S A M U E L H E IM A N AND W A L L A C E M . M c N A B B , D ep a rtm en t o f C hem istry and C h em ical Engineering, University o f Pennsylvania, P h iladelph ia, Pa.
T
HE free or uncombined cyanide content of a brass plating solution refers to the sodium cyanide in excess of that required to form the complex copper and zinc cyanides (2). The amount of free cyanide in the plating bath has a marked effect on the appearance and composition of the brass deposit, the cathode and anode efficiencies, the anode polarization, and the conductivity of the solution (15, 16,
. . .
In general, the free cyanide in any cyanide plating solution is determined by titration with silver nitrate, using potassium iodide as indicator (2,20). Inconsistent results are obtained, however, when this method is applied to brass plating solu
tions. The removal of the sodium carbonate before titration
A . B .
c.D.
E .
Fi g u r e 1. Di s t i l l a t i o n Ap p a r a t u s
300-m i. short-necked K jeldahl flask Connecting bulb, Southern Oil Co.
model
Condenser, 50 cm. long 250-m l. Erlenmeyer flask
Gas distributor. Miller {IS) has shown that this device ensures better absorption b y breaking up the large bubbles of gas.
with silver nitrate is said to overcome most of the difficulty (8, 8), although the interference of sodium carbonate may be avoided by suitably diluting the sample to be titrated (16).
Pan (16) has shown that ammonium hydroxide and potassium iodide influence the value of the free cyanide, and recom
mends that the titration be carried out in the presence of 0.37 N potassium iodide indicator in order to give accurate results. However, he neglected to consider the effect of free alkali or pH, which Blum and Ilogaboom (8) have pointed out makes the determination and calculation of free cyanide uncertain.
In contrast with this lack of agreement regarding the direct titration of free cyanide in brass plating solutions, the deter
mination of cyanide in copper and zinc plating baths has been satisfactorily worked out. Thompson (21) has shown that when a copper cyanide solution is titrated with silver nitrate, a reproducible value of free cyanide— that is, the cyanide in excess of that required to form the compound Na2Cu(CN)3— is obtained when 0.5 to 1.0 gram of potassium iodide per 100 ml. of solution is used as an indicator. If the same method of titration for free cyanide is applied to a zinc cyanide solution, inconsistent results are obtained, owing to the effect of variations in total alkalinity or pH on the equi
librium between sodium zincate and sodium zinc cyanide.
However, an accurate and reproducible value of the total cyanide may be obtained by adding an excess of sodium hydroxide to the solution and then titrating with silver nitrate (4). When this procedure for the determination of the total cyanide in a zinc plating solution is applied to a brass plating solution, the cyanide in the zinc complex plus the free cyanide should be obtained. One object of this investigation was to evaluate this method.
-Evolution M ethod for T otal Cyanide and A m m o n ia
Coates (7) has recommended an evolution method for determining the total cyanide in a brass plating solution, by means of which the uncombined cyanide can readily be calculated. Wick (22) has determined the total cyanide in a cyanide silver plating solution by distilling with sulfuric acid. It was thought desirable to investigate this evolution method for the determination of total cyanide, with the idea of making it as simple as possible in operation and detail, so that it could be used as a routine test.
Pagel and Carlson (14) have recently decomposed sodium cyanide quantitatively by the distillation of hydrocyanic acid from sulfuric acid solutions, and Morris and Lilly (18) have made further studies of this method.
DECEMBER 15, 1938 ANALYTICAL EDITION 699 Using the apparatus shown in Figure 1, tests were made
with technical zinc cyanide. Dilute sulfuric acid was added to zinc cyanide suspended in water and the hydrocyanic acid distilled into a sodium hydroxide solution. The sodium cyanide formed was titrated with standard silver nitrate.
The average of four distillations gave 99.88 per cent recovery of the cyanide content, as compared with the results obtained by titration of the total cyanide with silver nitrate in the presence of potassium iodide and sodium hydroxide.
In a similar manner, it was found that by distilling cuprous cyanide with a mixture of sulfuric and hydrochloric acids (1), or with hydrochloric acid alone, an average recovery of 99.73 per cent of the theoretical cyanide content of the cu
prous cyanide was obtained.
An old brass plating bath may contain iron as ferrocyanide, and the cyanide in this ferrocyanide will be included in the total cyanide as determined by the evolution method. Know
ing the iron content of the ¡dating solution, the sodium cya
nide equivalent to the ferrocyanide may be calculated, and accounted for in the calculation of the free cyanide. How
ever, in a given plating bath, the amount of ferrocyanide will not change appreciably, and for routine control work the correction will remain substantially constant and may be neglected.
thors have chosen the Na2Zn(CN)4 formula in calculating the free cyanide from the results obtained by the evolution and titration methods.
