one described
by Kelley, Jones, and Fisher.™ The cell is a cup that is sealed on top of
a two-way glass stopcock through which a mercury-pool cathode is sup-
plied from a reservoir or is sent to waste. The electrolysis anode is a
coil of platinum wire immersed in a tube sealed with a fine glass frit;
the anolyte is IN sulfuric acid. The reference electrode is a silver-
silver chloride-potassium chloride electrode separated by a glass-frit
bridge from the solution. The solution is stirred by a mechanical stirrer
that has a 4-cm-diameter glass disk positioned horizontally at the
mercury-electrolyte interface. A Tefion cap covers the vessel; a
nitrogen inlet, a sample port, and holes for the counter electrode (anode)
and reference electrode assemblies are provided.
Approximately 6 ml of clean mercury, 5 ml of IN sulfuric acid, and
the sample are placed in the cell. The solution is deaerated for 5 min in
a stream of nitrogen gas that has been passed through two chromous
sulfate scrubbing towers. The apparatus is adjusted so that reduction
ELECTROMETRIC METHODS 1177
at —0.3 volt vs. the reference electrode will be made. This step reduces
both copper and uranium. The titration is sitopped when the current
falls below 50 /na. The coulometer read-out voltage is then read, and the
coulometer is set to zero by shorting the capacitor. Adjustments are
made to give an oxidation at -1-0.175 volt to oxidize the copper and the
titration is continued until the current falls to 50 fta.. The difference in
the inumber of coulombs between the first and second titrations repre-
sents the uranium.
The precisions, expressed as the deviation from the standard value,
are in the range of ± 0.007 mg for 5-mg samples of uranium to ± 0.012
mg for 1.4-mg samples; the copper values are ±0.003 mg for 1-mg
samples to ± 0.004 mg for O.l-mg samples.
Procedure {Uranium in Nitrate Solution). This method was de-
veloped by Booman, Holbrook, and Rein.'" The titration is carried out
with the apparatus described by Booman,'^ which employs a controlled
cathode potential electrolysis using a mercury cathode and an electronic
coulometer. Two alternative procedures are described; one uses an
electrolyte of IM sulfuric acid and the other, an electrolyte of IM citric
acid and O.IM aluminum sulfate neutralized to pH 4.5 by potassium
hydroxide. The sample is added to 5 ml of electrolyte and deaerated
with a stream of oxygen-free nitrogen. The sulfuric acid procedure
calls for reduction at —0.25 volts vs. the reference electrode (a silver-
silver chloride electrode immersed in saturated potassium chloride).
The citrate procedure calls for a prereduction at —0.10 volts vs. the
reference for 20 min, followed by reduction at —0.60 volts for the Uran-
ium analysis.
The sulfuric acid electrolyte is used for solutions free of interferences
that contain more than 2 mg of uranium. Other samples require the use
of the citrate buffer electrolyte. Chloride, nitrate, and aluminum do not
interfere with the titration unless present in very large molar ratios
to uranium. Mercuric ion, cupric ion, ferric ion, and ceric ion can be
tolerated in small amounts. The most serious interference is from
ferric ion.
The precision, as expressed by the standard deviation of a single
result, for 75-mg samples of uranium in the sulfuric acid electrolyte is
±0.01 to 0.03 per cent; for 7.5-mg samples, it is ±0.03 per cent. In the
citrate medium, for 0.750-mg uranium samples, the precision is ±0.06
per cent; for 0.0750-mg samples, it is ±0.4 per cent, and for 0.00750-mg
samples it is ±0.2 per cent. A background correction for the residual
current found in the citrate electrolyses Is applied to the citrate
titrations.
Procedure {Prior Extraction of Uranium). The controUed-potential
coulometric method of Booman et al."* for uranium has been extended
by Booman and Holbrook "*'"^ to solutions containing large amounts of
Interferences by first extracting the uranium. The extractant is methyl-
isobutyl ketone, which extracts uranium in a single contacting from
a solution containing aluminum sulfate, ammonium hydroxide, and
tetrapropylammonium hydroxide. The exitractlon Is at least 99.8 per
cent complete. Uranium is effectively separated from all metal ions
except ruthenium and technetium. The organic extractant and the two
remaining metals are removed from the uranium by fusion with sodium
bisulfate-perchloric acid at 600° C.
1 1 7 8 ANALYSIS OP ESSENTIAL NUCLEAR REACTOR MATERIALS

For highly radioactive samples, a 0.750-ml sample is pipetted in a


shielded facility into a 15- by 150-mm test tube containing 60 ml of 2.8ilf
aluminum nitrate, l.OM ammonium hydroxide, and 0.005M tetra-
propylammonium hydroxide. The mixture Is vigorously contacted with
3.0 ml of methyllsobutyl ketone for 2 min and allowed to separate.
Then 2.5 ml of the organic phase is taken from the shielded facility,
and an exact 2.0-ml aliquot is placed in the coulometric cell and
evaporated to dryness with hot air. Fifty-five hundredths of a gram of
sodium sulfate and 0.20 ml of 72 per cent perchloric acid are added.
The electrolysis cell Is placed in a muffle furnace at less than 200° C and
heated rapidly to 600° C ; it is held there for 20 to 30 min. The fusion mix
is cooled and dissolved in 2 ml of water with gentle heating. After the
mix has cooled to room temperature, 0.50 ml of 0.251f aluminum sulfate
In 0.25^ sulfuric acid plus 4.0 ml of 1.2M potas^um citrate that has
been adjusted to pH 4.6 are added. The proper quantity of fresh
mercury Is added to the cell. Exactly 4.0 min are allowed for making
the preliminary adjustments of the cell electrodes, stirring rate, etc.
The cell is deaerated for 15 min, the sample is prereduced at —0.25
volts vs. S.C.E. for 20 min, and then the U(VI) is reduced at —0.65 volts
vs. S.C.E. for 14 min. One minute is allowed to determine the back-
ground correction. No bias has been observed In the results from im-
purities in the sample.
(2) Determination of Plutonium. This procedure was developed
by Scott i=« and is based on the titration of Pu (III) to Pu (IV). The
electronic apparatus is patterned closely to that of Booman et al.; ^^
modified slightly to allow oxidation and reduction at the working
electrode. Two different titration-cell designs are used. Both designs
employ isolated counter-electrode and reference-electrode compart-
ments. The compartments are connected with the titration compart-
ment by silica gel bridges and are filled with 1.07V sulfuric acid. The
counter electrode is a platinum-wire coil; the reference electrode is a
commercial calomel electrode. Both cells employ magnetic stirring
and have appropriate connections to allow introduction of the sample,
degassing by helium, and the use of an exhaust-gas spray trap of glass
wool to prevent plutonium-containing droplets from being exhausted
during degassing. The mercury cell employs a mercury electrode
pool; the other cell employs a platinum gauge cylinder. In both cells
the ratio of area of electrode to volume of electrolyte is kept large to
allow speedy titrations.
The titration medium used in the mercury cell is the citrate buffer
{IM citric acid plus O.IJ/ aluminum sulfate, neutralized with potas-
sium hydroxide to pH 4.5) used by Booman, Holbrook, and Eein ^^
for the titration of uranium. The titration medium in the platinum
cell is \N nitric acid or IN hydrochloric acid. When the nitric acid
medium is used, or when considerable nitrate is present, a trace of
sulfamic acid is added to prevent interference from nitrate ion.
ELECTROMETRIC METHODS 1179
Procedure {Samples Containing Primarily Plutonium). For samples
containing primarily plutonlum, the titrating medium and sample are
added to the cell and deaerated for 5 min with helium. An electrode
I)otentIal approximately 180 mv below E", the characteristic potential
of the P u ( I I I ) - P u ( I V ) couple in the electrolyte vs. the calomel ref-
erence electrode, is applied, and the prereduction electrolysis is carried
out until the current falls to the residual current level. The potential
of the working electrode Is now changed to a value 180 mv above E",
and the oxidation of Pu(III) to Pu(IV) is carried out. Ten minutes is
usually sufficient for the reaction. Additional reductions and oxidations
can be carried out on the sample if desired. It has been found that the
oxidation data for the mercury cell are more precise and accurate than
the reduction data ; the converse is true for the platinum cell. A blank
is found for the titration which is significant for low-level samples and
the most accurate work.
The characteristic potential of the plutonlum couple is found by mak-
ing the prereduction and carrying out the oxidation stepwise by increas-
ing the electrode potential by a small Increment and noting the number
of coulombs required to bring the solution to the set potential. The plot
of potential vs. coulombs gives a characteristic sigmoid curve from which
the characteristic potential Is determined graphically for the point where
the concentration of P u ( I I I ) is equal to the concentration of Pu(IV).
The potential can also be determined from the modified Nernst equation:
B'=B"-^ln^!iSII> (15.21)
ng Cpu(rv)
where E' is the observed potential, Cpnaui and CPU<IT) are the plutonlum
concentrations, and R, T, n, and % are the gas constant, absolute temper-
ature, number of electrons, and the faraday, resi)ectively. In this case
the concentration of Pu(IV) is proportional to the number of coulombs
passed, and the concentration of Pu(III) is proportional to the total
number of coulombs less the number passed at the point in question.
Thus EO' Is the potential of the midpoint of the potential-coulomb curve.
The determination of the characteristic potential is required only once
for a series of similar samples using the same titration media; also,
since the sample can be repeatedly analyzed, no sample is lost because
of the need to use it to determine the electrolysis conditions for a precise,
accurate determination.
Procedure {Irradiated Uranium Fuel Element Samples). For these
samples only the platinum cell can be used since the uranium titrates in
the citrate buffer used in the mercury cell. Five milliliters of O.IM
hydrochloric acid plus 500 /J1 of the sample containing 100 to 200 /»g per
milliliter of plutonlum are placed in the cell, and the solution is deaer-
ated 5 min with helium. The solution is prereduced at 580 mv vs. the
reference, at which potential the plutonlum is reduced to P u ( I I I ) but
F e ( I I I ) is not reduced to F e ( I I ) . The solution is now oxidized back
to Pu(IV) at 130 mv above E" and reduced at 130 mv below E". The
narrower range of potentials used prevents interferences from iron and
other materials in the sample. Even so, only a limited amount of iron
can be present.
A blank is found. This Is due in part to the residual current and Is
related to the titration medium and, in part, to the slow disproportiona-
tion of Pu(IV) to P u ( I I I ) and Pu(VI). The blank is thus partly a
1 1 8 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

function of plutonlum concentration, although In the 1 ^ acid solutions


the disproportlonatlon rate is very slow. The standard deviation of a
single result for titrations of about 10 mg of plutonlum Is ±0.05 per cent
for the mercury cell on a standard plutonlum solution made by dissolv-
ing pure Plutonium metal in hydrochloric acid. For the uranium solu-
tions at 50- to 100-/ig level, the standard deviation Is ±0.3 per cent.
The plutonlum values must be corrected for a small loss of 0.1 per cent
caused by migration Into the separated compartment and for a loss In
the deaeratlon by spray carrying some of the samples away. A further
correction based on the Nernst equation for Incompleteness of oxidation
or reduction owing to the voltage span is used. This Is about 0.2 per
cent if an electrical calibration of the instrument is used; it Is zero for
a chemical calibration.
(3) Other DeterTninations. Stromatt ®*' *^ has described the con-
troUed-potential titration of neptunium, which is similar to the titra-
tion described above for plutonlum. Shults " ' has described the con-
troUed-potential titration of europium which takes advantage of the
fact the europium has a valence of ( I I ) , in addition to the more cus-
tomary rare-earth valence of ( I I I ) . Shults^'' has also described a
method for plutonlum.
(f) Automatic Coulometric Titration Techniques. An advantage
of coulometric methods over conventional titration methods lies in
the fact that the control of the addition of the reagent in the titration
and the measurement of the amount of reagent added are essentially
the control and measurement of an electric current. Since precise
control and measurement of electric currents are quite advanced com-
pared to the precise control of the addition of small volumes of solu-
tion and the measurement of such volumes, automation of coulometric
titrations can be accomplished relatively easily. Highly developed
and reliable control circuitry and components are available to the
designer of automatic coulometric titration equipment.
However, it must be remembered that the addition of the titrant is
only one of a number of important operations required during a titra-
tion. Fully automatic titration equipment would require provision
for automatic sampling, automatic pretreatment of the sample (if
needed), automatic control of addition of the titrant, automatic meas-
urement of the amount of titrant added, and probably automatic data
reduction (computation) to give a direct read-out of the results of the
analysis for recordkeeping or for feedback into the process-control
system. With few exceptions, most "automatic titrators" perform only
a part of the titration automatically; the control of the titrant addi-
tion is often the only automatic feature.
The few fully automatic titration systems based on coulometric
techniques are continuous analyzers that continuously sample the ma-
terial being analyzed. Their output is current, but the principles
ELECTROMETRIC METHODS 1181

