EXPERIMENT 16

ESTIMATION OF COPPER AND ZINC

IN A MIXTURE BY GRAVIMETRY

Structure

16.1 Introduction
Objectives
16.2 Principles
16.3 Requirements
16.4 Procedure
16.5 Observations
16.6 Calculations
16.7 Result

16.1 INTRODUCTION
In the estimation of copper and zinc in a given mixture, we first estimate copper as
copper(1) thiocyanate (CuCNS) and then in the filtrate, we estimate zinc as zinc
ammonium phosphate (ZnNH4P04). The test solution, if not provided by the
counseilor, can be prepared by dissolving accurately 5-6 grams of copper sulphate
and 2-3 grams of zinc chloride in a migjmarn quantity of dilute HCl and then making
up the volume to 250 ma3* srandard volumetric flask. 50 cm3 of this solution can
be taken for estimation.

Objectives

After studying and performing this experiment, you should be able to:

estimate cu2+ and 2n2+ together by gravimetry.

16.2 PRINCIPLE
The test solution, containing copper and zinc, is first treated with sulphurous acid or
ammonium hydrogen sulphite to reduce Cu(I1) to Cu(1). Ammonium thiocyanate
solution is then added to precipitate copper as copper(1) thiocyanate. The reactions
that take place are shown below.

~ C U ~ + ( ~ ~ ) + H S O ~ ( ~2cu+(aq)
~ ) + H+ ~H O
S O( ~~( O
~ +~2) ~ + ( a g )

cu+(aq) +SCN-(U~- CuSCN(s)

After filtering the precipitate, diammonium hydrogen phosphate solution is added to
the filtrate to precipitate zinc as zinc ammonium phosphate:

ZnC12(aq) + (NH4)2HP04(aq)---,ZnNH4P04(s) + HCl(aq)

The precipitate is filtered, washed, dried and weighed. By knowing the mass of
CuSCN and ZnNH4P04 formed, we can calculate the concentrations of copper
sulphate and zinc chloride in the solution.

The names and atomic/molar masses of species involved in this experiment are given
below.
 Formula/Symbol Molar,Atomic mass Estimation of Copper and Zinc
in a Mixture by Gravimetry
CuS04.5H20 249.50
Copper(1) thiocyanate CuSCN
Zinc ammonium phosphate ZnNH4P04
Zinc chloride ZnC12
Zinc Zn
Copper Cu

16.3 REQUIREMENTS
You will need the following apparatus, chemicals and solutions for this experiment

Apparatus Chemicals
Beaker 500 cm3 2 Nos 10% Ammonium thiocyanate
Beaker 250 cm3 1 No. Aqueous ammonia
Bunsen burner 1 No. 10% Diamrnonium hydrogen phosphate
Desiccator 1 No. Conc. Hydrochloric acid
Filtration apparatus 1No. Methyl red indicator
Flask conical 250 cm3 1 No. Conc. Nitric acid
Glass rod 1 No. Ammonium hydrogen sulphite solution
Pair of tongs 1 No. Test Solution
Rubber police-man 1 No.
Sintered crucible (G-4) 1 No.
Tripod stand 1 No.
Wash bottle 1 No.
Watch glass 1 No.
Water bath 1 No.
Wire guaze 1 No.
Weighing bottle 1 No.
Weight box 1 No.

16.4 PROCEDURE
The experimental procedure involves the following steps:

(A) Estimation of copper

1. Pipette out 50 cm3 of test solution either assigned by your counsellor or
pre ared by you in a 500 cm3 beaker. Add into it 5 cm3 dilute HCl and 25
B
cm ammonium hydrogen sulphite solu.tign and ensure that smell of SO2
prevails.

11. Boil gently on a water bath. Remove the flame and add slowly 50 cm3 of 10%
NH4SCN soIution. Keep stirring the precipitate intermittently with a glass
rod. Allow the solution, containing the precipitate, to rest for 30-60 minutes.

