August 15, 1941 ANALYTICAL EDITION
(17) Philippoff, W., KoEEoid Z., 71, 1-16 (1935).
(18) Ibid., 75, 142-54 (1936).
(19) Ibid., 75, 155-61 (1936).
(20) Philippoff, W., and Kruger, H. E., Ibid., 88, 215-23 (1939).
(21) Robinson, J. R., Proc. Roy. Soc. (London) A170, 519-49 (1939).
(22) Schulz, G . V., 2.Elektrochem., 43, 479-85 (1937).
(23) Signer, R., 2.physik. Chem., 150, 267-84 (1930).
(24) Btaudinger, H., “Die hochmolekularen organischen verbindun-
gen Kautschuk und Cellulose”, Berlin, Julius Springer, 1932.
(25) Staudinger, H . , Papier Fabr., 36, 373-9. 381-8, 473-80, 481-5
(1938).
(26) Staudinger, H., and Schulz, G. Y.,Ber.. 68, 2320-35 (1936).
Colorimetric Determination of Copper with
Ammonia
A Spectrophotometric Study
J . P. JIEHLIG, Oregon State College, Conallis, Ore.
T HE determination of copper, which depends upon the
production of the intense blue color of the cupric am-
rnonia complex when ammonia is added to a solution of a
cupric salt, is one of the oldest colorimetric methods.
Among the first workers to use it was Heine (11) in 1830,
followed by Dehms (6) and Bischof (5’). More recently it has been
applied to t’he determination of copper in peas ( 4 ) ; in blast slags
and tailings (1); in preserves (19); in marine organisms ( 1 7 ) ;
in the human body (2); in iron, steel, and slag (20); in vege-
tables (9); and in rubberized fabrics (18). Snell (21) has claimed
that the method is most sensitive when 0.01274 mg. of copper per
milliliter is present and that a t this concentration the addition
of 0.000016 mg. of copper can be detected. It is doubtful, how-
ever, if the method is as sensitive as these figures would imply,
for t-oe and Crumpler (27), using a roulette comparator, found
that a solution containing 8 p. p. m. of copper could be distin-
guished only with difficulty from one containing 7 or 9 p. p. ni.
nnd with certainty from one containing 6 or 10 p. p. m.
The purpose of the work described in this paper was to
make a critical study of this method by means of the photo-
electric recording spectrophotometer (14,with particular
attention to the effect of diverse ions upon the color system.
Similar studies of other colorimetric methods have recently
been m d e (5,7’,8’12, 13,22, $4).
Apparatus and Solutions
All spectrophotometric measurements in the present work were
made at Purdue University with the instrument used by the
writer in two previous investigations (13).
A standard stock solution of cupric sulfate pentahydrate, each
milliliter of which contained 4 mg. of copper, was made by dis-
solving 15.7160 grams of the thrice recrystallized salt in re-
distilled water, adding 1 nil. of concentrated sulfuric acid, and
accurately diluting to 1 liter.
Ammonium hydroxide solutions of various concentrations,
such as 1, 2, 3, 4, and 6 M, were made by suitable dilution of the
concentrated solution of specific gravity 0.90.
Standard solutions of the diverse ions were prepared from the
chloride, nitrate, or sulfate salts of the cations and from the so-
dium, potassium, or ammonium salts of the anions. Redistilled
water was used in all case^. Each milliliter contained 10 mg. of
the ion in question.
To produce the color system 5 ml. of the standard copper solu-
tion in a 100-ml. volumetric flask were just neutralized with 15 M
ammonium hydroxide, diluted to the mark with 3 -If ammonium
hydroxide (35),and thoroughly shaken.
The spectral transmission curves were determined for a solu-
tion thickness of 1.961 cni. and a spectral band n-idth of 10 mp.
Compmsation for the absorption of the glass cell and solvent was
533
(27) Staudinger, H., and Sorkin, M.,I b i d . , 70, 1993-2017, 2518
(1937).
(28) Technical dssoc. of Pulp and Paper Industry, “Testing Meth-
ods, Recommended Practices, Specifications”, Tentative
Revision T206M (Apr. 15, 1935).
(29) Williamson, R. V., IND. EXG.CHEM.,21, 1108-11 (1929).
PRESENTED before the Division of Cellulose Chemistry a t t h e 99th Meeting
of t h e American Chemical Society, Cincinnati, Ohio. T h e studies reported
relate t o t h e program of work of t h e Cotton Quality a n d Standardization
Research Section, Agricultural Marketing Service, under direction of Robert
W.Webb.
obtained by placing in the rear beam of light a similar cc I filled
with 3 M ammonium hydroxide.
That the color reaction may be reproduced to a high de-
gree of precision is shown by the fact that eleven solutions of
the cupric ammonia complex, each containing 200 p. p. m. of
copper and prepared by the above procedure, gave trans-
mittancies at 620p (the peak of the absorption band), the
average deviation of which from the mean was only 0.1 per
cent.
Conformity to Beer’s Law
That Beer’s law is followed by the color system is shown
by the fact that a straight line resulted when the logarithms
of the observed transmittancies a t 620 m p for six solutions,
containing from 40 to 600 p. p. m. of copper, were plotted
against the respective concentrations. This is in agreement
with the work of other investigators (16’66, $7).
Effect of Ammonium Hydroxide
Different workers have used various concentrations of
ammonium hydroxide to produce the cupric ammonia com-
plex. Yoe (26) used 3 M , Heath (10) 2.1 M , and Snell ($1)
1.5 -11. Yoe and Crumpler (27) have pointed out that am-
monia solutions show an appreciable absorption of light in
the visible region.
I n a study of the effect upon the color of the concentration
of ammonium hydroxide, the transmission curves produced
by a series of solutions, each containing 200 p. p. m. of copper,
but made by use of 1 M, 2 M, 3 M, 4 M, 6 M , and Snell’s
approximately 1.5 M ammonium hydroxide, were compared.
I n each case the corresponding concentration of ammonium
hydroxide was used in the rear cell. The curves show that
the hue gradually changes as the concentration of ammonium
hydroxide varies. Both the maximum absorption and the
wave length of maximum absorption increase as the concen-
tration increases. This is in accordance with the findings of
Keigert ($3) and of Yoe and Barton ($6)who used only two
concentrations of ammonium hydroxide. Therefore, it is
necessary that the concentration chosen for the determination
be used throughout in making all the unknown as well as
standard solutions n-hich are to be used for comparison. In
the present work the 3 Msolution ($5) was selected. Because
of the high concentration of ammonia, no attempt was made
to determine pH values.
534 INDUSTRIAL AND ENGINEERING CHEMISTRY Vol. 13, No. 8

