Experiment Name:

Separation and Estimation of

Copper and Zinc from a Mixture
Theory:
To separate and estimate Copper and Zinc from a mixture it is needed to perform
three steps.
a) Standardization of sodium thiosulfate (Na2S2O3) with standard potassium
dichromate (K2Cr2O7) solution.
b) Determination of Copper (Cu) volumetrically in presence of Zinc (Zn).
c) Separation of Copper (Cu) and determination of Zinc (Zn) gravimetrically.
The determination of Cu from a solution is preferably done by idometric titration. In
volumetric titration, a known volume of a standard solution (one whose
concentration is known) reacts with a known volume of a solution of
unknown concentration. This procedure standardizes the latter
solution, by allowing a calculation of its concentration.
The strength of Na2S2O3 is determined by titrating it with standard
K2Cr2O7.
Determination of Zn is done by gravimetric analysis. The quantitative
determination of a substance by precipitation followed by isolation and
weighing of the precipitate is called gravimetric analysis.

a) Standardization of Sodium Thiosulfate with standard

Potassium dichromate solution:
In acidic media, excess KI reduces K2Cr2O7
and liberates equivalent amount of I2. The Na2S2O3 is oxidized by this liberated iodine. In
acidic media K2Cr2O7 is a strong oxidizing agent thats why HCl is added.
The reactions that occur are mentioned belowK2Cr2O7 + 14 HCl + 6 KI

= 2 CrCl3 +3 I2 +7 H2O+8KCl

6Na2S2O3 +3I2

= 3 Na2S4O6 + 6 NaI

This reactions is idometric because in idometric reaction I2 liberates with an oxidizing

agent (here K2Cr2O7) comes from KI.
I2 is less stable in H2O, so excess amount of KI solution is used.

I2

(aq)

+ I- (aq)

= I3 (aq) (deep brown)

I2 has higher atmospheric pressure as it melts away in air and oxidized by O2 . This
phenomena causes wrong calculation in experiment due to less amount of I- . So, the
conical flask is covered with watch glass .
4I-

+ O2

+ 4 H+

= 2I2

(g)

+ 2H2O

To make inert atmosphere CO2 layer is produced upon the conical flask( I- solution) for
preventing oxidizing of I- from NaHCO3 salt solution.
NaHCO3
+ HCl = NaCl + H2O + CO2
Here , K2Cr2O7 works as an oxidizing agent and it can oxidize properly in presence of
HCl acid.
Cr2O72- + 14H+ +6 I- = 2Cr3+ + 3I2 + 7 H2O
From the above eqn. we observe I is the reducing agent that comes from KI . This
reducing agent becomes oxidized into I2 . This liberated iodine reacts with Na2S2O3 .
I2 + 2Na2S2O3

Na2S4O6 + 2NaI

After completion of this reaction, starch is used as an indicator. Because of following the
above steps there remains some I2 into the conical flask, when starch is added it makes an
absorption complex with iodine, distinguished by deep blue color.
The iodine of this starch-iodine complex reacts with Na2S2O3 .
Starch

+ I2 = Starch-iodine absorption complex

Starch-iodine absorption complex + 2Na2S2O3 = starch + 2NaI + Na2S4O6

So, again the blue color will disappear and the solution will have light blue color or light
green due to the presence of Cr3+. By this specific color change the end point is identified.

b) Determination of Cu volumetrically in presence of Zn:

The determination of Cu from a solution is preferably done by idometric titration.
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 feed 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.
Since the stock solution is acidic; it has to be neutralized by alkaline solution. Then KI is
added and the iodine liberated by Cu is then titrated with Na2S2O3 solution which was

standardize before. From the volume of Na2S2O3 of known strength we can determine the
amount of Cu Present in stock solution.
2Cu2+ + 4KI = 2CuI + I2 + 4K+
2Cu2+ I2 Na2S2O3
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.

c) Separation of Copper (Cu) and determination of Zinc (Zn)

gravimetrically:
The determination of Zn from a solution is preferably done by
gravimetric titration. Here Na2S2O3 is a reducing agent . It reduced Cu++ to Cu+ .This Cu+
reacts with NH4CNS and creates the white precipitate of CuCNS. The H2SO4 in solution
is neutralized by NH3 solution. Zn++ reacts with (NH4)2HPO4 (diammonium hydrogen
phosphate) and form Zinc pyrophosphate (ZnHPO4). The precipitate of ZnHPO4 is
ignited in a porcelain crucible and it drives up to Zn2P2O7. From the amount of Zn2P2O7
we can calculate the amount of Zn.

