Proc. laldian Acad. Sci., Vol. 85 A, No. 2, 1977, pp.

55-57

Volumetric d e t e r m i n a t i o n o f c o p p e r by p r e c i p i t a t i o n v, it,t
ammonium thiocyanate
B. V. NARAYANA AND N. APPALA RAJU
Department of Chemistry, Sri Venkateswara University, Tirupati 517502
MS rcceived 30 June 1976; revised 12 August 1976

ABSTRACT

Potassium dichromate was employed for the determination of eopper

by preeipitation as cuprous thiocyanate. 1-0-10.0 mg of copper was
accurately determined by this procedure. The method was applied
for the analysis of coppcr in Dcvarda's alloy and chalcopyrites.

1. INTRODUCTION

VOLOMETRIC methods for copper vŸ oxidation of thiocyanate part in

cuprous thiocyanate are very few. 1-3 Raju and Reddy a described a poten-
tiometrie method for tlle estimatiorl of thiocyanate using dichromate.
This procedure has been made simple by Muralikrishna et al., 5 wko llave
estimated thiocyanate to a visual end point. We have made use of tkis
reagent, viz., potassium dichromate, for the accurate determination of
copper by precipitation as cuprous thiocyallate.

2. EXPERIMENTAL

AII the reagents used were of AR quality. The stock solution of

eopper was prepared by dissolving a knowrt weight of copper sulphate in
distilled water and diluting to a known volume. The solution was standar-
dised iodometrically.~~

PROCEDURE

An a[iquot of the solutiort contairting 1 90-10.0 mg of copper w~:s pipetted

out and the copper was precipitated as euprous thiocya.nate using a freshly
prepared 10f/o w/v ammortium thioeyanate solution, either by the cortven-
tional method using sulphur dioxidenb or by the procedure deseribed by
Raju et al. 7 The precipitate was filtered through a No. 4 sintered crueible
artd washed successively with cold water artd 2070 ethanol till ir was free
from soluble thioeyana,te. The preeipitate in the crueible was quantitative[y
dissolved with about 15-20 mi of liquor ammonia and the solutio~t was
55
A--I Fcb. 77
 56 B. V. NARAYANA AND N. APPALA RAJU

allowed to drop into a elean buchrter flask eontaining 10 mi of the standard

dichromate solution (0.025 M) and 45-50 mi of 9 M sulphuric aeid. The
erucible was washed with distilled water and the washings collected irtto the
same buchner flask. The flask was allowed to cool and stand at room
temperature for about 5-10 min and the excess dichromate was titrated with
mohr salt solution using 2-3 drops of 0.025 M ferroin indicator solution.
A 10rol microburette graduated in 0"02 mi was used in these titrations.

By this procedure, 1-10 mg of copper could be conveniently determined

with ah accuracy of _-]z0"56~. The reverse addition of dichromate solu-
tion to the anamoniacal copper thiocyanate solution resulted in low value
of copper.

ANALYSIS OF COPPER IN DEVARDA'S ALLOY

The alloy (0.2848 g) was tveated with a mixture of suiphuric, nitlic

and hydrochloric acids and the solution was evaporated to dense white
fumes. The residue was cooled, dissolved ir~. just the requisite quantity of
dilute sulphuric acid, filtered artd made up to 100 mi in a volumetric
flask. The copper content in the alloy solution was determined by the iodo-
metde procedure, ac Several aliquots of the alloy solution were analysed
for their copper content using the procedure described above. The percent-
age of copper in Devarda's alloy as obtained by the present method
(44.89) is comparable to that obtained by the iodometdc method (44.98).

ANALYSIS OF COPPER IN CHALCOPYRITES

The finely powdered ore (0-3309 g) was disollved in 25 mi of concen-

trated nitdc acid and the solution evapov~,.ted to about 5 mi. 10 mi of
concentrated hydrochloric acid and 10 mi of sulphudc acid (1 : 1) were then
added and the contents evaporated to dense white fumes. The residue was
treated cautiously with about 50 rol of water, cooled, filtered and made
up to 100 mi in a volumetric flask. The copper content in the ore solution
was determined by the iodometfic method. 6c Different aliquots of the
ore solution were analysed for their coppe: cor,.tertt with the procedure
given above. The conventional procedure of precipitation employirtg
sulphur dioxide 6b is found to be more convenient since the other method 7
involves the use of a complexing agent to mask the iron present. The
present method showed the copper content to be 32"93~ while the iodometric
method showed ir as 33.03~.

The method is more sensitive than the previous methods so far deve-
lopedfor the titdmetrie determination of eopper by precipitation as
 VOLUMETRIC DETERMINATION OF COPPER 57

cuprous thiocyanate. Moreover, tb.e end point ill this redox titratiort is more
clearly discernable than in the precipitatiort titration employing silver nitrate
reported ea.rlier. ~

ACKNOWLEDGEMENT

The authors are thankful to the University Grall.ts Commissio~. for the
awa.rd of a fellowship to or.c of them (BVN).

REFERENCES

1. Parr, J. Aro. Chem. Soc. 22 685 (1900).

2. Jamiesol~, G. S., l_,cvy, L. H. atld Wells, H. L., J. Aro. Chem. Soc. 30 760 0908).
3. Singh, B. and Singh, R., AnaL Chito. Acta 11 412 (1954).
4. Reddy, D. V., Rato, S. B. and Raju, N. A., Z. Anal. Chem. 2,44 123 (1969).
5. Muralikrish,'.a, U. and Bapar~iah, K. V., lndian J. Chem. 12 880 (1974).
6. Vogel, A. I., A Text Book of Quantitative Inorganic Analysis Including hzstrumental Analysi s
(Longmans, London) 3rd ed., (a) p. 358; (b) p. 497; (c) p. 359 (1961).
7. Venkata Reddy, D., Brahmaji Rao, S. a r a Appala Raju, N., Curr. Sci. 36 149 (1967).
8. Narayana, B. V., Ven kata Reddy, D. and Appala Ruju, N., Curr. Sci. 44 156 (1975).