involved are those of coulometric techniques rather than amperometric


techniques since the total amount, rather than a relatively small por-
tion, of the sample components being analyzed are reacted. Because
of the high sensitivities possible with coulometric techniques, the anal-
ysis of minor constituents of the sample is a principal application of
these analyzers.
Although many direct coulometric titrations require controUed-
potential electrolysis procedures, the direct determination of water
can be made without resort to special power supplies. Keidell ^°®' ^®°
and others '^' *® have found it feasible to determine small amounts of
water in gases and liquids. F o r gases, a sample of the gas stream is
passed over an adsorber composed of P2O5 spread in a thin film on a
suitable electrical grid. The water is electrolyzed to hydrogen and
oxygen; the current flow is proportional to the water content of the
film, which, in turn, is generally a direct function of the sample flow
rate and the water content of the gas. F o r liquids the water is stripped
from the sample by passing a suitable stream of dry gas through the
sample; the gas is then analyzed. Presumably, water contents of
solids could be determined by appropriate gas drying of the solid.
The integrated current is an accurate measure of the water content if
the gas is allowed to stay in contact with the absorbing film until it
bas been dried to a level below the detection limit. Continuous sam-
pling offers difficulties in maintaining linear adsorption over the en-
tire concentration range.
A commercially available water analyzer, the Beckman Instruments
electrolytic hygrometer, has a full-scale range of 0 to 1000 ppm of
water vapor, with narrower ranges available down to 0 to 10 ppm.
The Consolidated Instrument Company, Inc., Titrilog is a some-
what more sophisticated analyzer that employs an electrolytically
generated reagent, bromine, to titrate sulfur-bearing gases present
as contaminants in air or other gases. A metered gas stream is passed
through 0, titration cell in which the contaminants react with free
bromine. The bromine is replaced by electrolytic generation as it is
used; the current required is thus proportional to the amount of con-
taminants in the gas stream. Since a number of the contaminants
found in air samples will be titrated, the instrument is not highly
specific for the determination of a single impurity unless the gas
stream is pretreated by passage through scrubbers that selectively
remove the interfering contaminants. With proper scrubbing, the
analyzer can analyze for single contaminants as well as for total im-
purities. The control system is designed to maintain a small zero-
point concentration of free bromine in the titration-cell electrolyte.
As the concentration of bromine is decreased by reaction with the
1 1 8 2 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

sample, the control system increases the electrolysis current to restore


the zero-point concentration of bromine. This type of control action
is called "inverse feedback" since the controlled output increases with
decrease in signal and vice versa. Through the use of a high-gain
power amplifier, the decrease in bromine concentration from the zero-
point value is kept very small over a wide range of electrolysis cur-
rent. The commercial instrument has been described by Austin,
Turner, and Percy; ^"^ the original instrument has been described by
Shaffer, Briglio, and Brockman.**^ The original work was done to
develop an analyzer for mustard gas, a war gas that contains a titrata-
ble functional group (mercaptan).
An analyzer to determine the free chlorine in water samples has
been described by Eckfeldt, Proctor, and Perley.'" The water sam-
ple is metered into a cell containing electrolytically generated ferrous
ion. The control system maintains a constant ferrous-ion content by
regulating the generation current. The use of water samples requires
the continuous addition of iron solutions to maintain the electrolyte
concentration in the titration cell; the excess electrolyte is removed
continuously. Eckfeldt "^ has also described work on a continuous
analyzer in which the electrode potential is maintained constant.
None of the above systems has been reported as being in use for
atomic energy material analysis or in atomic energy material proc-
esses. However, instruments of this type, either developed separately
or modifications of the commercial units, would appear to have useful
applications in process control and automatic analysis in the process-
ing of atomic energy materials.
The controUed-potential titrators described by Booman'^ and by
Kelley, Jones, and Fisher " are essentially automatic titrators as the
term is commonly taken. The control of the current is a function of
the state of completion of the electrolysis, which is the basic condi-
tion for automatic control of the addition of titrant. Hence con-
troUed-potential methods are inherently automatic in so far as the
titration step is concerned if the power supply is controlled automat-
ically. This latter condition applies for all the latest methods
reported.
The use of constant current in automatic titrators (limited to the
automatic addition of reagent) is well established. The key to this
type titration is the trigger circuit that shuts off the titration at the
end point.
Automatic coulometric titrators using constant current have been
described by Bett, Nock, and Morris,^^ Carson,""-1"- "^^ ^"^ Gerhardt,
Lawrence, and Parsons,'" Kelley, Stelzner, Laing, and Fisher,"*
Leisey,'" Lingane and coworkers,**-^ Malmstadt and Eoberts,^^" Par-
sons et al.,^" Stelzner, ^^' and Wise, Gillis, and Reynolds.**
ELECTROMETRIC METHODS 1183

15—2.3 Voltaminetry
(a) General Considerations. Voltammetric methods of analysis
are based on the use of electrode reaction rates as measured by the
current-voltage relations shown by the electrode during the electroly-
sis. The controlling reaction rates are the rates of mass transfer of
the reacting species by diffusion and convection. Voltammetry in-
cludes polarography, in which the electrolysis current at constant
applied electrode potential is the measure of the substance being
determined, and chronometry, in which the time required for the
electrode potential to change by a characteristic amount during an
electrolysis at constant current is the measure of the substance. Closely
related to voltammetric methods is amperometry, in which the current
at constant electrode potential is used as an indicator in titration pro-
cedures. Polarographlc and amperometric methods are differentiated
from conductivity methods by the type of current control used. In
jK)larographic and amperometric methods, the current is limited by
the rates of diffusion and convection. I n conductometric methods,
the current is limited by the rate of electromigration. Voltammetric
methods eliminate, or at least minimize, the effect of electromigration
of ions.
To date no reactor-material analyses employing chronometry, a
relatively recently developed analytical technique, have been reported.
A basic understanding of the techniques involved can be obtained from
D e l a h a y ' ' " * and Gierst.^^"
Amperometry is discussed with indicator methods. The measure-
ment of the potential of a pair of electrodes through which is passing
a constant current is also used as an indicator method and is classi-
fied as a potentiometric system by most authors, although it could be
classified logically as a voltammetric system.
(b) Polarogra'phy. (1) General Discussion. If a well-stirred
solution containing material that can react at an electrode, say ferric
ion, is electrolyzed between two large inert electrodes, the current-
voltage curve will have the form shown in Fig. 15.12. If the potential
applied to the cell is less than the decomposition voltage {VD), then
the current remains small. At higher potentials the current is given
by Ohm's law:

r
where r is the resistance of the cell. When rapid stirring and a large-
area electrode are used, the current is limited only by the resistance
of the solution. The concentration of ferric ions at the surface of the
electrode remains equal to that in the body of the solution, and the
electrode is not concentration polarized.
1 1 8 4 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

i - SLOPE » r, THE INTER-


y NAL RESISTANCE OF
ELECTROLYSIS CELL

. . ^ ^ t f S i ^ ^ DECOMPOSITION POINT

APPLIED VOLTAGE

Fig. 15.12—General electrolysis current-voltage curve.

If the working electrode is very small and if the solution is un


stirred, the voltage-current curve will have the form shown in Fig.
15.13. Increasing the applied potential decreases the concentration
of ferric ion at the working electrode until this becomes zero, i.e., all
the ferric ion reaching the electrode reacts. A further increase in
applied potential can no longer increase the current, which is now
limited by the rate at which ferric ions from the body of the solution
reach the electrode surface. The current remains constant with in-
creasing applied potential until a potential is reached which allows
another electrode reaction to take place. The current in the constant-
current region is known as the limiting current, and the electrode is
said to be concentration polarized for the electrode reaction taking
place.

SOLVENT DE-
DIFFUSION-LIMITED

L
COMPOSITION
PART OF CURVE

LIMITING DIFFUSION

APPLIED VOLTAGE

Fig. 15.13—Microelectrode current-voltage electrolysis curve.


ELECTROMETRIC METHODS 1185

If other substances that can react at the electrode are present, a


continued increase in applied potential will result in additional elec-
trode reactions. These may also give a limiting current; however, the
continued increase in applied potential will eventually reach a value
v;here the solvent will react or one of the electrodes will undergo dis-
solution. The solvent reactions and electrode-dissolution reactions
are not subject to limiting current conditions; their onset limits the
potential range that can be used in analysis.
I n aqueous solutions the applied potential can seldom exceed about
± 3 volts with respect to the hydrogen electrode before oxygen or
hydrogen evolution occurs or the electrode itself undergoes reaction.
The p H of the electrolyte, the electrode material, and the condition
of the surface of the electrode all affect the potential at which water
decomposition will occur.
The limiting current is made up of three components: the migra-
tion current, the residual current, and the diffusion current. The
migration current is made negligible by adding a large excess of a
supporting electrolyte containing ions that do not readily undergo
reaction at the electrode. Since the number of these ions is many
times larger than the number of ions that can undergo reaction, they
carry almost 100 per cent of the migration current, making the mi-
gration current due to the reacting ions negligible. The use of a
supporting electrolyte is necessary in voltammetric analysis since the
migration-current contribution is very sensitive to changes in total
ionic concentration unless this is large.
The residual current is the current flowing at the applied potential
in the absence of the desired electrode reaction. I t is due in part to
reactions occurring at lower potentials, which are due to other materi-
als present in the electrolyte. The residual current also can include
a component due to the charging of a condenser; this condenser is
formed at the electrode-solution interface and gives a charging current
Avhen the dropping-mercury electrode is used.
The diffusion current is the portion of the limiting current of great-
est interest since it is, for most substances, proportional to the con-
centration of the substance in solution. This current includes any
contribution made by convective mass transfer. This contribution
must be held to a constant fraction of the total if the relation between
diffusion current and concentration is to remain linear. The wide-
spread use of the dropping-mercury electrode is, in part,,, due to the
ease with which the convection contribution can be kept relatively
constant by operating in an unstirred solution compared with operat-
ing in a solution that requires stirring.
The diffusion current is dependent upon a number of factors, such
as the area of the electrode, the concentration of the reacting material.
1 1 8 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

ihe diffusion coefficient of the reacting material, and the number of


electrons involved in the cell reaction. For analysis purposes polaro-
graphlc methods usually hold all but the concentration factor constant.
A datum of interest in polarography is the half-wave potential,
wliich is the applied potential, corrected for solution-resistance drop,
for which the electrolysis current, corrected for the residual current,
is one-half the limiting diffusion current. For a given material and
supporting electrolyte, this potential usually is a constant and can be
used to identify the material. If the electrode reaction is thermo-
dynamically reversible, this potential can easily be related to the
standard potential of the reaction, and considerable thermodynamic
information on materials can be deduced from data on the effects of
variations of the composition of the solution on the half-wave
potential.
The science and art of polarography have been described in detail
by Kolthoff and Lingane " and by Meites.^^ A recent review by Hey-
rovsky ^' is also of general interest. These references give details of
the techniques used in polarography, and the first gives the details of
a number of applications. The place of polarography is well estab-
lished in both analytical and physical chemistry, and a large amount
of work each year is reported.
(2) Afparatus. A number of laboratory supply houses carry com-
plete lines of polarographlc equipment and accessories, which can meet
most of the needs of routine analysis and many of the needs of the
research worker. The equipment needed for many applications is
simple and inexpensive; the investigator should not feel that the
more elaborate types of equipment described in the current literature
are needed to produce useful results.
Descriptions of a number of commercially available instruments
and a number of instruments developed by workers in the field have
been given in the literature.^^' ^'' ^^ A few critical points regarding
the techniques and apparatus require some comment here, but the
details will not be discussed.
The basic polarographlc cell consists of a polarizable microelec-
trode, a vessel to hold the electrolyte, and a nonpolarizable counter
electrode. To this basic design are added, depending in large part
upon the individual investigator's tastes and preferences, extra fea-
tures intended to make the manipulations easier or to aid in obtaining
more precise results. The cell is usually thermostatted to eliminate
the changes in diffusion currents caused by temperature fluctuations.
A third electrode, usually a reference type such as a calomel, is used
to make accurate determinations of the potential of the electrolysis
electrodes. Provision for reonoving dissolved oxygen is usually re-
quired. This is conveniently done by sparging the electrolyte with a
ELECTROMETRIC METHODS 1187

stream of an oxygen-free inert gas such as hydrogen or nitrogen. The


effectiveness of the sparge gas is increased by using gas-dispersing
devices such as porous disks or cylinders of glass or ceramic. The
tank gases usually have sufficiently low oxygen content to permit
their use without further purifications, although most workers use
purification trains to assure the sparge-gas quality. The vanadous
sulfate scrubbing train of Meites and Meites ^^^ is convenient and
effective. I n this train, which can also be used with chromous ion in
place of vanadous ion, the spent reductant solution is continually
regenerated by contacting with amalgamated zinc and acid. Traces
of hydrogen will be added to the gas stream when this type of train
is used. The classic method using a tube filled with copper turnings
heated to 450 to 500°C is highly effective although somewhat incon-
venient to use intermittently. Possibly the most convenient devices
for removing oxygen are units (Englehard Mfg. Co.) which catalyze
the reaction between oxygen and hydrogen at room temperature. For
gases other than hydrogen, hydrogen in small amounts is added to
the gas before it is passed through the unit.
A number of types of microelectrodes can be used in polarography,
but only two, the dropping-mercury electrode and the rotating micro-
electrode (usually platinum), are used extensively in analysis. The
stationary microelectrode is not used extensively because it is very
sensitive to vibration, which causes changes in the convection contribu-
tion, and because the current flow depends upon the length of time
the electrolysis has been carried out as well as on the concentration
of the reacting substance. The rotating microelectrode is not as re-
producible as the dropping-mercury electrode and is used chiefly in
indicator systems rather than in direct-measurement systems.
The dropping-mercury electrode uses a glass capillary tube of very
fine bore. A length of 2 to 3 in. of this tube is connected to the end
of a tube containing a column of mercury, and the free end is dipped
into the electrolyte solution. The mercury flows through the capillary
at a rate dependent upon the diameter of the bore, the pressure of
mercury, and the interfacial tension between the mercury and the
electrolyte solution. This rate is adjusted by proper selection of pres-
sure and bore size so that the mercury forms a series of small drops of
highly reproducible size. The reproducibility of the size is important,
but even more important is the reproducibility of the electrode surface,
which is new for each drop and hence is not changed by previous
deposition of material from solution.
The advantages of the dropping-mercury electrode are:
1. Because of the high overvoltage for hydrogen-ion reduction on
clean mercury surfaces, it is possible to reduce many substances that
would theoretically be reduced only at applied potentials greater than
660-457 O — 6 4 — 7 6
1 1 8 8 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

