INDUSTRIAL AND ENGINEERING CHEMISTRY

264
Table

111.

Precipitant
for Iron

Adsorption of Cobalt b y Iron Precipitates

Cobalt Present

Cobalt Found

Loss
70 of

t o l d cobalt

Ammonia
Zinc oxide
Sodium phosphate

184.0
47.2
184.0

61.2
40.8
182.2

66.74
13.56
0.98

not be separated aa the phosphate, since the pH of the precipitation, 6.3, is higher than that of cobalt, 5.3.
Few elements interfere with the determination of cobalt by CYnitroso-@-naphthol after the phosphate separation. Copper,
palladium and ferric salts are precipitated completely with the
cobalt, wdle silver, chromium, vanadium, uranium, and bismuth
are precipitated but not quantitatively. The more common elements which are likely to interfere are either removed with the
hydrogen sulfide group or as phosphate with the iron, except
chromium and vanadium. These two elements may be eliminated by a sodium hydroxide separation. Zinc, manganese, and
nickel do not interfere. If there are large quantities of other
elements present, however, the voluminous precipitate of cobalt
is apt to adsorb other ions, and it is then advisable tg carry out
this precipitation twice.
The ions of some metals will interfere with the electrolysis of
cobalt either by depositing with it or by precipitating as hydroxides or phosphates which retain cobalt. Unless zinc has previously been completely separated it will form complex cations in
excess ammonia and be deposited with the cobalt. Nickel will
also be deposited with the cobalt and may be determined by dissolving the cathode deposit in nitric acid and separating with
dimethylglyoxime in the usual manner. If a large excess of
phosphate has been used in precipitating iron, calcium, strontium, and magnesium will be precipitated in the ammoniacal
electrolytic solution and may occlude some cobalt. If a large
quantity of calcium is present it may be precipitated as the oxalate after the phosphate separation. If much magnesium is present an excess of phosphate must be rigorously avoided. Chromium will be precipitated as the hydroxide in the ammoniacal
electrolytic solution. Since this precipitate may occlude some
cobalt, the chromium should be previously separated with sodium
hydroxide and sodium peroxide. If large quantities of manga-

Vol. 18, No. 4

nese are present they may be removed by initial treatment with

nitric acid and potassium chlorate, or the separation of cobalt and
manganese phosphates can be carried out in the presence of
ammonium citrate ( I ) . When small quantities of manganese
are fully oxidized and the electrolysis is not unduly prolonged
after deposition of all the cobalt, manganese will not deposit on
tlfe cathode, provided also that the concentration of ammonia
in the electrolytic solution is kept high. Vanadium forms 9
complex with cobalt in the ammoniacal electrolytic solution and
it is then impossible to deposit any of the cobalt on the cathode.
Vanadium should be previously separated with sodium hydroxide
and sodium peroxide.
C O M P A R A T I V E RETENTIVE POWERS OF I R O N PRECIPITATES

Iron was separated from cobalt in various samples by the

method of precipitation in a liter flask and decantation. The
precipitants used were ammonia, zinc oxide, and sodium phosphate solution. The amount of iron present varied from 0.4 to
0.5 gram. The results are given in Table 111.
Many analytical texts recommend the separation of iron from
cobalt by the addition of zinc oxide to a volumetric flask containing the solution of the sample, followed by the withdrawal
of an aliquot portion of the supernatant liquid for the determination of cobalt. Table I11 indicates that this practice may be
unsatisfactory even for routine work. On the other hand, sodium
phosphate can be used for all routine work in this manner, since
the adsorptive power of ferric phosphate for cobalt is shown in
Table I11 to be very low.
LITERATURE CITED
(1 Fairchild, J. G., IND.ENG.CHEM.,ANAL.ED.,11,326-7 (1939).
(2) Ibid., 13, 83 (1941).
(3) Korth, V., and Wells, R. C., Ibid., 14, 859-60 (1942).
(4) Noyes, A . R., and Bray, W. C., System of Qualitative Analysis
for the Rare Elements, p. 389, New York, Macmillan Co I
1927.

(5) Scott, UT.

W., and Furman, N. H., Standard Methods of Cherni.
os1 Analysis, Vol. 1, p. 315, New York, D. Van Nostrsnd Co ,
1939.