Cu 2+

Cu +
Na2SO3

CuCNS (White precipitation)

NH4CNS

Zn2+ + (NH3)2HPO4 = Zn(HPO4) + 2NH3

Zn(HPO4) - H2O = Zn2P2O7

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

Procedure:

First we have to standardize Na2S2O3. Potassium dichromate is used

to titrate Na2S2O3. Starch is used as indicator here.
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 pale pink color, and a distinct permanent end
point is readily obtained.
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. 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.

Data Tables:
a) Standardization of Na2S2O3 by standard K2Cr2O7 with
starch as a indicator:
No of
Volume Initial
Final
Volume Average
observ of
burette burette of
(ml)
ation
K2Cr2O Readin Readin Na2S2O
7 (ml)
g (ml)
g (ml)
3 (ml)
1
10
0.0
12.1
12.1
2
10
12.3
24.6
12.3
12.23
3
10
24.6
36.9
12.3

Calculation:

Strength
of
Na2S2O3
(M)
0.08176

Here, Volume of K2Cr2O7, V1 = 10 ml

Volume of Na2S2O3, V2 = 12.23ml
0.4851 x 0.1
Normality of K2Cr2O7, N1 =

= 0.099
0.49
x N1

V1
Normality of Na2S2O3, N2 =

V2
10

.099

=
12.23
= 0.08176

b) Estimation of Cu volumetrically in presence of Zn, Titrating

with standard Na2S2O3:
No of
Volume Initial
Observ of
Burette
ation
mixture( Reading(m
ml)
l)
1
10
0.0
2
10
12.7
3
10
25.3
Calculation: 1 L 1 N
12.45ml 0.0817 N

Na2S2O3

Na2S2O3

0.06354 g Cu

0.06354 x 12.45 x 0.0817

= 0.06463 g Cu

In 10 ml solution remains 0.06463 g Cu

In 1 L solution remains

Final
Burette
Reading(
ml)
12.5
25.1
37.6

0.06463 x 1000
10
= 6.463g Cu / L

Volume
of
Na2S2O3(
ml)
12.5
12.4
12.3

Average
volume
of
Na2S2O3
12.45

c) Separation of Copper (Cu) and determination of Zinc (Zn)

gravimetrically:
Weight of the empty crucible = 41.6845 g
Weight of the crucible with Zn2P2O7 = 41.7672 g
Weight of Zn2P2O7 = 0.0782g
1 g of Zn2P2O7 contains 0.4292 g of zinc
0.0782 g of Zn2P2O7 contains 0.4292 x 0.0782 = 33.563x 10-3 g

Result:
The amount of Copper ( Cu) = 6.463g/l
The amount of Zinc (Zn) = 33.563x10-3g
Discussion:
Not only this experiment but also all experiment must be done very
carefully. When we estimated Cu and Zn we should be very careful from the
beginning of the experiment because When we standardizing Na2S2O3 by standard K2Cr2O7 then the standardization
must be correct if we dont standardize Na2S2O3 , then the estimation of Cu
would not be perfect.
In standardization of Na2S2O3 , NaHCO3 & HCl is added to create inert
environment , otherwise iodide I- make reaction with air.
2I- + O2 +4H+ = I2 + H2O
so, to create inert environment , this reaction happens,
NaHCO3 +HCl = NaCl + H2O + CO2
When Cu is estimated , then Na2S2O3 & CH3COOH is added for same
purpose, which described in
Na2CO3 + CH3COOH = CH3COONa + H2O + CO2
To indicate the end point starch is added at last . when Na2S2O3 is
standardized and Cu is determined. Starch make reactions with the remaining
iodide ion in the solution. If starch is added at first , then it makes reaction
with iodine & iodide ion will make wrong result.
When Cu is estimated , NH4CNS is added after adding starch, because it
makes reactions with Cu2I2 & I2 is produced . Otherwise , the correct result
will not achieves
2NH4CNS + Cu2I2 = 2NH3I + 2CuCNS + I2

 The mass of crucible and Zinc Pyrophosphate is weighted carefully for getting
proper result.
Cu is separated by filtration, it should be done carefully, if Cu remained in
solution the correct weight of Zn would not achieve

Merits:
The merit of a volumetric analysis is that , it can be done in a short time. If we
be careful to trace the end point then the result would be quite acceptable. In a industry
time is a very important factor . when approximate result is acceptable then we can use
volumetric analysis to determine Cu.
On the other hand gravimetric analysis has its own merits. By this process we can
determine the exact amount of a substance. In a laboratory of science when we need to
determine the exact amount then gravimetric analysis is mostly used.

Demerits:
Though volumetric analysis can be done within a short time, there is more
probability of getting wrong result. The wrong result can be caused by not using burette
and pipette correctly.
Again gravimetric analysis needs much time. We should heat the solution and wait to
obtain a good precipitate If we make mistake in weighting of crucible there would occur
a discrepancy in result.