1542

ANALYTICAL CHEMISTRY

acids, as it does in dilute aqueous solutions, that reaction could

account for the difference in the calibration line at high nitrogen
dioxide contents.
At one stage of the work the absorbances a t 1.423 microns of
about 30 samples containing up to 5% water were determined on
each of four modified Beckman DU spectrophotometers. The
variations among the instruments never exceeded 0.27, water
equivalent, and the average spread was only about 0.1% water.
Over the range of normal laboratory temperatures, the spectrophotometric determination of water in nitric acid is not significantly influenced by temperature.
Early in the work, before the techniques were precise enough
to show the nitrogen dioxide effect, the influence of dissolved nitrates of iron, nickel, and chromium was briefly investigated.
KO influence on the water determination was detected. It is
assumed, therefore, that dissolved nitrates do no more than suppress the extent of the self-dissociation of the acid.
The method has been in use in several laboratories for 2 years
or more.

assisted in developing the instrumentation and in making preliminary measurements. Twenty-three of the analyses used in
establishing the final calibration were performed by the Kava1
Air Rocket Test Station, Dover, N. J., through the courtesy of
J. D. Clark and H. G. Streim. The probable existence of the
effects of ionization equilibria was predicted to the authors by H.
E. Higbie of M. W. Kellogg Co., New York, K. Y.

ACKNOWLEDGMENT

RECEIVED
for review September 28, 1955. Accepted June 21, 1956, This
paper represents a part of the work done under Contract No. AF 18(600)-53
with the Air Research and Development Command, Wright Air Development
Center, Wright-Patterson Air Force Base, Ohio.

Ruby James made the bulk of the measurements on which this

paper is based, and most of the analyses. Walter B. Wade

LITERATURE CITED

(1) Dalmon, R., Freymann, R., Compt. rend. 211,472 (1940).

(2) Ellis, J. W., Phys. Rev. 38, 693 (1931).
(3) Gillespie, R. J . , Hughes, E. D., Ingold, C. K., J. Chem. SOC.
1950, 2552.
(4) Goulden. J. D. S., Millen, D. J.,Ibid., 2620.
(5) Ingold, C. K., hlillen, D. J., Ibid.. 2612.
(6) International Critical Tables, vol. 111, p. 133, XlcGraw-Hill,

New York. 1933.

(7) Kinsey,W. L., Ellis, J. W., Phys. Rev. 36, 603 (1930).
(8) Ibid., 51, 1074 (1937).
(9) Lynn, S., Mason, D. M., Sage, B. H., Ind. Eng. Chem. 46, 1953
(1954).

Spectrophotometric Determination of Potassium

with Sodium Tetraphenylborate
RONALD T. PFLAUM and LESTER C. HOWICK
Department o f Chemistry, State University o f lowa, lowa City, lowa

Potassium tetraphenylborate was investigated spectrophotometrically in an acetonitrile-water system. The

tetraphenylborate ion shows absorption maxima at 266
and 274 m,u, with molar absorptivities of 3225 and 2100,
respectively. Beers law is obeyed over a concentration
range from 5 X 10-6 t o 7.5 X 10-1 M . The results
obtained on the determination of potassium in selected
samples indicate the feasibility of employing the described system for such determinations. Spectrophotometric evaluations of the solubilities of tetraphenylborate salts in aqueous solutions were obtained.

Table I.

Summary of Potassium Determinations

Table 11.

ITHIX the past 5 years, sodium tetraphenylborate has

come into prominence as a precipitant for potassium.
Various methods for the determination of potassium based on
the insolubility of the potassium salt in aqueous solution and its
solubility in certain organic solvents have been advanced.
Gravimetric (2, 7 ) , titrimetric (6, 9 ) , turbidimetric (8),conductometric ( 7 ) , and voltammetric ( 1 ) methods have been proposed.
A spectrophotometric method is a logical and useful extension to
this existing list of measurements.
Tetraphenylborate salts are soluble in certain organic solvents.
Dissolution in acetonitrile leads to a solvent medium that is
especially well suited for spectrophotometric measurement.
This work is concerned primarily with an investigation of the
potassium salt in such an acetonitrile medium. I t was undertaken in order to elucidate the feasibility of a spectrophotometric
determination of potassium.
APPARATUS AND REAGENTS