mittancy for the solution of concentration c2. I n accordance

TABLEI. EFFECTOF DIVERSE
ANIONS with the procedure followed in two former studies by the
(20 mg. of copper in 100 ml. of solution) writer (IS) and by other workers a t Purdue University
Apparent Change Approximate (6, 7, 8, 12, 82, ZJ),a 2 per cent error was set as the maximum
in Copper Limiting
Ion Concentration Concentration Concentration allowable for negligible interference. Although visual meth-
P. p . ni. 70 P. p . ni. ods of color comparison often have a precision of not less than
Acetate 500 Negligible 5 per cent, it was thought advisable to set a lower figure to
Arsenate 500 (As) Negligible
Arsenite 500 (As) Negligible provide for other possible factors including the effect of the
Borate 250 (R208) Negligible ...
Benzoate 500 Negligible ... extinction coefficient.
Bromide 500 Negligible The interfering anions may be divided into four general
Carbonate 600 h-egligible
Chlorate 500 Negligible classes: those, such as citrate, cyanide, tartrate, and thio-
Chloride 500 Negligible
Chlorostannate 500 (Sn) Precipitates sulfate, which form complexes with copper without a change
100 (Sn) +6.0 0 in hue; those, such as pyrophosphate and salicylate, which
Chlorostannite 100 (Sn) Precipitates 0
Citrate 500 -6.5 form complexes with a change in hue; those, such as dichro-
100 -2.0 100
Cyanide 350 Decolorized mate, which cause a change in hue because of their own color;
100 -77 n 0
Dichromate 100 (Cr) Chyn; in hue 0 and those, such as chlorostannate, chlorostannite, tungstate,
Fluoride 500 Negligible and vanadate, which cause turbidity because of their OTW
Formate 500 Negligible
Iodide 500 Negligible ... hydrolysis or the precipitation of copper salts.
Molybdate 500 12.R
I n Figure 1, curve 2 shows the effect of 100 p. p. m. of cya-
200 i z . 0 200
Nitrate
~