Ammonium hydroxide is commonly added in very small quantities to a fresh brass plating bath at the time of prepa
ration in order to improve its initial operation (6). One pint of concentrated ammonium hydroxide per 100 gallons of solution is usually recommended. It is believed that a small quantity of ammonia forms in an old plating bath as a result of the decomposition of free cyanide (28).
More recently Pan (17) has shown that the presence of ammonia concentration of an old plating bath. Further
more, if a convenient method for the control of the ammonia concentration were available, some of the advantages recom
mended by Pan might be realized in practice. An evolution method to determine ammonia in cyanide solutions was therefore investigated.
Meeker and Wagner (11) have suggested the use of a boric acid solution instead of a standard acid solution for the ab
sorption of ammonia. Using this modification of the stand
ard evolution method, four distillations using c. p . ammonium chloride gave an average recovery of 99.74 per cent of the Erlenmeyer flask receiver, 10 ml. of concentrated hydrochloric acid, diluted to 100 ml., were poured into the distillation flask, and the connecting bulb was immediately replaced. The solu
tion was then distilled for 45 minutes, during which time about half the contents of the flask distilled over. After the distilla
tion, the condenser and gas distributor were rinsed with distilled
water, running the washings into the receiver. The sodium determined on the same sample.
Pr o c e d u r e f o r Am m o n i a. After cooling the flask to room similar to that used in practice, was made up with the follow
ing composition:
By calculation on the basis of direct analyses of the above reagents, 5 ml. of this solution contain 0.3140 gram of sodium cyanide (including the sodium cyanide equivalent to the cyanide in the cuprous cyanide and zinc cyanide).
Table I gives the results obtained on distilling 5 ml. of brass solution No. 1 as given in the procedure. An average of 99.1 per cent of the total cyanide in the plating solution was recovered. It is interesting to note that after the solution had stood for 2 months in the laboratory, about 1.5 per cent of the total cyanide had decomposed and was recovered as ammonia on distilling with sodium hydroxide.
The uncombined sodium cyanide in the brass plating solu
tion was calculated in the following manner: The copper and zinc contents of the solution multiplied by 2.312 and 2.998, respectively, gave the sodium cyanide equivalents in the cyanide complexes Na2Cu(CN)3 and Na2Zn(CN)4. The sum of these equivalents subtracted from the total cyanide content gave the free or uncombined sodium cyanide.
Five milliliters of this solution contain 0.3147 gram of total sodium cyanide by calculation, including the sodium cyanide equivalent to the cyanide in the cuprous cyanide.
Table I also gives the results obtained in analyzing this second solution for both total cyanide and ammonia by the evolution methods previously described. The average re
covery of total sodium cyanide, 99.09 per cent, is about the same as that with the first brass plating solution. The slightly low values obtained on the total cyanide recovery are probably due to hydrolysis of the sodium cyanide to ammonium formate during the distillation (10). This may account for the fact that the recovery of the total cyanide is about 1 per cent low and the ammonia recovery is about 1 per cent high.
700 INDUSTRIAL AND ENGINEERING CHEMISTRY VOL. 10, NO. 12
T itration M ethod for Free Cyanide
Five milliliters of brass plating solution No. 2 were titrated with 0.1 N silver nitrate solution in the presence of various
nide, Na2Zn(CN)4. [The zinc content of the solution multi
plied by 2.998 gives the sodium cyanide equivalent to the Na2Zn(CN)4.] Using 100 ml. as the total volume at the end of the titration with silver nitrate, in the presence of from 2.0 to 4.0 grams of sodium hydroxide and 1.5 to 3.0 grams of potassium iodide, the above calculated value of sodium cya
nide is obtained.
These results indicate that the cyanide content of the sodium copper cyanide, Na2Cu(CN)s, is not titrated under these conditions. It is possible, therefore, to determine the free cyanide by direct titration with silver nitrate in the presence of potassium iodide and sodium hydroxide, pro
vided the zinc content of the plating bath is known.
The presence of ammonia in cyanide plating solutions gives higher values of free sodium cyanide when determined by titration with silver nitrate (16, 21). A similar effect of ammonia has been observed in titrating the cyanide present as free sodium cyanide and sodium zinc cyanide in a brass plating solution using silver nitrate, sodium hydroxide, and potassium iodide as recommended above. Since only 5 ml.
of the plating solution are used in the titration, the amount of ammonia normally present in a brass plating bath is not liter) did not interfere with the sharpness of the end point or the accuracy of the method. The dilution of the sample being titrated was found to have only a slight effect on the value of the sodium cyanide. The effects of ammonia, sodium car
N ajC O j found titration found ammonia found
C c ./5 ml. Five milliliters of the brass plating solution were transferred to a 250-ml. Erlenmeyer flask and 20 ml. of 20 per cent sodium hydrox
ide solution, 20 ml. of 10 per cent potassium iodide solution, and 40 ml. of water were added. The solution was then titrated with 0.1 N silver nitrate solution to the appearance of a bluish opales
cence.