All spectrophotometric measyements were made a t room

temperature (approximately 25 C.) with a Cary Model 11

Potassium, Mg.
Present
Found

Sample

Solubilities of Tetraphenylborate Salts in

Pure Water at 25 C.
Salt
4

cs

K
Rb
T1

Solubility, M X 106
Experimental
Literature
10.7
2.79
17.8
2.33
5.29

3 . 2 8 (20 C.) (4)

1 8 . 2 (IO)
4 . 4 1 (20 C.) ( 4 )
2 . 9 (5)

recording spectrophotometer, using 1-cm. matched silica cells.

A Beckman Model G pH meter was used for all pH values.
Sodium tetraphenylborate was obtained from the J. T. Baker
Chemical Co. It was used as received for all work except for
obtaining the absorption curve of the reagent. I n this case,
reagent recrystallized from an acetone-hexane mixture was used.
Crystalline salts of ammonia, cesium, potassium, rubidium, and
thallium(1) were prepared by reaction of the respective chlorides
with the reagent in aqueous solution. Recrystallization of the
precipitated material was effected from an acetonitrile-water
system.
Acetonitrile was obtained from the Matheson, Coleman & Bell
Division of the Matheson Co. Purification was effected by
treating with cold saturated potassium hydroxide, drying over

V O L U M E 28, N O . 10, O C T O B E R 1 9 5 6

1543

determination of 2 to 30 p.p.m. (5 X 10-6 t o 7.5 X 10-4M) of

potassium in the measured sample with an accuracy of & 2%.
2.c
DISCUSSION

:I
W

z
a
m
a

1s

m
U

O.!

Figure 1. Absorption spectra of tetraphenylborate

salts in acetonitrile
Curve
1
2
3
4
5

Concn.,

.%f

10-4

1.2
2.4
3.6
4.8
6.0

Salt
CS
" I

Rb
Na
K

anhydrous potassium carbonate for 24 hours, refluxing over

phosphorus pentoxide for 2 to 3 hours, then distilling from
phosphorus pentoxide in an all-glass system. The fraction
boiling a t 81-81.5' C. was used as the pure solvent.
All other chemicals used were of reagent grade quality.
SUGGESTED METHOD

After appropriate preliminary treatment of the sample to yield

an aqueous solution of potassium ion, adjust the pH of the
solution to 4.0 to 5.0 with dilute sodium hydroxide and dilute
sulfuric acid.
Prepare a stock solution of sodium tetraphenylborate by
dissolving 1.0 gram of the reagent and 0.5 gram of aluminum
chloride hexahydrate or aluminum nitrate hexahydrate in 100
ml. of water. Filter the solution to remove any turbidity that
mag develop.
Add 5 ml. of the reagent solution to 5 ml. of the sample solution
in a 15-ml. graduated centrifuge tube. Centrifuge for 3 minutes
in a high speed centrifuge and remove the supernatant liquid by
pipet. Kash the precipitate twice with 3 ml. of a cold saturated
solution of the potassium salt, again removing liquid by pipet.
A constant volume of liquid (0.5 ml.) is left with the precipitate.
Dissolve the precipitate by adding 5 ml. of a mixture of 7573
acetonitrile and 25% water. Transfer to a 25-ml. volumetric
flask, rinse the centrifuge tube with additional solvent, and dilute
the sample to 25 ml.
Prepare a blank solution by an identical procedure, using the
solvent mixture to yield the 25-ml. volume.
Measure the absorbance a t 266 mp. Determine potassium
concentration from the absorbance value and a prepared calibration curve.
RESULTS

The results obtained with this method are shown in Table I.