Nitrite
500 Negligible nide ion, curve 3 the effect of 500 p. p. m. of thiosulfate ion,
500 Negligible
Orthophosphate 500 (P9OS) Negligible curve 4 the effect of 200 p. p. m. of tungstate ion, and curves 5
Oxalate 500 Negligible and 6 the effects of 100 and 500 p. p. m. of chromium as di-
Perchlorate 500 Segligib!e ...
Pyrophosphate 100 Chanee in hue 0 chromate ion.
Salicylate 100 Channe in hue 0
Silicate 500 (SiOz) -2.5 The effects of the common anions and their approximate
100 (SiOn) Negligible 250 limiting concentrations are listed in Table I.
Sulfate 500 Negligible ...
Sulfite 500 Segligible ...
Tartrate 500 -5.4
Thiocyanate
200
500
-2.3
Segligible
100 Effect of Cations
Thiosulfate 500 -8.7
400 -2.3 Cobaltous and nickelous ions are the only common cations
300 Negligible 330
Tungstatr 300 Turbidity which really interfere. They form soluble, colored ammonia
200 +6.0 complexes, causing a change in hue. I n Figure 2, curves 2
100 Negligible 100
Vanadate 50 (V) Turbidity 0 and 4 show the effects of 100 and 500 p. p. m. of nickelous ion
and curves 3 and 5 the effects of 25 and 100 p. p. m. of cobal-
tous ion. Although silver, cadmium, and zinc ions form am-
Stability of the Color
Six solutions, containing 40, 80, 120, 400, and 600 p. p. m.
uf copper, respectively, in 3 M ammonium hydroxide, were
stored in glass-stoppered Pyrex bottles and allowed to stand
in diffuse light. Curves made a t intervals for these solutions
gave no evidence whatever of fading or of other change in
color over a period of six weeks. Lack of time prevented
tests over a longer period. Apparently the color is stable in-
definitely. Such marked stability makes possible the use of
a series of permanent standards, which must, however, be
kept tightly stoppered to prevent loss of ammonia. Bny
action of the ammonia on the glass t o produce turbidity is
reduced to a minimum by using Pyrex containers.
Effect of Anions
In the ion-interference studies the curve produced by the
standard solution containing 200 p. p. m. of copper in 3 M
ammonium hydroxide was compared with the curve pro-
duced by a similar copper solution containing in addition a
known weight of the diverse ion. From the transmittancies
a t 620 mp of the standard solution and of each of the other
solutions and from the known copper concentration of the
standard solution, the apparent concentration of copper in
each of the solutions containing diverse ions was calculated
by the aid of a special color slide rule. The difference be-
tween this value and the actual concentration multiplied by
100 and divided by the actual concentration gave the per-
centage error. The calculation is based upon the formula
which expresses Beer’s law

where T I represents the transmittancy, expressed as a deci- FIGURE1. EFFECTOF ANIONS

20 mg. of copper with diverse ion diluted t o 100 ml. with 3 .If ammonium
mal, for the solution of concentration CI, and Tz the trans- hydroxide. 1.961-om. cell.
August 15, 1941 ANALYTICAL EDITION 535

nionia complexes, the latter are colorless and do not interfere.

Barium, lead, and strontium ions precipitate as sulfates, and TABLE11. EFFECTOF DIVERSECATIONS
aluminum, antimonous, beryllium, bismuth, chromic, ferric, (20 mg. of copper in 100 ml. of solution)
Approximate
ferrous, magnesium, manganous, mercuric, mercurous. .ipparent Change Limiting
thorium, uranyl, and zirconium ions precipitate as hydroxides in Copper Concentra-
Ion Concentration Concentration tion
or basic salts in the alkaline solution. I n the course of the P . p . m. 70 P . p . n.
determination (1O , Z l , 26), however, fuming down with sulfuric Ammonium 400 Segligiblen ..
acid, followed by addition of ammonium hydroxide and filtra- Cadmium
Calcium
500
500
Negligib!e
Segligible
tion, would remove all these ions and so prevent interference. Cobaltous 25 Change in hue 0
Lithium 2 50 Segligible ..
Niokelous 50 Change in hue 0
Potassium 500 Segligible ..
IW Silver 500 Negligible ..
Sodium 600 Negligible ..
Zinc 500 Negligible ..
a Provided chlorides do not exceed 400 p. p . m.
90