those required for hydrogen ion or water. As a result, the determina-


tion of substances more difficult to reduce than hydrogen ion and water
can be carried out.
2. Since mercury can serve as a solvent for many metals, it is pos-
sible to determine substances such as the alkali metals compounds in
which the free metal formed upon reduction reacts with the solvent
unless it is removed from contact with the solvent.
3. This solvent action of mercury also aids in maintaining the high
overvoltage for reduction of hydrogen ion and water which would
be lost if active metals such as zinc or nickel were deposited on the
electrode surface and remained there.
4. The reproducibility of the surface characteristics of each drop is
very high compared to the reproducibility of the surface of solid
electrodes.
5. The absence of stirring minimizes the effects of changes in con-
vection rates.
These advantages explain why the dropping-mercury electrode is
the usual preference in polarographic methods.
The disadvantages of this electrode are:
1. Mercury undergoes dissolution at relatively low oxidation poten-
tials in the presence of many common anions such as the halides.
2. The overvoltage for oxidation of hydroxyl ion on mercury sur-
faces is not as high as it is on smooth platinum.
3. The periodic fluctuation in current from the dropping-mercury
electrode introduces a component in the residual current, the con-
denser or charging current, which arises from the charging of the
condenser formed by the electrode double layer. This charge, which is
lost when the drop falls, can be a significant fraction of the total
limiting current.
4. The periodic fluctuation of the current is not at a constant fre-
quency over the applied potential ranges or from electrode to electrode.
This, plus the low frequency, makes the use of simple a-c measurement
equipment unsuitable. The use of more complex a-c equipment or
filtering circuits to allow use of d-c measuring equipment is subject to
the change in apparent value of the current with the particular equip-
ment used.
A recommended electrode arrangement is shown in Fig. 15.14. The
length and bore size of the electrode capillary is selected such that a
moderate pressure (about 10 psi, or 50 cm H g ) gives a drop weighing
6 to 10 mg every 3 to 6 sec. Tubing of the proper characteristics is
commercially available as "marine barometer tubing" from the Corn-
ing Glass Works and from a number of laboratory supply houses that
furnish polarographic equipment. Two to three inches of the tubing
is customarily used; the bore should be uniform over most of this
ELECTROMETRIC METHODS 1189

DROPPING-MERCURY
ELECTRODE LEAD
TO POLAROGRAPH

MERCURY RESERVOIR
(ADJUSTABLE LEVEL)

CONVENIENT LENGTH OF
FLEXIBLE TUBING WIRED
ON TO GLASS PARTS

8-TO 10-MM-0D
GLASS STANDPIPE
60 TO 100 CM LONG

FLEXIBLE TUBING
WIRED ON
GREASELESS STOPCOCK WITH
PRESSURE ADAPTER TO HOLD
PLUG (OPTIONAL)

DROPPING-MERCURY
ELECTRODE CAPILLARY
2 TO 3 IN. LONG

Fig. 15.14—Dropping-mercury electrode arrangement.

length, and the end dipping into the solution should be cut square to
the tube. Every precaution should be taken to keep the bore of the
capillary clean and free of foreign liquid and solid matter. The tip
should be kept free of greasy deposits such as are deposited from
fingerprints. All tubing, etc., which comes into contact with the
mercury should be thoroughly cleaned of dirt and any materials such
as sulfur that can react with mercury. Tygon tubing and pure gum
rubber steamed for several hours with oil-free steam are quite suitable
for the tubing portions of the arrangement. Polyethylene and other
hard, difficultly flexible tubings, although satisfactory from the chem-
ical-resistance standpoint, are difficult to fasten securely to glassware.
If the optional stopcock is used, a greaseless type should be employed.
The storage of the electrode can be in air if the tip is protected against
fumes and dusts; alternatively, clean distilled water is satisfactory.
Mercury can be saved if the stopcock shown is closed during storage
periods; the mercury in the standpipe will flow until the pressure head
1 1 9 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

600-RPM
CONSTANT-SPEED
MOTOR

MOTOR MOUNT

•j-IN-DIA. ROD 7
FOR MOUNTING /

CONTACT-BRUSH
ASSEMBLY

CONTACT RING
ON SHAFT

STAINLESS-STEEL
SHAFT COVERED
WITH PARAFFIN

SETSCREW TO HOLD
WIRE, COVERED WITH
PARAFFIN AFTER ASSEMBLY PLATINUM WIRE

Fig. 15.15—Rotating microelectrode assembly.

no longer can oVercome the interfacial tension of the mercury drop


and water. This procedure keeps the capillary filled with mercury at
all times and prevents the entry of water into the capillary.
A simple rotating electrode is shown in Fig. 15.15. The platinum
or other metal electrode is a piece of wire secured in place by the
setscrew at the bottom of the shaft. The lower part of the assembly
is coated with paraffin wax or another low-melting, relatively hard
wax to provide insulation. The tip of the electrode is carefully
scraped clean. Connection to the shaft is via a drop of mercury at
the top of the shaft with a wire dipping into it from the power source.
Rotation is by small air or electric motors; some means of determining
the speed is needed since the observed diffusion current is quite sensi-
tive to the speed; alternatively, a synchronous motor can be used.
The lack of surface renewal during electrolysis makes the rotating
electrode difficult to reproduce from run to run; the electrode behavior
is critically dependent upon the previous treatment of the electrode.
A number of counter electrodes have been proposed for use in
polarographic cells. The major requirements are that the electrode
have a constant potential with respect to the solution during electroly-
sis and that the electrode material not materially affect the composition
ELECTROMETRIC METHODS 1191

of the electrolyte by reacting with the ions present except as planned.


An electrode area of the order of 1 sq. in. is required to prevent polari-
zation effects; if a salt bridge is used to isolate the counter electrode,
the bridge must have low electrical resistance to prevent a large I R
drop in the electrolysis circuit. The use of a salt bridge is not re-
quired when an internal pool of mercury or a large-area silver elec-
trode is used as the counter electrode since either of these electrodes
will operate at constant potential if the supporting electrolyte contains
the proper concentration of some anion that forms slightly soluble
salts. This formation of a saturated solution of the salt stabilizes the
electrode potential by maintaining a constant concentration of the
mercury or silver ion in solution; the quantity of salt required at the
start of an electrolysis can usually be formed from the metal and the
dissolved oxygen in the electrolyte. The use of these internal mercury
or silver electrodes is limited to solutions in which a stable potential
for the electrode is obtained. These are generally solutions that do
not contain components that readily attack mercury or silver or that
do not form soluble complexes of silver or mercury with small instabil-
ity constants. Complexes with large instability complexes (e.g., cya-
nide) are permissible since the potential of the electrode is stabilized
over a large fluctuation in the concentration of silver or mercury ions.
Electrode materials other than silver or mercury find only limited
use in polarographic analysis; however, in special cases one of these
electrodes might be very convenient for routine analysis.
The electrical circuits used in polarography serve two basic func-
tions : to supply the voltage that is impressed on the polarized elec-
trode and counter-electrode pair and to measure the current flowing
in the electrolysis cell which results from the impressed voltage.
Conventional circuits employ a source of direct current, such as a
battery, to supply a bridge-type voltage divider from which a se-
lected potential can be taken to serve as the polarizing voltage. The
current is measured either by meters using D'Arsonval movements
in the microampere and submicrosampere ranges or by electronic
amplifiers in recorders. I n recent years interest has been shown in the
development of more elaborate circuits that provide for the taking
of the derivative of the current-voltage curve normally obtained by
conventional circuit arrangements for the use of alternating currents
of various wave shapes impressed upon the d-c polarization voltage,
for the use of controlled potentials at the polarized electrodes, for
the u.se of controlled currents in the electrolysis, for the use of oscil-
loscopes for displaying the current-voltage cutT^es, and for the pro-
vision of automatic compensation of the residual and condenser
currents. A number of these new circuits are employed in the instru-
1 1 9 2 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

ments developed by Kelly and coworkers ^^^'i'" which have been used
for the analysis of uranium solutions.
Alkire et al.^^^ have described an automatic polarographic analyzer
for uranium in solvent-extraction process waste streams; Bertram
et al.^" have described an automatic polarographic analyzer for
process streams containing large concentrations of uranium. Michel-
son and Koyama "^ have discussed the requirements of automatic
analyzers for uranium in process waste streams.
(3) Determinations. Polarographic techniques are suitable for the
determination of most oxidizable or reducible ions in the general range
of 10"^ to 10"° M concentrations. I n many cases only a few other ions
will interfere in the polarographic determination of any particular
ion because of the inherent selectivity of the electrode process, and in
many cases interferences from an ion can be eliminated by use of the
proper supporting electrolyte and pretreatment procedure without
resort to difficult separation procedures. F o r example, traces of ni-
trite ion interfere with the polarographic determination of uranyl
ion; this interference can be removed readily by sparging the solution
with a stream of oxygen-free gas containing methyl alcohol vapor,
which reacts to form methyl nitrite, which then evaporates from the
solution. The methyl alcohol left in solution does not interfere with
the determination of uranium. Since the solution must be sparged to
remove oxygen, this offers a simple and convenient way to remove the
nitrite interference. Ferric ion interferes with the polarographic
determination of uranyl ion. The interference can be removed in acid
electrolytes by the addition of hydrazine or other reagents that re-
duce the ferric ion but not uranyl ion; the excess hydrazine or fer-
rous ion does not interfere with the subsequent analysis. I n another
example, the half-wave potential of the U ( V I ) to U ( V ) reduction
can be shifted away from the half-wave potential of the F e ( I I I ) to
F e ( I I ) reduction through the use of an aluminum sulfate-citrate
buffer solution. The choice of the proper supporting electrolyte and
pretreatment comprises a large part of the work required to develop
a polarographic analysis of an ion.
Precisions of the analyses vary from 30 to 50 per cent (uncommon)
down through 3 to 6 per cent (common) to 0.1 per cent or less (un-
common). The precision depends largely on the care taken in sam-
pling and pretreatment and on the nature of the sample itself. Al-
though the precisions obtained are generally better with solutions that
are free of interfering ions, many samples of surprising complexity can
be analyzed without difficulty with precisions in the few per cent
range.
Uranium. A great number of procedures for determining uranium
by polarographic techniques have been described. Uranium gives a
ELECTROMETRIC METHODS 1193

well-defined wave for the reduction of uranyl ion to U ( V ) in acid


solutions (see Refs. 171, 172, and 174 to 187). The limiting diffusion
currents are usually proportional to the uranium concentration in the
range 10"' to 10"° M\ the half-wave potentials remain constant in most
media over the concentration range. The range of half-wave potential
varies between 0.0 to — 0.5 volt vs. the saturated calomel electrode for
solutions in which strong complexing of the uranium is absent.
Special techniques have been used to extend the range of useful con-
centrations ; thus the use of a square-wave a-c polarograph "^ permits
determination of uranium at the 10"' M level; the catalysis of the
reduction of nitrate ion ^^" has been used to extend the useful range
with more conventional equipment to 10"^ M. Only a limited amount
of work has been done in alkaline systems.""- ^"^
Polarographic techniques are widely used for the analysis of ores
and natural waters for uranium (see Refs. 88,188,189, and 191 to 201).
Generally, if precise results are to be obtained from these samples,
some separation of the uranium from impurities is required, as well
as concentration of the uranium of the sample to a small volume. The
use of complexing reagents in the determination of uranium polaro-
graphically has been studied with varying degrees of- success (see
Refs. 188,190,200, and 202 to 208).
I n summary, the polarographic methods for the determination of
uranium are useful for a wide variety of samples. Many materials
can be analyzed quickly and easily with polarographic techniques
with adequate precisions and accuracies to fit most needs. These
methods should be the first considered for samples in which uranium
in trace to relatively large amounts is to be determined. The original
papers should be consulted for the details of the procedures and results
obtained.
Plutonium. The polarographic determination of plutonium has
not been extensively studied since radiochemical methods of great
sensitivity and simplicity are available for the determination of
plutonium in small concentrations and titration procedures have been
developed to cover the higher concentration ranges for which the radio-
chemical methods are not suited. Fomin ^^ has described the polaro-
graphic determination of plutonium by the reduction of P u ( I V ) to
P u ( I I I ) in oxalate media. Since the electrode behavior of the
P u ( I V ) - P u ( I I I ) couple is known to be reversible, there is every
reason to feel that practical polarographic methods of analysis can be
developed if a need arises.
Other Elements. The usefulness of polarographic techniques in
the analysis of low concentrations has led to many applications in the
analysis of trace constituents in a sample. Norton and co-
1 1 9 4 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