The values given are the average of multiple measurements on
the various samples. The analyses indicate that potassium can
be determined with an accuracy within that usually assigned to a
spectrophotometric method. The method is applicable to the

Spectrophotometric Studies. il spectrophotometric investigation of various systems was undertaken as an initial step in
this study. Absorption curves were obtained for weighed
amounts of the various pure tetraphenylborate salts dissolved
in pure acetonitrile. Curves of ammonium, cesium, potassium,
rubidium, and sodium tetraphenylborate are shown in Figure 1,
from n-hich it is evident that all of these salts have the same
absorption characteristics. I t is concluded, therefore, that the
absorption maxima of the tetraphenylborate ion occur a t 266
and 274 mp. The molar absorptivities a t these maxima are
3225 and 2100, respectively. It was found, in addition, that
identical results were obtained when technical grade solvent was
used without purification.
Solutions containing varying concentrations of the potassium
salt (5.0 X 10-6 to 7.5 X l O - * X ) were prepared and measured
in order to determine the conformance to Beer's law. It was
found that Beer's law was obeyed over the concentration range
studied. Moreover, the solutions show a high degree of stability
with no apparent changes even after 5 days.
The effect of the addition of water to acetonitrile solutions of
the salts was also investigated. Varying amounts of water were
added to constant amounts of potassium tetraphenylborate in
acetonitrile, with subsequent dilution to constant volume with
the organic solvent. Absorption curves for a series of solutions
prepared in this manner are shown in Figure 2. The curves have
been displaced vertically, inasmuch as very little change occurs
in the absorptivity of the absorbing ion. However, a loss in the
definition of the curves results from the addition of increasing
amounts of water to the system. There is no apparent change in
the shape of the absorption curve up to 40% of water by volume.
Thus, analytical measurements could be carried out in a solvent
mixture of these proportions.
Solubility Studies. A study of the solubility characteristics
of tetraphenylborate salts was carried out. The recrystallized
ammonium, cesium potassium, rubidium, sodium, and thallium
(I) salts were studied. With the exception of the sodium compound, all are insoluble in water. All dissolve in acetone, acetonitrile, dimethylformamide, and dioxane. The thallium salt is
the least soluble in these solvents. All are insoluble in benzene,
carbon tetrachloride, and chloroform.
4 study of the solubility of the salts in aqueous solution was
carried out by saturating conductivity water with the respective
salts a t 25" C. After equilibrium was attained, portions of the
solutions were analyzed for tetraphenylborate ion content by
spectrophotometric measurement a t 266 and 27-1 mp. The
results of this study are presented in Table 11. d comparison
with reported literature data indicates that solubility values
from spectrophotometric measurement are comparable to those
obtained by conductometric (IO) and radiometric measurements ( 4 ) .
Precipitation Studies. A study was carried out of the precipitation reaction of potassium and the reagent in aqueous
media, as well as the effect of pH. For these purposes a stock
solution of potassium ion, 2 X 10-2J4, was prepared by dissolving
potassium chloride in conductivity water. A stock solution 4
X 10-*M in sodium tetraphenylborate was prepared by dissolving the reagent in water. Turbidity in the solution was
removed by filtration. Portions of 5 ml. of the potassium solution were added to 5 ml. of the reagent solution. Changes in pH
were made with dilute sulfuric acid and sodium hydroxide.
It was found that quantitative precipitation of potassium
occurred in a p H range from 1 to 9. Precipitation in cold solution is recommended for the p H range from 1 to 3 in order to
prevent the decomposition of the reagent (6). The reagent shows
a high degree of stability in neutral or basic solution.

1544

ANALYTICAL CHEMISTRY
reaction are summarized in Table 111. The data were obtained
a t pH 3.0 to 4.0 for solutions 4 X 10-3JI in potassium ion and
8 X 10-3M in reagent. Diverse cations vere added as the
chloride or perchlorate salts. Sodium salts of the anions were
employed.

Table 111.
Ion
C2H802Al+++

NHI

Gal-

cs
Co++
Cut+
Fe+*'
Lit
Rlg t *

WAVE LENGTH, rnfi

Figure 2.