Colorimetric Determination of Cobalt with

Ammonium Thiocyanate
R. S. YOUNG

AND

A. J. HALL, Central

A rapid and accurate colorimetric method is given whereby cobalt

may be determined in the presence of other common ions. This
method can bo extremely valuable in the laboratories of mining and
metallurgical indurtries where routine determinations of cobalt are
carried out. The useful range for this procedure lies within the
limits 0.01 to 4.0% cobalt.

THE

alkali thiocyanates have been used by many workers to

detect the presence of small quantities of cobalt. Potassium and ammonium thiocyanates form complexes with cobalt
which are represented by the formulas K&o(SCN)4 and (NH&
Co(SCN)(. These complexes may be extracted from aqueous
solutions by organic solvents. A rapid and accurate method for
the determination of cobalt in ores and concentrates has been developed in the Nkana laboratory by comparing the blue color of
these extracts of the cobalt complex by either visual or photoelectric means. The method has been investigated in great detail and applied successfully t o the determination of cobalt in
various mining and metallurgical samples in Northern Rhodesia
for the past three years.
The alkali thiocyanate complexes of cobalt were first described
by Skey ( 6 ) ,Morrell (4),and Vogel (9) in the years 1868 to 1879.

Laboratory, Nkana, Northern Rhodesia

Since that time a number of papers have appeared on this subject, but the most notable contributions have been presented by
Treadwell (8), Powell ( 5 ) ,Feigl and Stern (I), Tomula ( 7 ) , and
Gorski ( 2 ) .
Treadwell treated a solution of a cobalt salt with concentrated
ammonium thiocyanate and extracted the complex with amyl
alcohol or with a mixture of one part of am 1 alcohol to one part
of ether. A pure extract of the complex s%ows a characteristic
absorption spectrum. If ferric iron is present in the cobalt
solution, ferric thiocyanate is formed which colors the alcohol
extract red. The iron may be removed by treatment with
sodium hydroxide. Treadwell quotes Vogts analysis of the
ammonium thiocyanate complex which gives Co = lS.Ol%, S =
39.15y0 and r\a = 10.42%. This is calculated to the formuk
( N H ~ ) , ~ O ( S C ~ \This
; ) ~ . complex is easily decomposed even by
damp air to give cobalt and ammonium thiocyanates.
Powell considered the minimum concentration of ammonium
thiocyanate necessary for the formation of the cobalt complex
was 25% and preferred to use 30%. Varyin results were obtained according to the acidity or alkalinity of t%e cobalt solution.
Sodium pyrophosphate may be used to suppress the color due to
Iron.
Feigl preferred acetone as a solution medium for the coulplex
in drop reactions for the detection of cobalt. The color of the
complex is stronger if saturated solutions of ammonium thioryanate are used. The fixation of iron may be brought about by
the addition of phosphate, but all the methods for the suppression

A N A L Y T I C A L EDITION

April, 1946

of tjhe eolor due to iron are eff'ective only if the latter is present in
much less aniount than the cobalt.
Tomula carried out experiments to determine the maxiniurn
i,onreni,ration of thiocyanate which was necessary to produce the
greakst intunsity of color of the complex. For a cobalt concentration of 1.192 X 10-4 mole of cobalt chloride per liter a 5%
c,oncrntration of thiocyanate was sufficient. Acetone may be preerred as a solution medium for the complex. Sickel salts form a
green complex with the thiocyanate which is not soluble in acetone, but the presence of this green complex necessitates the use
of yellow filters in the colorimeter. Tomula quotes the work of
Dit2 as showing that the capacity of a solvent for preventing decomposition of a complex varies inversely as its dielectric constant.

265

the blue color of the copper sulfate solutions matches almost

identically the blue of the cobalt complex. Copper sulfate solutions are made up to match varying amounts of cobalt and are
kept in sealed test'tubes. The color of these will last for a considerable period, but the standards should be checked against
known amounts of cobalt from time to time.