111. Weigh a n empty and cleaned sintered glass crucible of porosity G- 4 and note
the mass. Filter the precipitate, obtained in step 11, through this crucible first
by draining off the supernatant liquid and then the precipitate with minimum
Chemistry Lab-V quantity of liquid. By this procedure the precipitate is kept away from
clogging the pores of the crucible.

IV. Wash the precipitate with 2-3% NH4SCN solution. Wait and check the
filtrate for any precipitate formed. If any precipitate appears, filter it again.
Finally wash the precipitate several times with 20% ethanol until the
precipitate is free from S C N ions. Preserve the filtrate for estimation of zinc.

V. Now heat the sintered glass crucible at a temperature of 100- 1 2 0 ' ~in an hot
air oven for at least an hour.

VI. Cool the crucible in a desiccator and then weigh. Repeat the process of
hkating, cooling and weighing until a constant mass of the crucible with
precipitate is obtained. '

(B) Estimation of zinc

I.. Evaporate on a water bath, the filtrate obtained in step IV in the estimation
of copper. Reduce the "olume of the solution to nearly 100 cm3 by
evaporation. Now add. 20 cm3 concentrated nitric acid and 15 cm3
concentrated HCl and again heat t o dryness on a water bath in a fume hood.

T o the residue, obtained in step I, add 100 cm3 of distilled water and dissolve
the a n t e n t s by shaking. Add 2-3 drops of methyl red indicator and then add
10% aqueous ammonia solution till smell of ammonia prevails and the colour
of the methyl red changes to yellow.

T o the solution obtained in step 11, add slowly 10% diammonium hydrogen
phosphate with adequate stirring with a glass rod. Digest the precipitate on a
water bath atleast for 30 minutes.

IV. Filter the precipitate, obtained in step 111, through a previously weighed
sintered crucible of porosity G-4. Drain out the supernatant liquid first and
then the precipitate with minimum quantity of liquid.

V. Wash the precipitate with 2-3% diammonium hydrogen phosphate (DAI-IP)

solution. Einally wash the precipitate with 50% alcohol t o remove the excess
of DAHP. Check if any phosphate ions are present in the washings.

VI. Heat the crucible and the precipitate a t temperature range 100- 1 2 0 ' ~in an
hot air oven. Cool the crucible in a desiccator and then weigh it. Repeat
heating, cooling and weighing till a constant mass of the c r u ~ i b l ewith
precipitate is obtained.

16.5 OBSERVATIONS

i) 1st mass of empty crucible

i i) 2nd mass of empty crucible
iii) 1st mass of crucible+ CuSCN
iv) 2nd mass of crucible + CuSCN
v) 1st mass of empty crucible
vi) 2nd mass of empty crucible
vii) 1st mass of crucible / ZnNH4P04
viii) 2nd mass of crucible $ ZnNH,PO,
 Estimation of Copper and Zinc
16.6 CALCULATIONS in a Mixture by Gravimetry

Calculations for copper

Mass of CuSCN obtained = iv) - ii)= ...............g = W g

From stoichiometrywe know, .

CuS04.5H20 I cu2+ s CuSCN '

249.5 g = 63.54 g = 121.62 g

249.5~~
Hence, w g of copper(1) thiocyanate = g of copper(I1) sulphate.
121.62.

This much copper(I1) sulphate is present in 50 cm3 of test solution. Hence,

concentration of copper(I1) sulphate in test solution

249.5~1000x mass of CuSCN

Concentration of CuS0,.5H20 = g dm-3
121.62~volume of test solution

Calculations for zinc

Mass of ZnNH4P04 obtained = viii) - vi) =............g =w' g

From stoichiometry we know
znc12=zn2+=ZnNH4P04

Hence, w ' g of ZnNH4P04 E 136'37xw' g of-zncl, .

178.34
This much ZnC12 is pl'esent in 50 cm3 of test solution.
Hence, concentration of ZnC12 in test solution

136.37~1 0 0 0 ~
mass of ZnNH4P04
Concentration of ZnC12 = g dm-3
178.34~Volume of test solution

16.7 RESULT
You can report your result in the following manner:
Concentration of copper(I1) sulphate in the test solution = ...... g dm-3
Concentration of zinc chloride in the test solution = ......g dm"