tration must be used for the standards as for the unknown

80
solutions. A 3 M solution is recommended.
The color system follows Beer’s lam.
70
The color is stable in diffuse light for a t least six weeks and
undoubtedly for a much longer time. The use of a series of
permanent standards is therefore possible.
eo
The color reaction may be reproduced to a high degree of
5 precision.
c’ A study of the effect of sixty common ions shows that only
a few, especially cobaltous, nickelous, and dichromate,
seriously interfere with the color and that a considerable
a number of others cause precipitation or turbidity, but in the
40 course of the determination this latter group mould be re-
c
f moved.
P
30 hcknowledgmen ts
I - Cu ALONE The writer wishes to express his sincere appreciation to
2- C u t l O O p p m N I *+ &I. G. Mellon of Purdue University, in whose laboratory this
3- C u 25ppm Cot‘ investigation was conducted, and to thank him for the
4-Cu+500ppm NI **
5 - C ~ + 1 0 0 p p m Ce If
privilege of using the Purdue spectrophotometer. Thanks
are also given to J. T. Koods and T. P. Marsh for their aid
in adjusting the spectrophotometer.
400 440 480
WAVE
520
LENGTH
560
IN m H
600 640 680 700 Literature Cited
Austin, A., Mining w o r l d , 33,753 (1910).
FIGURE2. EFFECTOF CATIONS Bergeron and L’Hote, L., Compt. rend., 80, 268 (1875).
LO rrlp of copper u i t h diverse ion diluted t o 100 ml. with 3 31 ammoniun. Bischof, G., 2. anal. Chem., 6, 459 (1867).
hydroxide. 1961-cm. cell. Rodner, R., and Moor, C. G., Analyst, 22, 141 (1897).
Byers, D. H., and Mellon, M . G., ISD.ENG.CHEX.,Anal. Ed.,
11, 302 (1939).
The ammonium ion when introduced as the sulfate has a Dehms, F., 2. anal. Chem., 3, 218 (1864).
negligible effect upon the color, but 200 p. p. m. of ammonium Dragt, G., and Mellon, >I. G.. ISD.ENG.CHEM.,Anal Ed., 10,
256 (1938).
ion as chloride cause an error of +2 per cent in the concen- Fortune, W. B., and Mellon, M. G., I b i d . , 10,60 (1938).
tration of copper, while 500 p. p. m. of ammonium ion as Hanak, A,, 2. L’ntersuch. Lebensm., 59, 511 (1930).
chloride cause an error of +3.3 per cent. For larger amounts, Heath, G. L., J . Am. Chem. SOC.,19,24 (1897).
such as 1000 p. p. m. and 1500 p. p. m., this error remains con- Heine, Bergwerksfreund, 1, 33 (1830).
Howe, D. E., and Mellon. 31.G., ISD.EKG.CHEM.,dnal. Ed.,
stant at +3.3 per cent. Therefore, not more than 200 p. p. m. 12,448 (1940).
of ammonium ion as ammonium chloride should be present. Mehlig, J. P., Ibid., 10, 136 (1938); 11, 274 (1939).
Milbauer and Stanek (15) hare apparently erroneously Michaelson, J. L., and Liehhafsky, H , Gen. Elec. Rev., 39,
stated that the intensity of the color decreases with increas- 445 (1936).
Milbauer, J., and Stanek, V.,2. anal. Chem., 46, 644 (1907).
ing amounts of ammonium chloride. The transmission Muller, R. H., IND.ENG.CHEM.,Anal. Ed., 7, 223 (1935).
curves prove that there is an increase in intensity. Yoe and Rose, W. C., and Bodansky, M.,J . Bid. Chem., 44, 99 (1920).
Barton (26) have obtained a similar result. Ruthing, A., Chem.-Ztg., 54, 403 (1930).
I n Table I1 are listed the effects and approximate limiting Serger, H., Ibid., 35, 935 (1911).
Sisco, F. T., “Technical Analysis of Steel”, p. 272, New York,
concentrations of the common cations which do not cause McGraw-Hill Book Co., 1925.
precipitation. Snell, F. D. and C. T., “Colorimetric hlet.hods of Analysis”, Vol.
I, p. 145, New York, D. Van Nostrand Co., 1936.
Summary Swank, H. W., and Mellon, M. G., IND.ENG.CHEM.,Anal. Ed.,
9,406 (1937); 10,7 (1938).
h spectrophotometric study shows that the ammonia Weigert, F., Ber., 49, 1529 (1916).
method for the colorimetric determination of copper is very Vright, E. R., and Mellon, M.G., 1x0. EKG.CHEM.,Anal. Ed.,
satisfactory with few limitations. The procedure of Yoe (26) 9,261, 375 (1937).
is recommended. Yoe, J. H., “Photometric Chemical Analysis”, Vol. I, p. 176,
New York, John Wiley & Sons, 1928.
The concentration of the ammonium hydroxide used for Yoe, J. H., and Barton, C. J., IND. EKG.CHEM.,Anal. Ed., 12,
dilution must be carefully controlled because of the ability 456 (1940).
of the ammonia solution to absorb light. The same concen- Yoe, J. H., and Crumpler, T. B.. Ibid.,7, 281 (1935).