A solution of copper sulfate in xater containing 8 grams of

cupric sulfate pentahydrate per liter will match an extract containing 0.02 mg. of cobalt per 10 ml. By progressively increasing
the strength of the standard solutions by 8 grams of cupric sulfate
pentahydrate, a range of standards is obtained which will match
extracts of the cobalt complex a t intervals of 0.02 mg. of cobalt.
I t has not been found practicable to take this set of standards beyond 0.40 mg. of cobalt. This means that the final standard
will contain 160 grams of cupric sulfate pentahydrate per liter.
In Table I are given the weights of samples taken and the dilutions according to the percentage of cobalt present in the sample.
The number of milligrams of cobalt present in an extract is
ascertained by matching the color vith that of the standard solutions. To obtain the percentage of cobalt present in the sample
this number of milligrams is taken multiplied by one of the factors
given in the final column of Table I according to the weight of
sample taken and the dilution. For example, let us assume that a
0.5-gram sample is taken, and its solution is diluted to 50 ml.
From this solution 5 ml. are taken to give the cobalt complex.
The extract of this complex matches a standard corresponding to
0.24 mg. of cobalt. By multiplying 0.24 mg. by 2 a percentage of
0.48 for cobalt is obtained. Since 0.24 mg. of cobalt were present
in the aliquot the percentage of cobalt in the qample is seen to be
100
0.00024 X 10 X 0.5 = 0.48%.

PHOTOELECTRIC.
A calibration curve for the color intensities
of the extracts of the cobalt complex may be drawn up by means
of an absorptiometer.

M/LL/~~
CaR
cwM
Lt ~
Figme 1.

Calibration Curve for Ammonium

Cobaltothiocyanate

In :he method given by Gorski for the detection of small

amounts of cobalt 15 ml. of ethyl alcohol and 5 ml. of a 5 S solulion of potassium or ammonium thiocyanate are added to 5 ml.
oj the test solution. The concentration of thiocyanate in the
mixlure is now 1 h'. By this method 0.003 mg. of cobalt may he
det rrrr. iri (4.

For this work a Spekker photoelectric absorptiometer was used

with 1-cm. glass cells and Spekker red filter No. 1. The absorption of light by the complex was in each case compared with the
absorption of a blank mixture of amyl alcohol and ether extracted
from the reagents. I n the construction of the curve 10-ml. extracts of the cobalt complex ranging from 0.02 to 0.50 mg. of
cobalt were used. In this case the increment of cobalt content
was again 0.02 mg. Only the intermediate points of the calihration curve are shown in Figure 1.

Table

I.

Weights and Dilutions of Samples According to Percentage

of Cobalt Present

REAGENTS

Cohalt
in SamDle

Sample
Taken for
Analysis

An~rlicrliumThiocyanate Solution. Dissolve 600 grams of

ammonium thioc anate, NH4CKS, in 1 liter of water.
Sodium PhospEate Solution. Dissolve 83.3 grams of tribasic
sodium phosphate dodecahydrate, NasP04.12Hz0, in 1 liter o f
Wale:
Rodrurn Thiosulfate Solution. Dissolve 200 grams of sodium
thiosulfate, Na2S20a.5H20,
in 1 liter of water.
Combined Sodium Phosphate and Thiosulfate Solution. To
increase the speed of the analysis the sodium phosphate and thiosulfate solutions may be combined in one. It is not advisable to
incluife the ammonium thiocyanate in this also. Dissolvg 125
grams of ~ a 2 S 2 0 3 . 5 H and
2 0 31.25 grams of Na3P0,.12H:0 in 1
!iter c9f water.
Ammonium Acetate Solution. Dissolve 700 grams of animo~ m m
acetate, N H ~ C Z H ~ in
O Z1,liter of water.
Tartaric Acid Solution. Dissolve 50 grams of tartaric acid,
C I H ~ Oin~ ,100 ml. of water.
Amyl Alcohol-Ether Mixture. Mix 3 parts by volume of amyl
alrohol with 1 part of ethyl ether.

Grams

0 . 0 1 to 0 . 2 0
0.16 t o 0 . 8 0
0.80 to3.20

2.0

METHODS OF COMPARISON

TISVAL. The color of the cobalt thiocyanate comples fades

after e short time and therefore a permanent set of standards
cannot be made up from organic solutions of the complex. Solutione oi copper sulfate may be used as permanent standards, since

0.5
0.5

Dilution
*lf1.
50
50
200

Aliquot
Taken for
.inalzsis
Jf 1.

