Introduction:

The separation and estimation of copper and zinc from a mixture involves two
steps(a) Determination of copper volumetrically in presence of zinc
(b) Separation of copper and determination of zinc gravimetrically

In the process of estimation of copper, volumetric titration is used. In

volumetric titration, a known volume of a standard solution (one whose
concentration is known) reacts with a known volume of a solution
whose concentration is unknown. This procedure standardizes the
latter solution, by allowing a calculation of its concentration.
Titration of copper solution is done by standard solution of
sodium thiosulphate (Na2S2O3). For this purpose, first, we have to standardize sodium
thiosulphate by standard solution of potassium dichromate (K2Cr2O7). This is an
oxidation-reduction titration.
Determination of zinc is done by gravimetric analysis. Gravimetric analysis is a
process of producing and weighing a compound or element in as pure a form as possible
after some form of chemical treatment has been carried out on the substance to be
examined. Traditional gravimetric determinations have been concerned with the
transformation of the element, ion or radical to be determined into a pure stable
compound which is suitable for direct weighing or for conversion into another chemical
form that can be readily quantified.

(a) Determination of Copper volumetrically in presence of ZincFor determining the amount of copper, Iodometry is used. Iodometry is an
application of iodine chemistry to oxidation-reduction titrations for the quantitative
analysis in certain chemical compounds, in which iodine is used as a reductant and the
iodine freed in the associated reaction is titrated, usually in neutral or slightly acid
mediums with a standard solution of a reductant such as sodium thiosulfate or sodium
arsenite; examples of chemicals analyzed are copper(III), gold(VI), arsenic(V),
antimony(V), chlorine, and bromine.
For determining copper in the solution the liberated iodine ions are titrated by
standard sodium thiosulphate (Na2S2O3). For this, first we have to standardize Na2S2O3.
Potassium dichromate is used to titrate Na2S2O3. Starch is used as a indicator here.

2Cu2+ + 4KI = Cu2I2 + I2 + 4K+

2Cu2+ I2 2Na2S2O3

For the determination of copper liberated iodine ions are produced by adding
potassium iodide (KI) into the copper salt solution. Sometimes free mineral acid is
present in the solution, for that a few drops of dilute sodium carbonate (Na2CO3) solution
or 1:1 ammonia solution must be added until a faint permanent precipitate remains. This
precipitate is removed by means of a drop or two of ethanoic acid. KI is then added and
the titration continued. For accurate results, the solution should have a pH of 4 to 5.5.
When titrating with Na2S2O3 the color of the solution becomes faded from brown. Then
1or 2 ml of starch is added and titration is continued until the blue color begins to fade.
This time 1 ml of 10% ammonium thiocyanate (NH4CNS) is added and immediately the
blue color of the solution will become intense. Now the titration is completed as quickly
as possible. The precipitate possesses a light green color, and a distinct permanent end
point is readily obtained.
(b) Separation of Copper and Determination of Zinc gravimetricallyHere, first we have to separate copper from the solution then we can determine
zinc gravimetrically.
For separating copper 1 or 2 g of sodium sulphite (Na2SO3) is added which
reduces Cu2+ to Cu+. Then 15 ml of freshly prepared ammonium thiocyanate (NH4CNS)
solution is slowly added from a burette with constant stirring. NH4CNS reacts with Cu+
to precipitate CuCNS. The precipitate should be white and the mother liquor should be
colorless.
Na2SO3
Cu

2+

NH4CNS
Cu

CuCNS
(White precipitation)

Finally, the precipitation is filtered through an ordinary filter paper, washed with
1% NH4CNS and discarded.
For gravimetric analysis the filtrate is first evaporated to about 100 ml. Zinc is
precipitated in the form of zinc pyrophosphate (Zn2P2O7) by adding 15 ml of 10%
diammonium hydrogen phosphate((NH4)2HPO4). But the reaction between zinc and
(NH4)2HPO4 take place in neutral condition. For this, before adding (NH4)2HPO4, we have

to neutralize the solution by adding ammonia solution and check the neutrality by methyl
orange indicator.
Now the precipitate is filtered through Whatman No.40 and transferred to a
previously ignited and weighed porcelain crucible along with the filter paper. Finally, the
crucible is ignited taking usual precautions. Now from the residual of the ignition we can
calculate the amount of zinc present in one liter of supplied sample.

Chemicals:
Na2S2O3, K2Cr2O7, KI, NH4OH, NH4CNS, Na2SO3, NH4CNS, (NH4)2HPO4, methyl
orange.

Calculations:
(a) Determination of Copper volumetrically in presence of ZincStandardization of Na2S2O3 by standard K2Cr2O7 solution
No. of
Volume of
Burette reading
Volume of
Obs.
K2Cr2O7
Na2S2O3
Initial
Final
ml
ml
1
10
11.8
21.6
9.8
2
10
21.6
31.5
9.9
3
10
31.5
41.4
9.9
Here, Volume of K2Cr2O7, V1 = 10 ml
Volume of Na2S2O3, V2 = 9.86 ml
Normality of K2Cr2O7, N1 = 0.1 N
V1

N1

Normality of Na2S2O3, N2 =
V2
10

=
9.86
= 0.1014 N

0.1

Average Volume of
Na2S2O3
ml
9.86

Determination of copper
No. of
Volume of
Burette reading
Obs.
Copper
Initial
Final
Solution
ml
1
10
0.0
5.1
2
10
5.1
10.1
3
10
10.1
15.1
1L 1N

Na2S2O3

5.03 ml 0.1014 N

Volume of
Na2S2O3
ml

Average Volume of
Na2S2O3
ml

5.1
5.0
5.0

63.54 g Cu
63.54 x 5.03 x 0.1014
Na2S2O3

1000
= 0.032 g Cu

In 10 ml solution remains 0.032 g Cu

In 1 L solution remains

0.032 x 1000
10
= 3.2 g Cu / L

(b) Gravimetric analysis of ZincWeight of the empty crucible = 39.693 g

Weight of the crucible with Zn2P2O7 = 39.698 g
Weight of Zn2P2O7 = 0.005 g
1 g of Zn2P2O7 contains 0.3132 g of zinc
0.005 g of Zn2P2O7 contains 0.3132 x 0.005 = 1.566 x 10-3 g

5.03