Professional Documents
Culture Documents
ELECTROMETRIC METHODS
By W. N. Carson, Jr.*
Hg2Cl2(.oiia)+2e^Hg(Hquid)+2C1-
Hgciiq),Hg2Cl2(aolid) I KCl(X),Hg2Cl2(8aturated) I K C 1 ( ! F )
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
890-4870-^64- -T3
1 1 4 0 ANALYSIS OF ESSENTIAL NUCLEAR REACTOR MATERIALS
nF (reduced) ^ '
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,
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
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
«=r^' it (15.6)
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
(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.
(15.11)
r2
ELECTROMETRIC METHODS 1159
ELECTROLYSIS I
D-c POWER CELL e.
SOURCE ^
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
=^-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
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)
^ = ^ (15.19)
TITRATE
OUTPUT
POWER SHUNTS
D-C VOLTAGE SUPPLY
CONTROL
ELEMENT
CONTROL VOLTAGE
AMPLIFIER REFERENCE
VW-
<2>
AMMETER
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
o
REFERENCE
VOLTAGE
COULOMETER
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
5-MM GLASS
SLEEVE HELD IN LEAD TO SILVER
PLACE WITH CLAMP- ANODE COIL
STIRRING BAR
TEFLON COVERED
MAGNETIC
STIRRER
COVERED WITH
PLASTIC BAG
- LEAD TO SILVER
ANODE
-STIRRING BAR
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
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
6 9 0 - 4 5 7 O—64 75
1 1 7 2 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
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
. . ^ ^ t f S i ^ ^ DECOMPOSITION POINT
APPLIED VOLTAGE
SOLVENT DE-
DIFFUSION-LIMITED
L
COMPOSITION
PART OF CURVE
LIMITING DIFFUSION
APPLIED VOLTAGE
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
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
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
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.
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
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
CCS
w
Material Titration reaction Titrant Indicator type Indicator electrodes References m
o
^'--^'"+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
JV
TITRANT, ML
TITRANT, ML
I I
C Cf
TITRANT, ML
TITRANT, EQUIVALENTS
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