Factor for

5
5
5

0,s
2

Cobalt

PROCEDURE

Decompose the cobalt samples with 10 ml. of nitric acid and 20

ml. of hydrochloric acid, adding a few drops of bromine or hydrofluoric acid if necessary. Decompose samples having a high iron
content with a solution of nitric acid and potassium chlorate.
Take the samples down to dryness but do not bake. Traces of
nitric acid have no effect on the formation of the thiocyanate complex.
Take up the samples in approximately 25 ml. of water, and add
exactly 1 ml. of hydrochloric acid for every 50 ml. of subsequent
dilution of the sample. To effect solution boil the samples gently
for a few minutes. Cool the solutions and wash out into appropriate measuring cylinders or calibrated flasks. The amount of
dilution of the samples depends on the amount of cobalt present
and can be read off from Table I.
After dilution the p H of the sample solutions is 1.0 to 0.9.
This is one of the most important steps in the analysis. In
samples where the percenta e of cobalt is entirely unknown and
the first dilution attempted kas proved insufficient, it is of no use
to try further dilution unless the pH is adjusted by the careful

IN D u sT R I A L A N D E N G IN E E R I N G

266

addition of more acid with the help of a pH meter. It is better

otherwise to weigh out another and smaller amount of sample.
COBALT
SAMPLES
WITH LESS THAN
40% IRON. Measure out
5 ml. of sodium thiosulfate solution, 3 ml. of sodium phosphate
solution (or 8 ml. of the combined sodium thiosulfate and phosphate solution), and 10 ml. of ammonium thiocyanate solution.
Add with vigorous agitation 5 ml. of the solution of the sample.
The pH is now 3.5 t o 4.0 and the concentration of ammonium
thiocyanate is 26%.

Table

II.

Gravimetric and Colorimetric Determinations of Cobalt in

Metallurgical Products

Mill tails
Mill feed
Cobalt oxide ore
Primary cobalt concentrate
Secondary cobalt concentrate
Cobalt concentrate
Copper concentrate
Cobalt gravity concentrate
Cobalt gravity tails
Copper reverberatory slag
Cobalt reverberatory slag
Cobalt reverberatory matte
Electric furnace slag
U.S. Bureau of Standards h-o ,115

Per Cent Cobalt

Gravimetric Colorimetrir Difference
0 00
0 06
0 06
0 14
0 00
0 14
0 56
0 55
+o 01
-0 02
0 70
0 68
0 00
3 04
3 04
0 00
2 40
2 40
0 00
0 64
0 64
-0 15
10 15
10 00
- 0 01
0 21
0 20
1 47
1 44
-0 03
0 64
0 63
+o 01
3 79
3 84
+o 05
2 21
2 24
+ O 03
0 00
0 08
0 08

Add 10 ml. of the .amyl alcohol-ether mixture and shake the

whole thoroughly again. Transfer to a separatory funnel, run off
the lower aqueous layer, and discard. Transfer the solution of
the cobalt complex t o a test tube or a 1-cm. absorptiometer cell.
For visual comparison match the intensity of color of the test
solution with the standard copper sulfate solutions. The comparison may be carried out in a LaMotte comparator for hydrogen-ion determinations with a source of artificial light, or the
tubes may simply be held against a white background out of
direct sunlight. It will be found possible to take a reading halfway between any two standards if the color of the test solutions
ies between them.
I n the photoelectric comparison, absorption of the test solution
is compared with an amyl alcohol-ether blank. The amount of
cobalt present in the test solution is then read off from the calibration curve.
By either means of comparison the amount in milligrams of
cobalt present in the extract is obtained and the percentage of
cobalt in the sample is given by multiplying by the appropriate
factor shown in the last column of Table I.
COBALTSAMPLESWITH 1 I O R E T H A N 4070 IROS. Carry Out
the analysis of these samples in exactly the same way as for samples with less iron, but in this case add 2 ml. of ammonium acetate
solution and 3 drops of tartaric acid solution. The pH is still 3.5
t o 4.0 and the concentration of ammonium thiocyanate is 24%.
INTERFERING I O N S