Effect of addition of water to potassium tetraphenylborate in acetonitrile

Curve
1
2
3
4
5

% Water
0
20
40
60
80

The insoluble potassium salt can be quantitatively separated

from the aqueous phase by filtration with a fine-porosity sinteredglass filter. Separation can also be effected by centrifugation in
a high speed centrifuge. The presence of aluminum ion in the
solution, as proposed by Kohler (6) and Findeis and De Vries
( I ) , is helpful in causing the separation of the precipitate. Aluminum ion is apparently precipitated together with the potassium
salt and is not soluble in pure acetonitrile. The mixed precipitate dissolves completely in an acetonitrile-water medium.
The effects of the presence of diverse ions on the precipitation

Amount
Permissible,
P.P.M.
2000
2000
0
2000

0
1000
1000
1000
2000
2000

Effect of Diverse Ions

Ion

++
3+
+
XO:-

Rb

SO, - X-(Br-, C1-, I - )

Amount
Permissible,
P.P.hI.
0
1000
2000
0
0
2000
0
2000
2000

Only a few ions interfere in the system. Interferences result

from the interaction of the particular ion with the reagent. Of
the ions interfering, silver, mercury(II), and thallium(1) can
readily be removed by simple preliminary treatment of the
sample. Certain of the amines and ammonia are likewise easily
removed through preliminary treatment. Cesium and rubidium
ions, although usually present only as traces in a sample, are
precipitated together with the potassium. Certain amines,
cesium, potassium, or rubidium can be quantitatively determined with sodium tetraphenylborate in the absence of the other
species.
LITERATURE CITED
(1) Findeis, A. F., De Vries, T., AXAL.CHEM.28, 209 (1956),
(2) Flaschka, H., 2. anal. Chem. 136, 99 (1952).
(3) Geilmann, W., Angew. Chem. 66,454 (1954).
(4) Geilmann, W., Gebauhr, W., 2. anal. Chem. 139, 161 (1953).
(5) Hahn, F. L., Ibid., 145, 97 (1955).
(6) Kohler, M., Ibid., 138, 9 (1953).
(7) Raff, P., Brotz, W., Ibid., 133, 241 (1951).
(8) Rubia Pacheco, J. de la, Blasco Lopez-Rubio, F., Chemist
AnaEyst 44,58 (1955).
(9) Rudorff, W., Zannier, H., 2. anal. Chem. 140, 1 (1953).
(10) Rudorff, W., Zannier, H., 2. Naturforsch. 8b, 611 (1953).
RECEIVEDfor review M a y 5 , 1956. Accepted July 18, 1956. Division of
Analytical Chemistry, 129th meeting. I C s . Dallas, Tex., April 19;1G.

Spectrochemical Analysis of Thermionic Cathode Nickel Alloys

by a Graphite-to-Metal Arcing Technique
EDWIN

K. JAYCOX A N D BETTY E. PRESCOTT

N. J.

Bell Telephone Laboratories, Inc, Murray Hill,

A technique is described for the determination of aluminum, cobalt, chromium, copper, iron, magnesium,
manganese, silicon, and titanium in thermionic cathode nickel alloys, in the general concentration range
from 0.003 to 0.2% for each element. In this procedure
10 mg. of nickel metal is placed in the crater of a graphite cup and burned to extinction in the direct current
arc. The precision is adequate for the determination
of the metals listed in the concentration ranges normally encountered in cathode nickel alloys. The speed
of the analysis is considerably increased over that of
the dry oxide powder technique.

HE chemical composition and the analysis of the nickel

alloys used for the thermionic cathodes in electron tubes has

long been of primary concern to the manufacturers of these
devices. The ease of activation, the ultimate degree of thermionic activity, and the emission life of thermionic cathodes
are markedly dependent upon trace constituents present in the
nickel base to which the alkaline earth emitter is applied. Trace
constituents, particularly magnesium, silicon, aluminum, and
titanium, react with the alkaline earth compounds (barium,
strontium, and calcium oxides) of the coating to produce free
alkaline earth metal thought to be essential for high thermionic
activity. Other elements such as iron and manganese may