workers ^'^"-^^^ have described polarographic methods for determining


iron ( I I I ) , nickel, manganese, copper, and chromium in uranyl sulfate
solutions. Bane ^^' has described the use of polarographic techniques
for the determination of lead, cadmium, and zinc in beryllium metal.
I n addition to the above determinations, the voluminous literature on
polarography describes many other trace analyses, some of which may
be applicable to problems arising from the analysis of reactor mate-
rials. Although not directly concerned with reactor materials, the
analysis of cooling and boiler water used in reactors calls for the
determination of trace amounts of various substances; a common
deleterious impurity is oxygen, for which Carritt and Kaniwisher ^^*
have described a polarographic procedure.
15—2.4 Direct Conductometric Methods
The usefulness of direct conductometric methods is limited to a
large degree by the inherent lack of selectivity of conductance measure-
ments. This lack of selectivity arises from the nature of electrolytic
conductivity; all the ions in a solution help carry the current in pro-
portion to their transport number in the solution. I t follows that the
direct methods are limited largely to the determination of concentra-
tions of ionic solutes in solutions containing only one solute or to
the determination of the ionic solutes present as impurities in samples
in which such ionic impurities are significant. An example of the
latter is the very common use of conductivity measurements to deter-
mine the purity of water following distillation or deionization. This
is the only use of direct conductivity methods employed to any extent
in reactor-material processing.
Strictly speaking, it is desirable that no net electrode reaction occur
during the measurements, hence the use of alternating currents in
making conductivity measurements is widespread, in spite of the very
real difficulties associated with a-c measurements.
15—2.5 Dielectric-constant Measurement Methods
The dielectric-constant type of electrometric method is useful for
the determination of the composition of binary mixtures of two mate-
rials that have widely separated dielectric constants. The measure-
ment of the dielectric constant is usually based on the change in the
capacity of an air type condenser, i.e., a condenser whose normal di-
electric is air. Tuned tank circuits of high Q are used; these are
circuits in which capacitative (or inductive) reactance is many times
larger than ohmic resistance, a condition that makes the tuning of the
circuit very sharp. The circuit goes into and out of resonance at a
given frequency with a small change in the capacity of the test or tun-
ing condensers. A calibrated tuning condenser is used to compensate
for the change in the test condenser; the change can be correlated with
ELECTROMETRIC METHODS 1195

the composition of the sample through the use of an appropriate cali-


bration curve.
A typical method is the one described by Kelley et al.^^'' for the
analysis of tributyl phosphate ( T B P ) in a kerosene solvent. These
solutions are widely used in reactor-material processes for the sepa-
ration of uranium and plutonium from acid solutions. The instru-
ment used was one developed at the Oak Ridge National Laboratory
for this determination; the circuitry consists of a crystal-controlled
oscillator operating at 1000 kc loosely coupled with the high-Q tank
circuit, which is tunable with a pair of condensers. The measuring
cell is a copper box surrounding a 50-mmf air condenser; this meas-
uring cell condenser is connected to the instrument by a coaxial cable.
One tuning condenser, of 200 mmf, is used to zero the instrument
against the standard or reference material (usually the solvent), the
other condenser, of 100 mmf, is used to measure the change of capaci-
tance caused by the "sample. A vacuum-tube voltmeter is used to
detect the resonance condition.
I n use the reference material is placed in the cell, and the 100-mmf
measuring condenser set to its "zero" position. The instrument is now
tuned to resonance by the 200-mmf condenser; resonance is indicated
by a maximum deflection of the voltmeter. The sample is now placed
in the cell, and the instrument is returned to resonance by the 100-mmf
measuring condenser. The difference in dial readings of this con-
denser serves as the measure of the change of capacity in the cell; the
operator enters this difference into the calibration curve and reads off
the composition of the sample. The dial units are arbitrary.
For the T B P determination, the kerosene solvent used in making the
sample solutions is used as the reference. Since different grades of
kerosene with varying dielectric constants are on the market, it is
necessary to use the same kerosene in calibrating and zeroing the
instrument as is used in the sample. Each kerosene must bo cali-
brated separately. Calibration is performed by mixing known
amounts of the materials together and determining the dial settings
to establish the calibration curve. If no interaction between solvent
and solute occurs, the calibration curve is essentially a straight line,
provided the measuring condenser is linear.
Because of its high dielectric constant, water present as an in-
purity in the sample can give large errors. The water content of
organic samples must be stabilized before accurate results can be
obtained. Usually, it is difficult to remove the water; hence the pro-
cedure is to saturate the sample with water under prescribed condi-
tions. For the TBP-kerosene samples, this is done by contacting the
sample with an equal volume of water three times. This procedure
1 1 9 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERULS

removes any traces of acid or salts that may be in the sample. The
solutions are clarified by passing them through filter paper to remove
suspended water droplets before the measurements are made. Ob-
viously, the samples used in the calibration must be treated in the
same manner.
The agreement of the analysis of TBP-kerosene mixtures was within
±0.2 per cent of the value obtained by an alternate method based
on the determination of phosphate after destruction of the organic
matter; this latter method is considered the reference method for the
determination of T B P in organic solvents.
Some additional notes on procedure can be given. For T B P mix-
tures the temperature effect is small, but this may not always be the
case. Other polar materials, such as other phosphorus esters or
amines, can be determined through the use of the correct calibration
curve. Amines may give trouble in the water-washing step if care
is not taken to prevent the removal of amine salts by the water. I n
amine samples the washing could be made with dilute caustic, followed
by filtration of the sample through anhydrous sodium sulfate to re-
move the water and traces of caustic. Filtration through sodium sul-
fate is recommended for those systems that show marked water
solubility since the sensitivity of the method for the solute is en-
hanced by removal of the water from the solvent system.

15-3 IISDIRECT METHODS

Indirect methods of electroanalysis can be divided into two classes:


(1) those methods in which the electrode phenomena are used in such
a manner that the electric current serves as the equivalent of a chemi-
cal reagent in the analysis and (2) those methods in which the elec-
trode phenomena are used to detect changes caused by the addition
of reagents to the sample solution. Methods in the first class are
called reagent methods in this discussion; methods in the second class
are called indicator methods. A well-known example of a reagent
method is the precipitation of copper metal by electrodeposition on a
platinum electrode in the analysis of copper alloys. Although the
electrodeposition of copper was described "'' as early as 1801, the use
of the procedure in analysis ^" was not made until after 1864. An
equally well-known indicator method, the determination of the oxi-
dation-reduction potential of a solution using a platinum electrode,
was apparently first described by Bancroft "^ in 1892. The platinum
electrode is still in common use for the same purpose.
15—3.1 Reagent Methods
Ashley '^' ^^® and DeFord ^^-^^ have reviewed the literature on elec-
troanalytical methods including those in which electricity is used
ELECTROMETRIC METHODS 1197

as a reagent. A large part of the modern work is being done on con-


t rolled-potential electrolysis. The pioneer work using controlled elec-
trode electrolysis as a reagent v/as done by Haber ^^° in 1898; he de-
scribed methods for the preparation of various organic materials.
Sand ^^^ and Fischer ^^^ were the early pioneers in the application of
controUed-potential electrolysis to analysis problems. These early
methods were highly inconvenient since the operator had to control
the potential manually during the electrolysis. Interest in this type
of electrolysis lagged until the development of the modern electroni-
cally controlled equipment. A large number of equipment designs
are recorded in the literature; in addition, a number of commercial
devices are available for routine and research work.
A typical application of controlled-potential electrolysis in analysis
is given in the work of Alfonsi ^^^ on his system for the analysis of
copper alloys. The application of controlled-potential electrolysis
as a reagent method to reactor-material analyses is limited; most such
electrolyses are used in coulometric determinations. Since uranium
can be reduced to U ( I V ) or oxidized to U ( V I ) in acid solutions
without difficulty, controlled-potential systems are not needed for mak-
ing valence adjustments. Rulfs, De, and Elving ^^* and Sutton ^^^
have reported the use of electrolysis for the adjustment of the valence
of uranium prior to its determination by titration. I n other meth-
ods 226-228 electrolysis of uranium solutions prior to determination of
the uranium is used to remove impurities which are deposited on a
mercury cathode, such as iron, copper, and nickel, and which other-
wise would interfere in the determination.
Ko 229' 230 j^j^g described an electroyltic precipitation of heavy metals
as the hydrous oxides on counting planchets. The precipitates are
ignited to stable oxides prior to use in an alpha-particle energy analy-
sis. The energy analysis requires a relatively large sample to produce
good counting statistics for short counting times; the sample must
be deposited in a thin, uniform film so that the alpha-energy spectrum
of the material is not degraded by self-absorption of the alpha parti-
cles by the sample. Ko's procedure can be used for thorium, uranium,
plutonium, neptunium, americium, and curium; it was developed by
an extension of the earlier work of Miller and Brouns.^^^ Plutonium
solutions are preoxidized by an electrolytic pretreatment.2^2 "phe
hydrous oxides are deposited by the reaction of the heavy-metal ions
with electrolytically generated hydroxl ions; the planchet is used as
an anode, and hydroxyl ion formed in the electrode reaction.

2H20 + 2e-^20H- + H2
precipitates the heavy metal as an adherent film. The localized con-
centration of hydroxyl ion serves to direct the precipitation to the
1198 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

electrode rather than throughout the bulk of the solution. The anode
is depolarized during the electrolysis by oxidation of formate ion

HCOO-->CO. + H++2e
Note that one equivalent of hydrogen ion is generated for every two
equivalents of hydroxyl ion, leaving a net gain of one equivalent of
hydroxyl ion for the passage of 2 faradays of electricity through the
solution. The slow gain in hydroxyl ion aids in making the deposit
adherent and uniform. Quantitative deposition of the heavy metal
is readily obtained.
15-3.2 Indicator Methods
The use of electrometric indicator methods in analysis is well estab-
lished. The methods can be divided into three general classes: po-
tentiometric systems, in which the potential of the indicator electrodes
is measured; amperometric systems, in which the current flowing
through the electrode is measured; and conductometric systems, in
which the conductance of the titration solution is measured. Each
of the systems has particular merits; however, the potentiometric sys-
tems find the largest number of applications in routine analysis.
Historically, these are also the oldest systems; dating from Ban-
croft's work.2^^
The major advantages cited for electrometric indicator systems
compared to colorimetric indicator systems are: potentially greater
precision and sensitivity of many electrometric indicators, particularly
in dilute solutions; availability of electrometric indicator systems for
a number of titrations for which no suitable colorimetric indicator has
been found; and adaptability to automation techniques. On the other
hand, it should be noted that colorimetric indicator systems have as

Fig. 16.16—Zero-current potentiometric indicator circuit.


M. pH meter R. Reference electrode
S. Sensitive electrode C. Titration vessel
ELECTROMETRIC METHODS 1199

1 1
M R
B

E E'

— • —

— -
itzt
c
Fig. 15.17—Constant-current potentiometric indicator system.
C. Titration cell B. Battery 1 Constant-current
E, E'. Micro platinum electrodes R. Ballast resistor J source
M. pH meter

good precision and sensitivity as electrometric indicators for many


titrations and that the colorimetric titrations are, in general, per-
formed faster with less operator fatigue when such indicators can be
used. Also, most of the most commonly used titrants have suitable
colorimetric indicators systems, and several do not have satisfactory
electrometric counterparts. The investigator should include studies
on both types of indicator systems when developing a method for the
analysis of a sample.
The popularity of potentiometric indicator systems stems largely
from the availability of the modern electronic p H meter. Com-
mercial instruments of good quality and moderate costs are avail-
able. These meters have removed a large part of the drudgery
associated with the original methods of making the measurements. Al-
though the p H meter has been designed primarily for potentiometric
systems, it is equally useful in the other two classes of indicator
systems. Figures 15.16 to 15.19 give examples of circuits that can be
used to incorporate a p H meter in potentiometric, conductometric,
and amperometric indicator systems. All these circuits take advan-
tage of the fact that a p H meter is simply a voltmeter with a very
high input impedance; in use negligible current is drawn from the
input-circuit element by the meter. Miiller^* has reviewed in part
a number of these unconventional uses of the p H meter, including a
unique polarographic application by Adams, Eeilly, and Furman.^^*
A large number of automatic titrators have been made available
commercially. Several of these employ burets that are filled, zeroed,
and read after the titration by the operator; the automatic equip-
ment merely performs the titration to an end point. Other units
employ syringe type delivery units, which are filled and zeroed auto-
matically, the volume of titrant delivered being read from a counter
or other indicator attached to the syringe delivery drive. Both
1 2 0 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

CCS

Fig. 15.18—D-c conductometric indicator system


0. Titration cell Pt. Platinum probe electrodes
CCS. Constant-current source W. Tungsten working electrodes
M. pH meter

electrometric and colorimetric units are available. I t should be noted


that it is possible, with suitable auxiliary equipment, to convert any
automatic titrator that uses a p H meter or its equivalent as the input
to the control section for use with other electrometric types of end
points and for use with colorijnetric indicator systems.

Fig. 15.19—pH meter amperometric indicator system.