Copper does not interfere with the production of the blue color
of the cobalt complex even when it is present in amount equaling
60% of the sample.
Iron, if present in amount greater than 40% of the sample, will
interfere unless ammonium acetate and tartaric acid are used.
Chromium, manganese] nickel, zinc, titanium, molybdenum,
and uranium do not give colored complexes which are soluble in
amyl alcohol and ether. Other common elements such as silica,
aluminum, calcium, magnesium, phosphorus, bismuth, arsenic,
lead, and the alkalies are without effect.
Vanadium under these conditions also forms a blue complex
which is extracted by the amyl alcohol-ether solution. If, however, ammonium acetate and tartaric acid are added to the reagents this blue complex is not formed, and vanadium will not
interfere with the determination of cobalt.
SENSITIVITY

The smallest amount of cobalt which can be conveniently

determined by either visual or photoelectric comparison is 0.02
mg. It can be seen from the calibration graph obtained from the

c H E M 1sT R Y

Vol. 18, No. 4

absorptiometer readings that the relationship between the color

intensity of the cobalt complex and the cobalt content of the extracts is not linear but follows a curve of wide radius. The last
three standards employed in the visual comparison are slightly
more intense in color than corresponding extracts of cobalt, so
that accurate determinations cannot be carried beyond 0.40 mg.
of cobalt at the most. By use of an absorptiometer accurate
determinations can be obtained up to 0.50 mg. of cobalt.
Using the range 0.02 to 0.50 mg. of cobalt, accurate determinations have been carried out on S k a n a samples between 0.01 and
4.0070 cobalt. By taking smaller weights of sample, it has been
possible t o estimate cobalt up to 10% with a sufficient degree of
accuracy for rapid works practice.
RESULTS

A number of results of the colorimetric method, obtained by

both visual and photoelectric comparisons, are given in Table 11,
compared with the percentages of cobalt obtained by careful
gravimetric analyses.
DISCUSSION

A pH of 1.0 to 0.9 for the solution of the sample was found by

experiment t o be the optimum for the formation of the cobalt
complex. If the pH is higher than this the color is not so strongly
developed, while if it is lower it is impossible to suppress with
small amounts of phosphate the color due to iron. A final pH of
3.5 t o 4.0 in the solution of reagents and sample is well beloiv the
precipitation pH of cobalt phosphate, which is about 5.3.
Sodium thiosulfate has been found to be an efficient reducing
agent for the iron. Other reagents such as stannous chloride and
hydrogen sulfide gas have been tried out but were not found so
satisfactory.
A concentration of 24 to 26% ammonium thiocyanate is sufficient t o produce the maximum color intensity for amounts of
cobalt ranging from 0.02 to 0.40 mg. For quantities of cobalt up
t o approximately 0.14 mg. a concentration of 17% ammonium
thiocyanate is sufficient, but beyond this 26% concentration must
be used. It is not so convenient in routine analyses to alter the
concentration of a reagent according to the samples and therefore
a standard concentration of 24 to 26V0 ammonium thiocyanate
has been given in the procedure. Increasing the amount of thiocyanate beyond 26% did not further intensify the color.
The dielectric constant of amyl alcohol at 0 C. and infinite
wave length is 17.4 (3). The dielectric constant of ethyl ether is
4.68. A mixture of these two organic liquids will then have a
lower dielectric constant and greater capacity for preventing decomposition of the complex than methyl alcohol, ethyl alcohol, or
acetone which have dielectric constants of 35.0, 28.4, and 26.6,
respectively. A mixture of 3 parts by volume of amyl alcohol t o 1
part of ether has been found to give a maximum intensity of color.
The use of ammonium acetate and tartaric acid solution makes
it possible to determine cobalt on samples high in iron and
vanadium. By this method small amounts of cobalt may be
determined in steels and in the iron precipitates in a gravimetric
analyqis of cobalt.
LITERATURE CITED

Feigl, F., and Stern, R., 2. anal. Chem., 60, 1-43 (1921).
Gorski, M., 2.anorg. Chem., 81, 315-46 (1913).
Handbook of Chemistry and Physics, 26th ed., pp. 1840-1,
Cleveland, Chemical Rubber Publishing Co., 1942.
Morrell, T. T., 2 . anal. Chem., 16, 251 (1877).
Powell, A. D., J . Soc. Chem. I n d . , 36, 273-4 (1917).
Skey, JY., Z . and. Chem., 7 , 250-1 (1868).
Tomula, E. S., I b i d . , 83, 6-14 (1931).
Treadwell, F. P., 2.anorg. Chem., 26, 108-10 (1901).
Vogel, H. W.,
Ber., 12, 2313-6 (1879).
I