The free sodium cyanide in the brass plating solution may be calculated as follows: The number of milliliters of silver nitrate used in the titration multiplied by 1.960 equals the number of grams per liter of sodium cyanide on the basis of the free cyanide, plus the sodium cyanide equivalent to the sodium zinc cyanide, Na2Zn (C N )t. The latter may be found by multiplying the zinc content of the bath (expressed in grams per liter) by 2.998.
The free sodium cyanide may be obtained by difference.
Su m m ary
The total cyanide and ammonia content of a brass plating bath may be determined by evolution methods. The error error by the titration method is about 2 per cent.
In the evolution method, the accuracy of the determination of free cyanide depends upon the accuracy of the zinc and copper determination. The accuracy obtained by the titra
tion method depends upon the accuracy of the zinc deter
The free cyanide may be determined by either the evolu
tion or the titration method with sufficient ease and accuracy for practical routine control purposes.
Ackno'wledgmen t
The authors are indebted to A. Kenneth Graham for helpful suggestions, and gratefully acknowledge a grant from the Faculty Research Committee of the University of Penn Analyzing Plating Solutions," 4th ed., p. 12, 1938.
(9) Kolthoff, I. M., and Sandcll, E. B., “ Textbook of Quantitative Inorganic Analysis,” p. 545, New York, Macmillan Co., 1936.
(10) Krieble, V. K ., and Peiker, A. L., J. Am. Chem. Soc., 55, 2326
(20) Springer, Metallwaren-Ind. Galvano-Tech., 35, 312-14 (1937).
(21) Thompson, M. R., Monthly Rev. Am. Electroplaters’ Soc., 18,
Rideal Stewart and Alsterberg Modifications o f the W inkler Method
C. C. ItU C H H O F T , W . A L L A N M O O R E , a n d O . R . P L A C A K
Stream P ollu tion In vestigation s, U . S. P ublic H ea lth Service, C in cin n ati, O hio
A
MONG the many modifications of the Winkler method _ advocated for the determination of dissolved oxygen in the presence of nitrite, probably the most widely used is the Rideal Stewart method. Because it has been recognized for some time that in the presence of organic matter this modification gives low results, other modifications have been proposed. Noll (5) proposed the use of urea for the destruction of nitrites but, as Alsterberg (1) has pointed out, its use requires a long period of contact (approximately 24 hours) and is, therefore, impracticable. Alsterberg substituted sodium azide for urea and found that the destruction of nitrite could be accomplished in a few minutes. Ohle (6), summariz
ing methods used for the determination of dissolved oxygen in the presence of nitrite, did not consider the azide method important. However, as pointed out by Brandt (8), this modification has been used extensively in Germany on river studies.
In the course of previous work (4) on the determination of the solubility of oxygen in sewage, a number of modifications of the Winkler method were used. This work has since been extended to include the azide modification. The results obtained were so promising that it was decided to make a comparative study of the sodium azide and Rideal Stewart modifications during the course of a survey of the Scioto River.
The results obtained by these two methods on samples from this polluted stream are given in the present paper.
Experimental M ethods
In this study the samples of water were collected from regu
lar sampling stations distributed along the Scioto River from 3 to 115 miles from Columbus, Ohio. The samples of water that were to be used for comparative dissolved oxygen determinations by the two methods were obtained simultane
ously in two standard 300-ml. bottles contained in one stand
ard sampling apparatus for collecting samples for dissolved
oxygen determinations. All samples were tightly stoppered and immediately transported by automobile to a central laboratory at Chillicothe, Ohio, for analysis upon arrival.
The maximum elapsed time between collection and analysis of any of these samples was 3 hours. All samples from the was destroyed in acid solution before the Winkler procedure and consequent liberation of iodine, in order that the free iodine might not react with any organic matter present during the time interval allowed for nitrite destruction and thus tend to give low results. The following procedure was found to be entirely satisfactory even though the nitrite concentration might be as high as 4.0 p. p. m. sulfate solution and 3.0 ml. of alkaline potassium iodide solution are next added and the sample is shaken for 20 seconds. Follow
ing this the precipitate is allowed to settle and the sample is acidified with 2.0 ml. of concentrated sulfuric acid. The liber
ated iodine on a volume of solution equivalent to 200 ml. of the original sample is titrated immediately with 0.025 N sodium thio- sulfate, using starch indicator.
The 10-minute interval of standing after mixing the sodium azide solution with the acidified sample is necessary for the completion of the azide nitrite reaction and destruction of the nitrite.