M. pH meter RM. Measuring resistor
C. Titration cell R. Counter electrode
RA. Adjustable resistor E. Polarized electrode
ELECTROMETRIC METHODS 1201

I n addition to the automatic coulometric titrators, the work of


Malmstadt,'-'"'' -•"- Decker and Susano,2=*' Waterbury,2='«' 239 and Wise 2*"
in the development and the use of automatic titrators for reactor-
material analyses should be mentioned.
(a) Potentiometric Sy.stenh'<. Potentiometric systems have been
discussed in detail by Bates,^ Chariot,^ Cooke,'* Ewing," Kolthoff and
Laitenin'" and Kolthoff and F u r m a n ; ^* the recent literature has
been reviewed by Furman,'**' 2" and Reilley.2^2-244 Table 15.3 is a
limited list of reactor-material and related analyses employing the
various potentiometric indicator systems.
Tlie two types of potentiometric indicator systems are the classical
zero-current type and the newer constant-current type. The zero-
current types emjjlo}' a sensitive electrode and a reference electrode.
The sensitive electrodes used include pH-sensitive electrodes, such as
tlie glass electrode, which are used in acid-base titrations; redox po-
tential-sensitive electrodes, such as gold or platinum, which are used
in redox titrations; and single-ion-sensitive electrodes, such as the
silver electrode, which are used in the precipitation or complex-ion
formation type titration.
The change in potential of the sensitive electrode with the addition
of titrant is highly nonlinear and ideally follows an equation of the
form:
A' = A'" + ^ l n / ( ( 7 , < : V , K e q ) (15.22)
where C = t h e measure of the titrant added at any stage of the
titration
^ ' r = l h e measure of the titrant for which the equivalents
of titrant added are tlie same as the equivalents of
titrated materials in tlie sample; i.e., this is the
amount of titrant required to react stoichiometri-
cally with the sample taken
K e q = t h e equilibrium constant for the titration reaction
/i'=tlie potential of the indicator electrodes at any stage
of tlie titration; it is the i)otential corresponding to
tlie addition of C measures of titrant
A'" = tlie potential of the indicator system for which
f{C, Cr,Keq) is unity
/(. %')B, and T= constants

The function /(^'.^'j',Keq) is obtained by setting up the product quo-


tient, Q, in terms of the three variables. The quantity Q is the product
of the concentrations of the products formed in the titration reac-
tion divided by the product of the concentrations of the reactants
and is similar in form to the equilibrium constant for the reaction.
For any stage of the titration, the actual concentrations must be com-
>
Table 15.3—POTENTIOMETRIC INDICATOR SYSTEMS IN REACTOR-MATERIAL ANALYSES t-l

w
Material Titration reaction Titrant Indicator type Indicator electrodes References m
o

Uranium U(IV) to U(VI) KaCraOr Zero current _. Pt vs. calomel 245-247 CD


00
U(IV) to V(VI). Ce(IV) Zero current _ Pt vs. calomel 248-260 H
UdV) to U(VI) . - Fe(III) Zero current Pt vs. calomel 251, 252
U(IV) to U(VI) Fe(CN),+5 Zero current Pt vs- calornel 253
U(IV) to U(VI) K^CT^O^ Zero current Pt vs. W 264 >
U(IV) to U(VI) Ce(IV) Zero current Au vs. Pt[Ce(IV)].. 266
U(VI) to U^Ois NaOH Zero current- Glass vs. calomel 102, 166 a
U(VI) to U(IV) CrClj Zero current- -- _ Pt vs. calomel 257-259 f
U(IV) to U(VI) Br2 Constant current Pt-Pt. .-- - - 28, 110 H
Plutonium Pu(III) to Pu(IV) Ce(IV) Zero current Pt vs. calomel 79, 113, 239, >
240, 260 w
Pu(III) to Pu(IV) . KjCrjOr Constant current Au—Au 261 >
o
Pu(VI) to Pu(IV) Fe(II) Zero current Pt vs. cfl-lornftl 238 H
O
Constant current Pt vs. Pt 121 w
PU(VI) to PU02(I03)2 IO3- 2jero current Glass vs. calomel 262
Thorium Th(IV) to Th(Mo04)2 M0O4-2 Zero current Mo vs. calomel- 263
ELECTROMETRIC METHODS 1203

puted or estimated using the equilibrium constant and sample size;


a general expression is not useful for illustration here.
The plot of C vs. E gives a sigmoid curve. The datum of interest
from the analysis standpoint is the value of GT; this is obtained from
the experimental data in a number of ways. The potential for which
G is equal to GT is known as the end-point potential; hence a deter-
mination of this potential is used to determine GT- The end-point
potential occurs at the inflection point of the G vs. E curve if the
system is behaving properly (if it does not, then the titration cannot
be performed). This inflection point can be found by inspection of
the G vs. E plot; it is taken as the center of the steepest part of the
curve. For well-defined titration curves with a very steep slope at the
end point, this procedure is satisfactory since a relatively large error
in determining the end-point potential will give only a small error
in the determination for GT- For less favorable cases in which the
curve is not symmetrical or does not have a steep slope at the end
point, plotting the derivative curve of the titration gives a less sub-
jective and perhaps a more precise determination of the end point.
The derivative curve is obtained by plotting the quotient A £ ' / A C VS.
G; where t^E is the change in potential of the indicator electrode sys-
tem which occurs with the addition of the increment of titrant AC.
The derivative curve has a cusp form; the apex of the cusp occurs at
GT- Experimentally, the precision of this method of obtaining the
end point is dependent upon the size of A6' at the end point; the
smaller the increment, the more precisely the cusp apex can be located.
A derivative titration procedure can be used. I n this type titration,
two similar sensitive electrodes are used, and the potential difference
between them is measured. The titration equipment is arranged such
that one electrode is immersed in solution containing the last increment
of titrant added and the other electrode is immersed in a small volume
of solution that does not have the last increment of titrant mixed with
it. A plot of the potentials vs. the total titrant added gives a deriva-
tive curve; often, however, plotting is not needed since the increment
giving the largest change in potential contains the end point. For
small increments, the volume of titrant u p to and including this
increment is taken as GT without serious error. During the titration
the solutions are mixed after the potentials have been read and prior
to the addition of the next increment of titrant.
Plotting the titration or derivative curves need only be done in the
vicinity of the end point. I n some very favorable cases in which the
titration curves have very steep slopes at the end point with considera-
ble change in potential, plotting the titration curve is not necessary
since the increment giving the largest change in potential can be
6«0-457 O—64^—77
1204 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

taken as the end point, provided that a truly small increment


(AC/Cr'=«0) is used.
The second derivative of the titration curve shows a discontinuity at
the end point; the sign abruptly changes from -f to — or vice versa.
Malmstadt 235.236 \y^g devised an automatic titration control circuit
based on this behavior. AVith this circuit no knowledge of the
potential of the end point is needed.
Plotting the titration or derivative curve in less favorable cases can
be avoided by titrating in small, equal increments across the end point.
The end point can be then located analytically through the use of the
following interpolation equation:

^'--^'"+2A-r/+6-)^ ^''--''^
where 6'r = the titrant measure at the end point
A = the maximum change in potential per increment of titrant
B= the change in potential for the increment added just before
.4
(7= the change in potential for the increment added just after
A
Z? = tlie measure of titrant per increment
r'B=the total measure of titrant up to the end of increment B
This equation can be used with derivative type indicator systems.
The mechanism by which gold and platinum electrodes develop
their response to redox potentials appears to involve the formation
of oxides 2"* on the surface of the electrode, although the mechanism
is far from being settled. Platinum electrodes often show poor re-
s])onse to strong reducing agents such as chromous ion since platinum
catalyzes the reduction of water or hydi'ogen ion by the reducing
agent:
Cr^' + K-^Cr-' + VzIl,

When this occurs, the platinum electrode potential will be partly due
to the redox potential of the solution and partly due to the hydrogen-
evolution reaction. In practice, the observed potentials will be too
positive (oxidizing). This trouble can be avoided through the use
of a mercury pool as the sensitive electrode since the evolution of
liydrogen on this metal has a high overvoltage.
The use of single-ion-sensitive electrodes in analysis is limited to
titrants for which an ion-electrode material pair exists. Silver is
probably the most used electrode metal of this type since silver ion
is extensively used as a titrant for substances that form insoluble
silver compounds. The precipitation titration of thorium with
ELECTROMETRIC METHODS 1205

molybdate '^'^^ has been followed using a potentiometric indicator sys-


tem composed of a molybdenum-metal-sensitive electrode and calomel
reference electrode.
The calomel electrode is the most commonly used reference electrode
in potentiometric indicator systems. The use of a silver wire as a
reference electrode is convenient if the solution contains a moderate
amount of an anion such as chloride that forms an insoluble silver
salt and if neither the titrant nor the titrated material reacts ap-
preciably with free silver or silver ion. For these cases no salt bridge
is required; this is a distinct advantage in routine titration methods.
So-called "bimetallic systems" can be devised for potentiometric
indicator systems. The most common is the tungsten electrode vs.
a platinum electrode. The tungsten electrode shows only a limited
redox response and serves as the reference electrode. Voss and
Greene ^'* describe a precise potentiometric titration of uranium using
this bimetallic system.
Another type of bimetallic system employs two sensitive electrodes,
one of which is kept immersed in the titrant during the titration;
this is connected electrically via the titrant solution in the buret tip to
the titration solution. Since the composition of the titrant does not
change, the potential of the electrode is constant, and the electrode
serves in all respects as a reference electrode. The advantage of this
technique lies in the decrease in the number of components that must
be placed in contact with the titration solution; specifically it elimi-
nates the the reference-electrode salt bridge. The automatic titration
of uranium described by Cooper 2== employs the platinum plunger of
the titrant syringe as the reference electrode.
The use of polarized electrodes in potentiometric indicator systems
was first described by Willard and Fenwick.2''° Figure 15.17 shows
the basic circuit used in this type of electrometric indicator. A pair
of small electrodes, usually of platinum or gold, is used in most cases,
although a reference electrode can be used in place of one of the metal
electrodes. Reilly, Cooke, and Furman ^""^ have described a system in
which the electrodes were polarized with a small constant current;
they called the system the "derivative polarographic system.'" Con-
siderable work has been done since on this method, which, however,
has been renamed "constant-current potentiometric indicator system"
in a more systematic classification of electrometric indicator systems.
The constant current used usually is derived from a B battery-re-
sistor combination as show in Fig. 15.17.
Figures 15.20 to 15.23 show the titration curves obtained in typical
titrations employing the constant-current potentiometric indicator
system. Figure 15.20 shows the titration curve obtained for the ti-
1 2 0 6 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

JV
TITRANT, ML

Fig. 15.20—Titration curve (constant-current potentiometric indicator system)


for titration of Fe(III) with C r ( I I ) . Titrant and sample couple are both
reversible.

tration of F e ( I I I ) with C r ( I I ) . These ions are parts of the re-


versible redox couples F e ( I I ) - F e ( I I I ) and C r ( I I ) - C r ( I I I ) , and the
curve is typical of titrations in which both the titrant and the titrated
couples are reversible. As can be seen, the curve has a form that
resembles closely the derivative of the titration curve using a zero-
current potentiometric indicator; it was this form that led to the
name "derivative polarographic system." The peak of the curve
is usually very sharp requiring only a small increase in total titrant
added to go from the beginning of the peak to the end of the peak.
This indicator system is somewhat inconvenient to use in routine
manual titrations where titrant and the titrated substance give this
type of response since it is very easy to overrun the end point and
miss the peak completely.
Figure 15.21 gives the titration curve obtained in the titration of
U ( I V ) to UO2** with C e ( I V ) . The uranium couple is nonreversible,
but the C e ( I V ) - C e ( I I I ) couple is reversible. Again the end point
is very sharp; the knuckle of the curve where the potential drops is
not observed except in dilute solutions with small increments of dilute
titrant. Figure 15.22 shows the titration curve obtained in titrating
ELECTROMETRIC METHODS 1207

TITRANT, ML

Fig. 15.21—Titration curve (constant-current potentiometric indicator system)


for titration of U(IV) to UO^
sample couple is nonreversible.

F e ( I I ) with KMnOi; here the manganese couple is not reversible.


The curve in Fig. 15.23 is one that is obtained in the titration of
PuOa*^ to P u ( I V ) with F e ( I I ) ; the plutonium couple is partially
reversible, and a marked rise in indicator potential just before the
end point is reached is observed. Bichromate behaves in a similar
manner.
Bertin,-*'" Bishop,-''^ Duyckaerts.-^''^ and (iaugin2"''' "° have reported
additional theoretical studies and practical applications of the indi-
cator system. The very high sensitivity and compactness of the
electrode system has made this system vei-y useful in microtitrations.
particularly for titrations in which the sample must be diluted exten-
sively before titration.
(b) Amperometric /Systems. These systems have been discussed
in detail by Kolthoff' and Lingane ^' and Delahay.' Laitinen,2"-2"
Reilley,2* and Stock 2'* have reviewed the recent work employing
these systems.
Amperometric systems employ electrodes that operate in the diffu-
sion-limited region of the current-voltage curve in much the same
manner as polarographic systems. Since the sensitivity of these elec-
trodes with respect to concentration is very high (10"^ to 10-^M),
1 2 0 8 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

amperometric systems are widely used in the titration of dilute solu-


tions and in the titration of small amounts of materials. Also they
are widely used in precipitation or complexing type titrations since
the conventional potentiometric systems often do not have as high a
sensitivity as that obtainable from amperometric systems. The pri-
mary requisite for an amperometric indicator system is the presence
of a material in the titrating solution that reacts at the electrode at
some impressed voltage. The titrated material or the titrant can fur-
nish the electrode-active material; in some cases a pilot ion can be
added which will give a well-defined current during the titration
until an excess of reagent is added, whereupon it is titrated.
The dropping-mercury electrode can be used in ami^erometric titra
tions, but it is not as useful as the rotating electrodes or stationary elec-
trodes in stirred solutions. Since the solution must be stirred for
each addition of titrant, the use of stationary electrodes is common;
some care must be taken to regulate the rate of stirring to obtain reli-
able indicator behavior. Stationary-electrode systems are widely
used in coulometry (see Eefs. 49, 50,75, 85,103,106,108,109, and 111),
particularly in titration with electrolytically generated halogens for
which amperometric systems have high sensitivity.

I I
C Cf
TITRANT, ML

Fig. 15.22—Titration curve (constant-current potentiometric indicator system)


for titration of Fe(III) with KMn04. Titrant couple Is nonreversible; sample
couple is reversible.
ELECTROMETRIC METHODS 1209

TITRANT, EQUIVALENTS

Fig. 15.23—Titration curve (constant-current potentiometric indicator system)


for titration of PuOf to Pu(IV) with F e ( I I ) .

Cooke, Reilley, and F u r m a n " ' have described a very sensitive


technique for obtaining an end point in low-level coulometric titra-
tions of 0.01 to 0.001 /xg of F e ( I I ) per milliliter. The platinum indi-
cator electrodes are polarized at a potential corresponding to the
zero-current potentiometric end point observed for the system in more
concentrated systems. The solution is pretitrated by electrolytic
generation of reagent until the indicator current is zero. The .sample
is added, and the electrolysis is continued until the indicator current
is again zero. As long as the potential at which zero current is
obtained is not changed going from the pretitration end point to the
titration end point, considerable variation in the potential setting can
be tolerated. This indicator system was used by Furman, Reilley, and
Cooke ^^ in the coulometric titration of uranium.
A uranium titration that utilizes amperometric end point has been
described by Kolthoff and Johnson,2^^ who employed wi-nitrophenyl-
arsonic acid as the titrant. This reagent is reduced to the hydroxyl-
amino and amino derivatives at the polarized electrode. Uranium,
thorium, and zirconium can be determined. Morachevskii and
Tserkovnitskaya -'"^ and Smit and Klinkhamer "'' have also described
the amperometric titration of uranium.
The determinatioh of thorium by titration with ethylenediamine-
tetraacetate ( E D T A ) has been reported by Flaschka and Barakat.^"
1 2 1 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

With this system a lead-EDTA complex is added to the sample and


the lead ion released is titrated with a standard E D T A solution.
The polarographic wave of the lead is followed for the indicator.
Thorium was also titrated amperometrically with molybdatp by Gor-
don and Stine.2™
Kolthoff and Sambucetti ^^° have described a rotating aluminum
electrode that offers promise in the amperometric titration of fluoride
or aluminum. Olsen and Elving 2**i have described an amperometric
titration of zirconium in the presence of fluoride ion.
The so-called "dead-stop indicator system" widely used in the ti-
tration of iodine with thiosulfate or in Karl Fischer titrations has
been renamed the "biamperometric indicator system." ^^- It will be
interesting to see whether or not this name supplants the original
name.
(c) Gonductometric Systems. Conductometric indicator systems
are employed in titrations for which a large change in ionic conduct-
ance of the solution will occur. The general form of the titration
curves are well known and require no comment here.
Several types of conductivity equipment can be used. The most
commonly used is the a-c bridge with either an audio or an electronic
null indicator. A number of commercial instruments of various de-
grees of complexity are available; precise bridges are not necessary
for titrations.
Taylor and Furman -**' have described a d-c conductivity circuit
that deserves more attention in analysis. This circuit employs a p H
meter for the detection clement; it is shown in Fig. 15.18. A con-
stant current is passed through the working electrodes (tungsten in
the reference), and the I R drop between two platinum probe elec-
trodes is measured. Since essentially no current is drawn from the
probes by the p H meter, the electric field between the working elec-
trodes remains unaltered when the measurement is made. Also, since
a constant current is used, any changes in the IR drop across the
probe electrodes is caused by a change only in R. A wide variation
in initial conductivity can be compensated for when the measurements
are made by changing I. The reading of I R can be plotted just as
well as R since I is constant. A titration curve can be obtained in
much less time than it would take to manually balance a bridge. Car-
son ^"2 ]ias determined the free nitric acid concentration of uranyl
nitrate solutions automatically using this type of indicator system.
Ten to 25 /tl of sample was added to 100 ml of water; and a slight ex-
cess of fluoride ion over the amount needed to complex the uranyl ion
was added. Tlie conductometric indicator cuiTent was adjusted to
give a small initial deflection on a recording p H meter, and the titra-
tion was made by adding standard O.IA^ sodium hydroxide solution
ELECTROMETRIC METHODS 1211

from a Gilmont mioroburot operated by a small synchronous motor.


The recorder-chart-drive and buret-drive motors were switched simul-
t aneously; the amount of reagent added was thus proportional to the
length of chart. A smooth jjeak rounded at the apex but with straight
sides was obtained, and the extrapolation to determine the end point
could be carried out without difficulty. The large volume of solution
in the titration vessel makes correction of the volume for the addition
of the titrant unnecessary. Precisions of ± 2 to 3 per cent for
10 /xl samples containing 2M uranyl nitrate and 0.2M free acid were
obtained. However, the amount of fluoride ion added in excess is
highly critical, and a knowledge of the uranium content of the sample
is required.
Recently, high-frequency systems have been developed for conducto-
metric systems. These have been discussed by Reilley in Delahay's
book.' A particular advantage of these systems is that they do not
have electrodes immersed in the electrolytic solution and thus obviate
a number of difficulties involved in the use of immersed electrodes.
The over-all response of these electrodeless systems is similar to con-
ventional conductometric systems in that the phenomena of interest
occur in regard to the solution as a whole rather than at an electrode
interface. Both the conductance of the solution and the dielectric
constant of the solution contribute to the response; it is possible to
measure the contributions separately and thus emphasize the one re-
sponse over the other. For general titration work the mixed response
i'i usually satisfactory, and a simple instrument can be used. Com-
mercial instruments are available. Indicator applications are similar
to the more conventional conductometric systems. Uranium has beeji
determined with a high-frequency conductometric indicator system
by Hara and "West ^^^ using trisodiuni ethylenediaminetetraacetate.
Trisodium citrate has been used by Bobtelsky and Simchen ^^^ for
titration of uranium and other metals using a conventional conducto-
metric indicator system. Kubota and Surak -**'' have determined
fluoride conductometrically following distillation of the fluoride from
interferences. Lanthanum ion is used as the titrant.

REFERENCES

1. R. G. Bates, tJlcctronietric pH Dvtvrminatwh, John Wiley & Sons, Inc.,


New York, 1934.
2. J. CM. Bockris, Modern Aspects of Electro<^hetnistry, Academic Press Inc.,
New York, 1954.
.J. O. Chariot, Modern Electrochemical Methods. D. Van Nostrand Co.. Inc.,
Princeton, N.J., 1958.
4. B. E. Conway, Electrochemical Data, Elsevier Press, Inc., New York, 1952.
5. W. D. Cooke, in Physical Methods in Chemical Analysis, Vol. I l l , p. 71, W. G.
Bert (Ed.), Academic Press Inc., New York, 19.56.
1212 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

6. A. J. deBethune, T. S. Licht, and N. Swendeman, J. Electrochem. Soc., 1 0 6 :


616 (1959).
7. P a u l Delahay, Neiiy Instrumental Methods in Electrochemistry, Intersclenoe
Publishers, Inc., New York, 1954.
8. M. Dole. The Glass Electrode, John Wiley & Sons, Inc., New York, 1941.
9. G. W. Evi'ing, Instrumental Method of Chemical Analysis, McGraw-Hill
Book Company, Inc., New York, 1954.
10. G. W. Ewing, /.SfA Journal, 5 (10) : 46 (1958).
11. I. Feldman, Anal. Chem., 2 8 : 1859 (1956).
12. S. Glasstone. Introduction to Electrochemistry, D. Van Nostrand Co., Inc..
Princeton. N.J., 1942.
13. H. S. H a r n e d and B. B. Owen, The Physical Chemistry of Ele'trolytic Solu-
tions, 3d ed.. Reinhold Publishing Corporation, New York, 19.58.
14. F . K. H a r r i s . Electrical Measurements. John Wiley & Sons, Inc.. New York,
19.52.
1.5. J. Heyrovsky. ^V•i(•»^e, J 3 2 : 123 (July ]t)60).
16. I. M. Kolthoff and H. A. Laitenin, pll and Electrotitrations. 2d e<l., .John
Wiley & Sons, Inc.. New York, 1941.
17. I. M. Kolthoff and J. J. Lingane, Polarography, 2d ed., Iiiterscience Pub-
lishers, Inc., New York, 1952.
18. I. M. Kolthoff and N. H. F u r m a n , Potentiometric Titrations. 3d ed., John
Wiley & Sons, Inc., New York. 1958.
19. G. N. Lewis and M. Randall, Thermodynamics and Free Energy of Chemical
Suhstances, McGraw-Hill Book Company, Inc.. New York, 1923.
20. J. J. Lingane, Elcetroanalytical Chemistry. 2d ed., Interscience Publishers.
Inc., New York, 1958.
21. Louis Meites, Polnror/raphie Techniques. Interscience Publishei's, Inc., New
York, 195.5.
22. F . E. Moore, Automatic Control, 1 3 ( 2 ) : 23 (1960).
23. H. H. Miller. ORNL Master Analytical Manual. USAEC Report TIIl-7015
(Sect. 1 ) .
24. C. N. Reilley, Ami>erometry, p. 317, in Trace Analysis, a Symix)sium on
T r a c e Analysis, J. H. Yoe and H. J. Koch ( E d s . ) . New York Academy of
Medicine. 1957.
25. E. H. Swift, Anal. Chem., 2 8 : 1804 (19.56).
26. O. J. Hills and D. J. G. Ives, Nature, 1 6 5 : .530 (1950).
27. C. K. Rule and V. K. LaMer, J. Am. Chem. Soe., 5 8 : 23;?0 (19:?6).
28. W. N. Carson, J r . . . 4 n a i . Chetn., 2 5 : 466 (19.5;^).
29. W. N. Carson. Jr., C. E. Michelson. and K. Koyama. Anal. Chem.. 2 7 : 472
(1955).
•'«). R. L. Seidel. USAEC Report KAPI^M-SMS-9:!. Sept. 10. V.r,^.
: n . R. D. Tevebaugh, USAEO Report CC~342. Nov. 15,1942.
.32. pH Scale, British S t a n d a r d 1647, British S t a n d a r d s Institution, London,
19.50.
3:5. ASTM Method E70-52T. American Society for Te-^tin;; Materials. Phila-
delphia. l!l.52.
:!4. D. A Maclnnes and M. Dole, Anal. Chem., 1 : 57 (1929).
.•^.5. W. N. Carson, Jr., and C. E. Michelson. T T S A E C Report HW-267a3. J a n . 10.
19,53.
:!6. K. J. Hnhii and K. Koyama. Ind. Eny. Chem.. 4 9 ( 1 1 ) : 6:^A (19,57).
37. C. E. Michelson and W. N. Carson. Jr.. U.S P a t e n t No. 2.8.59,164. Nov. 4.
1958.
38. R. H. Miiller. Anal. Chem.. 2 9 r 9 ) : 77A (19.57).
ELECTROMETRIC METHODS 1213

39. M. B. Jones, B. F. Rider, and H. C. Hendrickson, I'SAEC Report KAPL-1497.


19,56.
40. L. Szebell^dy and Z. Somogyi, Z. anal. Chem., 1 1 2 : 313, 323. 385, ;W1, :i95,
400 (19.38).
41. v . R. Evans and L. C. Bannister, Proe. Roy. Soc. (London). A 1 2 5 : ,S70
(1929).
42. J. J. Lingane, J. Am. Chem. Soc., 6 7 : 1916 (1945).
43. J. J. Lingane and L. A. Small. AnaJ. Chem.. 21: 1119 (1949).
44. 3.3.Ungane, Anal.Chim. Acta.11-.28S (19.54).
4.5. J. J. Lingane and A. M. Hartley. Anal. Chim. .leta, 1 1 : 475 (1954).
46. J. J. Lingane, .Anal. Chem., 2 6 : 622 (1954).
47. J. J. Lingane, Arioi. C/iewi., 2 6 : 1 0 2 1 (19.54).
48. J. J. Lingane and R. T. Iwamoto, Anal. Chim. Acta, 1 3 : 465 (1955).
49. J. J. Lingane and Fred C. Anson, .Uial. Chem.. 2 8 : 1871 (19,56).
.50. J. J. L i n g a n e a n d A . J. Bard,A»a«. r/i/wi. .Icfff, 1 6 : 2 7 1 (19.57).
.51. J. J. Lingane,.4>ia?. Cftcm., 3 0 : 1716 (195S).
,52. J. J. Lingane, Anal. Chim. Acta, 1 8 : ,349 (195S).
.53. J. J. Lingane, Anal. Chim. .ieta, 1 9 : 394 (19,58).
,54. J. J. Lingane, Anal. Chim. Acta, 2 1 : 227 (19.59).
55. N. H. F u r m a n , W. D. Cooke, and C. N. Reilley. Anal. Chem., 2 3 : 945 (19.51).
,56. N. H. F u r m a n , W. I). Cooke, and C. N. Reilley, .inal. Chem.. 2 3 : 1665 (1951).
57. N. H. F u r m a n , C. E. Bricker, and R. V. Dilts. Anal. Chem.. 2 5 : 482 (19.5.S).
,58. N. H. Fiirman, Anal. Chem., 2 6 : 84 (19,54).
.59. D. D. DeFord, .inal. Chem.. 2 6 : 135 (1954).
60. D. D. DeFord, Atuil. Chem.. 2 8 : 660 (1956).
61. D. D. DeFord and R. C. Bowers. Anal. Chem.. 3 0 : 613 (195.S).
62. D. D. DeFord, Anal. Chem., 3 2 : 31R (1960).
6.3. S. E. Q. Ashley, Anal. Chem., 2 2 : 1379 (19.50),
64. P. S. Tutundzlc, Anal. Chim. Acta, 1 8 : 60-68 (19,58).
63. J. O. A. Page and J. J. Lingane. Anal. Chim. .Icta. 1 6 : 17,5-179 (1957).
66. L. Meites, Anal. Chem., 2 7 : 1110 (19,53).
(>7. L. Meites, Anal. Chem., 2 4 ; ia57 (19.52).
68. N. Belt. W. Noch, a n d C. Morris. A nalyst. 7 9 : 607 (1954).
69. J . S. Parsons, W. Seaman, N. M. Amieh. Anal. Chem.. 2 7 : 17.54 (1955).
70. W. W. Soroka, Analoy Methods in Computations and Simulation. McGraw-
Hill Book Company, Inc., New York, 1954.
71. G. A. Philbrick, OAP/R Electronic Analoy Computers, G.A.P. Researches.
Inc., Boston. Mass.
72. G. L. Bwnuan, Anal. Chem.. 2 9 : 213 (1957).
73. M. T. Kelley, H. C. Jones, and D. J. Fisher, Anal. Chem., 3 1 : 488 (1959).
74. A. J. Bard, Anul. Chim. Acta, 2 1 : 365 (19,59).
73. W. N. Carson, Jr., Anal. Chem., 2 2 : 1 5 6 5 (19,50).
76. D. D. DeFord, C. J. Johns, and J. N. P i t t s , Anal. Chem., 2 3 : 941 (19,51),
77. D. D. DeFord and J. N. Pitts, Jr., U.S. P a t e n t No. 2,744,061,1956.
78. J. B. E h l e r s and T. W. Sease, Anal. Chem., 2 6 : 513 (1954).
79. G. E, Gerhardt, H, C. Lawrence, and J. S. Parsons, Anal. Chem., 2 7 : 1752
(1955).
80. F . A. Leisey, Anal. Chem., 2 6 : 1607 (1954).
81. D, A. Maclnnes, C. Yang, and L. A. Pray, Phys. Chem., 6 1 : 662 (1957).
82. D. J. Meier, R. J. Myers, and E. H. Swift, J. Am. Chem. Soc., 7 1 : 2340 (1949).
83. A. S. Meyer, Jr., and C. M. Boyd, Anal. Chem., 3 1 : 215 (1959).
84. J . N. P i t t s , D. D. DePord, T. W. Martin, and E. A. Schmall, Anal. Chem.,
26:628(1954).
1214 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

85. W. J. Ramsey, P. S. F a r r i n g t o n , and E. H. Swift, Anal. Chem., 2 2 : 332


(1950).
86. C. N. Reilley, W. D. Cooke, and N. H. F u r m a n , Anal. Chem., 2 3 : 1030 (1951).
87. C. N. Reilley, W. D. Cooke, and N. H. F u r m a n , Anal. Chem., 2 4 : 1044
(1952).
88. E. Bloche, P. Leveque, and H. Provisor, Bull. soc. ehim. France, 1 6 : 831
(1949).
89. L. G. Cole, M. Czuha, R. W. Mosly, and D. T. Sawyer, Anal. Chem., 3 1 :
2048 (1959).
90. E. L. Eckfeldt, W. E. Proctor, Jr., and G. A. Perley, paper presented a t 50th
Anniversary Meeting, Electrochemical Society, Philadelphia, 1952.
91. E. L. Eckfeldt, Anal. Chem., 3 1 : 1453 (1959).
92. T. S. Merritt, Jr., and E. L. Martin, Anal. Chem., 3 0 : 487 (1958).
93. P. A. Shaffer, Jr., A. Briglio, Jr., and J. A. Brockman, Jr., Anal. Chem., 2 0 :
1008 (1948).
94. R. Strommatt, USAEC Report HW-59447, Feb. 2,1959.
95. R. S t r o m m a t t , Anal. Chem., 3 2 : 134 (1960).
96. S. W. Feldberg and C. E. Bricker, Anal. Chem., 3 1 : 1852 (1959).
97. J. Epstein, H. H. Sober, and S. D. Silver, Anal. Chem., 1 9 : 675 (1947).
98. E. N. Wise, P. W. Gillis, and C. A. Reynolds, Jr., Anal. Chem., 2 5 : 1344
(1953).
99. A. B r u n s t a d , in USAEC Report TID-7516, pp. 137-160,1956.
too. W. N. Carson, Jr., and R. Ko, Anal. Chem., 2 3 : 1019 (1951).
101. W, N. Carson, Jr., and H. S. Gile, Anal. Chem., 2 7 : 122 (1955).
102. W. N. Carson, Jr., unpublished data.
103. P. S. F a r r i n g t o n and E. H. Swift, Anal. Chem., 2 2 : 889 (1950).
104. R. R. Austin, G. K. T u r n e r , and L. E. Percy, Instruments, 2 2 : ,568 (1949).
10.5. A. J. B a r d and J. J. Lingane, Anal. Chim. Acta, 2 0 : 463 (1959).
106. P . S. F a r r i n g t o n , D. J . Mayer, a n d E. H. Swift, Anal. Chem., 2 5 : 591 (19-53).
107. J. K. Lee, R. N. Adams, and C. E. Bricker, Anal. Chem., 3 0 : 240 (19.58).
108. R. J. Myers and B. H. Svpift, J. Am. Chem. Soc., 7 0 : 1047 (1948).
109. J. W. Sease, C. Niemann, and E. H. Swift, Anal. Chem., 1 9 : 197 (1947).
110. W. N. Carson, Jr., and L. T. Blouin, USAEC Report HW-32634, Aug. 2, 19.54.
111. K. Rowley and E. H. Swift, Anal. Chem., 2 6 : 373 (19,54) ; 2 7 : 818 (19,55).
112. R. V. Dilts and N. H. F u r m a n , Anal. Chem., 2 7 : 1275,1596 (1955).
113. A. B . Dreeben, USAEC R e p o r t AECD-3887, Feb. 17,1953.
114. D. G. Davis and J. J. Lingane, Anal. Chim. Acta, 1 8 : 245 (1958).
115. R. C. Sellm and J. J. Lingane, Anal. Chim. Acta, 2 1 : 536 (1959).
116. P. S. Tiitundyic and S. Niladenovia, Anal. Chim. Acta, 1 2 : 283, 390 (19,55).
117. G. M. Arcand and E. H. Swift. Anal. Chem., 2 8 : 440 (1956).
118. D. M o n n i e r a n d P. Swahlen, Helv. Chim. Acta, 3 9 : 1865 (19.56).
119. W. N. Carson, Jr., Anal. Chem., 2 5 : 1733 (1953).
120. W. D. Cooke and N. A. F u r m a n , Anal. Chem., 2 2 : 896 (1950).
121. W. N. Carson, Jr., J. W. Vanderwater, and H. S. Gile, Anal. Chem., 2 9 :
1417 (1957).
122. W. D. Shults and P. F . Thomason, USAEC Report ORNI.-1846, March 1955.
123. Kenneth W. E d w a r d s and David M. Kern, Anal. Chem., 2 8 : 1876 (1956).
124. P. A r t h u r and J . F . Donahue, Anal. Chem., 2 4 : 1612 (1952).
125. H. V. Malmstadt and C. B. Roberts, Anal. Chem., 2 7 : 741 (1955).
126. J . S. P a r s o n s a n d W. Seaman, Anal. Chem., 2 7 : 210 (1955).
127. J. H. Kennedy and J. J. Lingane, Anal. Chim. Acta, 1 8 : 240 (19.58).
128. G. M. Arcand, Anal. Chim. Acta, 1 9 : 267 (1958).
ELECTROMETRIC METHODS 1215

129. D. G. Davis and J. J. Lingane, Anal. Chem., 3 1 : 1460 (1959).


130. J. M. D u n h a m and P. S. F a r r i n g t o n , Anal. Chem., 2 8 : 1510 (1956).
131. A. J. B a r d and J. J. Lingane, Anal. Chim. Acta, 2 0 : 581 (1959).
132. A. M. H a r t l e y and J. J. Lingane, Anal. Chim. Acta, 1 3 : 103 (1955).
133. C. N. Reilley and W. W. Porterfleld, Anal. Chem., 2 8 : 443 (1956).
134. H. H. Stein, Dissertation Abstr., 16(12) : 2376 (1956).
13,5. D. D. D e F o r d and H. Horn, Anal. Chem., 2 8 : 797 (1956).
136. E. P. Przybylowicz and L. B. Rogers, Anal. Chem., 2 8 : 299 (19.56).
137. E. P. Przybylowicz, Anal. Chem., 3 0 : 65-69 (1958).
138. E. P. Przybylowicz, Anal. Chem., 3 0 : 1 0 6 4 (1958).
139. E. P. Przybylowicz, Anal. Chim. Acta, 1 8 : 596-606 (1958).
140. R. L. Kovalkowski, J. H. Kennedy, and P. S. F a r r i n g t o n , Anal. Chem., 2 6 :
626 (1954).
141. K. W. K r a m e r and R. B. Fischer, Anal. Chem., 2 6 : 415 (1954).
142. P. S. Tutundzic, I. Doroslavacki, and O. Tatic, Anal. Chim. Acta, 1 2 : 481
(1955).
143. J. W. Miller and D. I). DeFord, Anal. Chem., 3 0 : 295 (1958).
144. M. T. Kelley, R. W. Stelzner, W. R. Laing, and D. J. Fisher, Anal. Chem.,
3 1 : 2 2 0 (1959).
145. R. W. Schmid and C. W. Reilley, Anal. Chem., 2 8 : 52 (1956).
146. K. Helrich and W. Rieman, Anal. Chem., 1 9 : 651 (1947).
147. W. D. Cooke, C. N. KeUley, and N. H. F u r m a n , Anal. Chem., 2 3 : 1662
(1951).
148. C. N. Reilley, W. D. Cooke, and N. H. F u r m a n , Anal. Chem., 2 3 : 1223 (1951).
149. W. D. Cooke, F . Hazel, and W. M. McNabb, Anal. Chem., 2 2 : 654 (1950).
1.50. L. Meites, Anal. Chem., 6 1 : 128,5-1286 (19,59).
151. L. G. F a r r a r , P. F . Thomason, and M. T. Kelley, Anal. Chem., 3 0 : 1511
(1958).
152. W. D. Shults and P. F . Thomason, Anal. Chem., 3 1 : 492 (1959).
1,53. G. L. Booman, W. B. Holbrook, and J. E. Rein, Anal. Chem., 2 9 : 219 (1957) ;
and USAEC R e p o r t IDO-14369, May 1,1956.
154. G. L. Booman and W. B. Holbrook, USAEC Report IDO-14435, Apr. 8, 1958.
155. G. L. Booman and W. B. Holbrook, Anal. Chem., 3 1 : 10-16 (1959).
156. F . A. Scott and R. M. Peekema, USAEC Report HW-58491, Dec. 10, 1958;
and Proceedings of the Second International Conference on the Peaceful
Uses of Atomic Energy, Geneva, 1958. Vol. 28, p. 473, United Nations.
New York, 1959.
1.57. W. D. Shults, .inal. Chem., 3 1 : 1095 (19.59).
158. W. D. Shults, B. D. Hobbs, E. L. Blevins, and P. F . Thomason, USAEC
Report ORNL-2776, September 1959.
159. F. A. Keidel, paper presented at the I'ittsburgh Conference on Analytical
Chemistry and Spectroscopy, 1956.
160. F . A. Keidel, Anal. Chem., 3 1 : 2043 (1959).
161. W. N. Carson, Jr., Anal. Chem., 2 5 : 226 (1953).
162. W. N. Carson, Jr., Anal. Chem., 2 6 : 1673 (1954).
163. R. W. Stelzner, Methods 10030026-1, and 9003026-1, ORNL Master Analyti-
cal Manual, USAEC Report TID-7015 (Sect. 7 ) .
164. P a u l Delahay, Anal. Chem., 27: 478 (1955).
165. L. Gierst, Anal. Chim. Acta, 1 5 ( 3 ) : 262-270 (1956).
166. I. Meites and T. Meites, Anal. Chem., 2 0 : 964 (1948).
167. M. T. Kelley and H. H. Miller, Anal. Chem., 2 4 : 1 8 9 5 (1952).
168. M. T. Kelley and D. J. Fisher, Anal. Chem., 2 8 : 1 1 3 0 (1956).
169. M. T. Kelley and D. J . Fisher, Anal. Chem., 3 0 : 929 (1958).
1216 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

170. M. T. Kelley, H. C. Jones, and D. J. Fisher, Anal. Chem., 3 1 : 1475 (1959).


171. G. J. Alkire, K. Koyama, K. J. Hahn, and C. E. Michelson, Anal. Chem., 3 0 :
1912 (19,58).
172. H. W. B e r t r a m , M. W. Lerner, G. J. Petretic, E. S. Roszkowski, and C. J.
Rodden, Anal. Chem., 3 0 : 354 (19,58).
173. C. E. Michelson and K. Koyama, USAEC Report HW-42637, Apr. 24, 1956.
174. G. J. Alkire and W. N. Carson, Jr., USAEC Report HW-12183, J a n . 17, 1949.
17.5. R. M. Burd and G. W. Goward, USAEC Report WAPD-205, April 1959.
176. P . J. Elving and E. C. Olson, Anal. Chem., 2 8 : 338 (1956).
177. D. J. Fisher and P. F . Thomason, Anal. Chem., 2 8 : 1 2 8 5 (1956).
178. W. B. H a r r i s and I. M. Kolthoff, .J. Am. Chem. Soc, 6 7 : 1484 (1945).
179. W. B. H a r r i s and I. M. Kolthoff, J. Am. Chem. Soc, 6 8 : 1175 (1946).
180. W. E. H a r r i s and I. M. Kolthoff, J. Am. Chem. Soc, 6 9 : 446 (1947).
181. S. B. Kilner, USAEC Report AECD-2059,1942.
1S2. J. K. K\^ iatkowski, J. Owens, and C. Casto, USAEC Report AE('l)-:i!)1!).
J a n . 16,1945.
183. W. R. Lasko and C. P. Susano, USAEO Report AECD-4161, Feb. 1, 1946.
184. E. D. Marshall, F . S. Voss, and B. M. Baer, USAEC Reports AECD-3207
and K-,5S5(Rev), Mar. 31,1950.
185. H. II. Miller, Method Nos. 1219220-1 and 900719220-1 ORNL Master Analyt-
ical Manual, USAEC Report TID-7015 (Sect. 1 ) .
186. M. Shinagawa and T. M u r a t a , Pororoj/«ro/S, 5 ; 41 (1957).
187. H. A. W^right and F . Elliott, British Report I G O - A M / W - 9 7 , J u n e 19, 1957.
188. G. W. 0. Milner and J. H. Nunn, Anal. Chim. Acta, 2 1 : 266 (1959).
189. F . Hecht, J. Korkisch, R. Patzak, and A. T h i a r d , Mikrochim. Acta, 1 9 5 6 :
1283.
190. J a n Dolezal and J i r i Adam, Chem. listy, 4 8 : 32 (1954).
191. M . L B o r l e a , i S J e e r c a S c i . , 2 6 ( 1 0 ) : 3097 (1956).
192. V. Cirilli, Rieerea Sci., 2 7 ( 3 ) : 674 (1957).
193. N. K. F u r m a n and G. P. Haight, Jr., USAEC Report M ^ 2 4 5 , October 1947.
194. K. Krarik, Suomen Kemistilehti,B22: 1 (1956).
195. J. Korkisch, A. Thiard, and F . Hecht, Mikrochim. Acta., 1 9 5 6 : 1422.
196. J. Korkisch, F . F a r a g , and F . Hecht, Mikrochim. Acta., 1 9 5 8 : 415.
197. J. Korkisch, F . F a r a g , and F. Hecht, Z. anal. Chem., 1 8 1 : 92 (1958).
198. J. Korkisch, M. R. Zaky, and F . Hecht, Mikrochim, Acta. 1 9 5 7 : 485.
199. D. I.-Legge, Anal. Chem., 2 6 : 1617 (1954).
200. G. W. C. Milner, Anal. Chim. Acta, 2 1 : 266 (19.59).
201. Yu. V. Morachevski and A. A. Sakharov, Zhur. Anal. Khim., 1 3 : 83 (1957).
202. M. A. DeSesa, D. N. Hume, A. C. Glamm, Jr., and D. D. DeFord, Anal. Chem.,
2 5 : 9 8 3 (1953).
203. J. Hojman, V. Drazte, and A. Muk, Bull. Inst. Xuclear Sci. "Jioris Kidrich.'
Belgrade,8(3) : 23 (1958).
204. .1. Ho,iman, Hull. Inst. Nuclear Sci. •lions Kidrich," Pelgrade. 6 : 113
(1956).
205. J. A. Lewis, British Report CRL/AE-,56, March 1950.
206. J. T. P o r t e r II, USAEC Report K A P L - M - J T P - 3 , Aug. 5,19.58.
207. R. C. Probst, USAEC Report DP-236, September 1957.
208. H. I. Shalgosky, Analyst, 8 1 : 512 (1956).
209. V. V. Fomin, S. P. Vorol'ev, and M. A. Andreeva, Atomnaya Energ., 4 ; 57
(1958).
210. A. D. Horton and P. F . Thomason, USAEC Report ORNI^1887, Oct. 3, 1955.
ELECTROMETRIC METHODS 1217

211. A. D. Horton, P. F . Thomason, and M. T. Kelley, USAEC Report O R N L -


1746, Sept. 24,1954.
212. A. D. Horton a n d P. F . Thomason, USAEC Report ORNL-1754, Oct. 24, 1955.
213. R. W. Bane, Anal. Chem., 2 7 : 1022-1024 (1955).
214. D. E. C a r r i t t a n d J. W. Kaniwisher,A«aL C/iem., 3 1 : 5 (1959).
2 1 5 M. T. Kelley, P. F . Thomason, A. I. Horton, and T. L. Horton, USAEC
Report ORNL-599, 1950.
216. W. Cruikshank, Ann. Physik,!: 105 (1801).
217. W. T. Gibbs, Z. anal. Chem., 3: 327 (1864).
218. W. D. Bancroft, Z. physik. Chem., 1 0 : 387 (1892).
219. S. E. Q. Ashley, Anal. Chem., 2 4 : 91 (1952).
220. F . Haber, J. Elektrochem.,4:: 506 (1898).
221. H. J. Sand, J. Chem. Soc, 9 1 : 373 (1907).
222. A. Fischer, Z. angew. Chem., 2 0 : 1 3 4 (1907).
223. B. Alfonsi, Anal. Chim. Acta, 1 9 : 276, 389, 569 (1958) ; 2 0 : 217 (1959).
224. C. L. Rulfs, A. K. De, and P. J. Elving, Anal. Chem., 2 8 : 1139 (1956).
225. J . Sutton, Canadian Report MC-186,1945.
226. J. Gurney, T. W. Bartlett, E. D. Marshall, and R. H. Lafiferty, Jr., USAEC
Report K-1106,1954.
227. M. I. Richmond and C. J. Rodden, USAEC Report AECD-3318, Sept. 23,
1948.
228. C. L. Rulfs, A. K. De, and P. J. Elving, J. Electrochem. Soc, 1 0 4 : 80 (1957).
229. R. Ko, Nucleonics, 1 4 : (7) : 74 (1956).
230. R. Ko. Nucleonics, 1 5 ( 1 ) : 72 (1957).
231. H. W. Miller and R. J. Brouns, Anal. Chem., 2 4 : 536 (1952).
232. R. Ko, Anal. Chem., 2 8 : 274 (1956).
233. W. D. Bancroft, Z. physik. Chem., 1 0 : 387 (1892).
234. R. N. Adams, C. N. Reilley, and N. H. F u r m a n , Anal. Chem., 2 5 : 1160 (1953).
2 3 5 H. V. M a l m s t a d t and E. R. Pett, Anal. Chem., 2 6 : 1348 (1954).
236. H. V. M a l m s t a d t and E. R. Fett, Anal. Chem., 2 7 : 1957 (1955).
237. J. S. Decker and C. D. Susano, USAEC Report ORNL-2031, J a n . 26, 1956.
238. G. R. W a t e r b u r y , Anal. Chem., 3 1 : 1138 (1959).
239. G. R. W a t e r b u r y and C. F . Metz, Anal. Chem., 3 1 : 1144 (1959).
240. B. N. Wise, USAEC Report LA-1176, Sept. 11,1950.
241. N. H. F u r m a n , AM.aJ.C^em., 2 3 : 2 1 (1951).
242. C. N. Reilley, Anal. Chem., 2 8 : 671 (1956).
243. C. N. Reilley, Anal. Chem., 3 0 : 765 (1958).
244. C. N. Reilley, Anal. Chem., 3 2 : 185R (1960).
245. W. S. B a r n h a r t , E. S. Gantz, T. DeVries, and M. Mellon, USAEC Report
A-2711, Mar. 8,1946.
246. J. H. Cooper, Method Nos. 1219222 and 900719222, ORNL Master Analytical
Manual, USABC Report TID-7015 (Sect. 1 ) .
247. J. C. White, Method Nos. 1219223 and 900719223, ORNL Master Analytical
Manual, USABC Report TID-7015 (Sect. 1 ) .
248. R. B. H a h n and M. T. Kelley, USAEC Report AECD-3311, Dec. 29, 1951.
249. I. P e r m a n , " / . Stefan" Inst. Repts. (Liuhljana), 2 ( 5 ) : 27 (1955).
250. L. Silverman and M. E. Shideler, Anal. Chim. Acta, 1 5 : 181 (1956).
251. R. F . Cellini and J. A. L6pez, Anales real soc. espan. fis. y quim. (Madrid),
Ser. 3 5 2 , 3 : 1 6 3 ( 1 9 5 6 ) .
252. W. R. Grimes, USAEC Report AECD-2804, Apr. 1,1947.
253. V. Simon and E. Priplatova, Chem. listy, 5 0 ( 6 ) : 907 (1956).
254. F . S. Voss and R. E. Greene, USAEC Report AECD-4030, Aug. 25, 1953.
1 2 1 8 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS

255. J. H. Cooper, Method Nos. 1219221 and 900719221, ORNL Master Analytical
Manual, USABC Report TID-7015 (Sect. 1).
256. R. Kunin, USAEC Report A-3254, May 8,1945
257. R. Belcher and R. Goulden, Ind. Chemist, 2 7 : 157,178 (1951).
258. H. K. Bl-Shemy and S. E. Zayam, Analyst, 80(1) : 365 (1955).
259. R. H. Lafferty, Jr., and R. Winget, Jr., USAEC Report A-4018, Apr. 1, 1946.
260. H. E. Boaz, USAEC Report LA-507, May 10, 1946.
261. C. E. Pietri and J. A. Baglio, Talanta, 6:159 (1960).
262. M. E. Smith, USAEC Report LA-1864, January 1955.
263. C. V. Banks and H. Diehl, Anal. Chem., 19: 222 (1947).
264. J. K. Lee, R. N. Adams, and 0. E. Bricker, Anal. Chim. Acta, 17: 321. (1957).
265 H. H. Willard and F. Fenwick, J. Am. Chem. Soc, 44: 2516 (1922).
266. Colette Bertin, AnaJ. Chim. Acta, 5: 1 (1951).
267. E. Bishop, Michrochim. Acta, 1956, 619.
268. G. Duyckaerts, .inal. Chim. Acta, 8: 57 (1953).
269. R. Gaugin, Anal. Chem., 5: 200 (1951) ; 7 : 408 (1952).
270. R. Gaugin, Anal. Chim. Acta, 18: 29 (1958).
271. H. A. Laitinen, Anal. Chem., 2 8 : 666 (1956).
272. H. A. Laitinen, Anal. Chem., 30: 657 (1958).
273. H. A. Laitinen, Anal. Chem., 32:181R (1960).
274. J. T. Stock, Microchim J.,2: 229 (1968).
275 I. M. Kolthoff and R. A. Johnson, / . Electrochem. Soc, 98: 138 (1951).
276. Yu. V. Morachevski and I. A. Tserkovnitskaya, Zhur. Anal. Khim., 13: 337
(1958).
277. W . M . S m i t a n d J . Klinkhamer, Rec trav. chim., 7 3 : 1009 (1954).
278. H. Flaschka and M. F. Barakat, Z. anal. Chem., 156, 169, 321 (1957).
279. L. Gordon and C. R. Stine, Anal. Chem., 25:192 (1953).
280. I. M. Kolthoff and C. J. Sambucetti, J. Am. Chem. Soc, 8 1 : 1516 (1959) ;
Anal. Chim. Acta, 2 1 : 233 (1959).
281. E. C. Olson and P. J. Elving, Anal. Chem., 26: 1747 (19.54).
282. P. Delahay, G. Chariot, and H. A. Laitenen, Nomenclature and Classifi-
cation of Elcetroanalytical Methods, tentative report presented to Com-
mission on Electrochemical Data at Munich IVPAC Conference, 1959.
283. R. P. Taylor and N. H. Furman, Anal. Chem., 24: 1931 (1952).
284. R. Hara and P. W. West, Anal. Chim. Acta, 12: 285 (1955).
285. M. M. Bobtelsky and E. A. Simchen, Bull, soc chim. France, 17: 870 (19,50).
286. H. Kubota and J. G. Surak, Anal. Chem., 3 1 : 283 (1959).

Additional Reading
Freedman, R. W., Anal. Chem., 3 1 : 214 (1959).
Furman, N. H , and A. J. Fenton, Jr., Anal. Chem., 29: 1213 (1957).
Ginnochio, B. J., Method No. 1219724, ORNL Master Analytical Manual USAEC
Report TID-7015 (Sect. 1).
Laitinen, H. A., and L. C. Hall, Anal. Chem., 29: 1390,1893 (1957).
Leisey, F. A., and J. F. Grutsch, Anal. Chem., 2 8 : 1553 (1956).
Maxwell, J. A., and R. P. Graham, Chem. Revs., 4 6 : 471-498 (1950).
McEwen, D. J., and Thomas DeVries, Anal. Chem., 21:1347 (19.59).
Meites, L., and S. A. Moros, Anal. Chem., 3 1 : 23 (1959).
Metz, C. P., Anal. Chem., 29:1741 (1957).
Reilley, O. N., and W. 6. Scribner, Anal. Chem., 27:1210 (1955).
Sekarten, I., and J. Vordicek, Chem. listy, 57(4) : 513 (1953).
Shultz, W. D., P. F. Thomason, and M. T. Kelley, Anal. Chem., 2 7 : 1750 (1955).
Susano, C. D., and J. J. Decker, USAEC Report ORNL-2031, Jan. 26, 1956.

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