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IS 9252 (1979): Method for determination of zinc

(volumetric) [CHD 1: Inorganic Chemicals]

“!ान $ एक न' भारत का +नम-ण”

Satyanarayan Gangaram Pitroda
“Invent a New India Using Knowledge”

“!ान एक ऐसा खजाना > जो कभी च0राया नहB जा सकता ह”

है”
ह
Bhartṛhari—Nītiśatakam
“Knowledge is such a treasure which cannot be stolen”
( Reaffirmed 1998 )
 IS f 9252 - 1979

Indian Standard
METHOD FOR DETERMINATION OF
ZINC ( VOLUMETRtC )

Chemical Standards Sectional Committee, CDC 1

Chuirnran Representing
DR H. L. BAMI Central Forensic Science Laboratory, New Delhi

Du K. NARAYANABWANY( Alternateto
Dr H. L. Bami )
AQRICULTURAL MARKETINO Central Agmark Laboratory, Nagpur
ADVISER
SHRI 'I'. V. MATEEW ( Alternate )
SHRI A.K. BHATTACXARYA National Test House, Calcutta
SRI&IK. c. SEAL ( ifherflatc )
SHRI B. N. BH~~TTWHAILYY~ Geological Survey of India, Calcutta
SHRI v. hf. &fUCHAR National Physical Laboratory ( CSlR ), New Delhi
SHRI D. S. C~ADHA Directorate General of Health Services, New Delhi
SMT DEBI MUICIIERJICE ( Alternate )
DR M. S. CHADEA Bhabha Atomic Research Centre, Bombay
Snrtr R. s. CHATI& Municipal Corporation of Greater Bombay
CHEMIST & M r: T ‘1 I, I, ci R o 1 s ‘I’, Railway Board ( Ministry of Raiiways )
S o pi T H C~XITRAL RAILWAY,
SECUN~~RA~~D
ASSISTANT DIREC~OI~ ( MET ),
RDSO, LUCKNOW ( Alternate )
SERI D. R. GUPT~ Central Revenues Control Laboratory, New Delhi
SHIU KESHAV Pxasm ( AlterWe )
SIIRI C. HINGARI~ The Century Spg & Mfg Co Ltd, Bombay
SI~RI 0i-d I’RASAI) ( Alterwe )
DRB. N. MATTOO Maharashtra State Forensic Science Laboratory,
Bombay
Dn M. S. MAUIWALA (Alternate)
UR P. R. PABRAI Central Indian Pharmacopoeia Laboratory,
Ghaaiabad
SHRI J. K. P*%Tw~ Sarabhai M. Chemicals, Vadodara
SRRI D. RAMAMURTHY Bharat Heavy Electricals Ltd, Tiruchchirapalli
StiRI M. B. UNNI ( .-fhnate )
SHJ~IG. K. RAO Ministry of Defence ( DGI )
DR A. K. SEN ( Alternate )
( Continued on page 2 j

0 Copyright 1979
INDIAN STANDARDS INSTITUTION
This publication is protected under the Indian CoQyright Act ( XIV of 1957 ) and
reproduction in whole or in part by any means except with written permission of the
publisher shall be deemed to be an infringement of copyright under the said Act.

.*.
IS : 9252 - 1979

( Continuedfrom pags 1 )

Members Representing
DI% G. KAMANA RAO Indian Drugs & Pharmaceuticals Ltd, New Delhi
SHI~I RAN~ASWAMY ( Alternate )
D& M. P. SAHAKARI Italab Pvt Ltd, Bombay
SHRI S. S. HONAVAE ( Akrnuts )
DX B. R. SANT Regional Research Laboratory ( CSIR ),
Bhubaneshwar
DH. T. P. PXAEJAD( Alternate )
SHHI H. M. SEAIRE Natiozlmby;ganic Chemical Industries Ltd,

DE V. SRINIVAEAN Glaxo Laboratories ( India ) Ltd, Bombay

DR S. V. VOLTA ( Alterrule )
DH. R. T. THAMPY Shriram Institute for Industrial Research, Delhi
DR G. M. SAXENA, Director General, IS1 ( Ex-o#cio Member )
Director ( Chem )

Secretary
SHRI N. K. SHARMA
Deputy Director ( Chem ), ISI

2
 IS : 9252 - 1979

Indian Standard
METHOD FOR DETERMINATlON OF
ZINC ( VOLUMETRIC )

0. FOREWORD

0.1 This Indian Standard was adopted by the Indian Standards Institution
on 9 August 1979, after the draft finalized by the Chemical Standards
Sectional Committee had been approved by the Chemical Division
Council.

0.2 Zinc in small quantities is associated with a large variety of materials

of industrial importance, such as basic chemicals, ores, clays, and non-
ferrous alloys. The accuracy of the volumetric method compares favou-
rably with that of the gravimetric method. The volumetric method is
more rapid when many samples are to be analysed.

0.3 This standard is intended to achieve uniformity of the method of

determination of zinc prescribed in various Indian Standards.

0.4 In the preparation of this standard assistance has been drawn from
JIS M 8124-1965 ‘Methods for determination of zinc in ores’, published b)
Japanese Standards Association.

0.5 In reporting the result of a test or analysis made in accordance with

this siandard, if the final value, observed or calculated, is to be rounded
off, it shall be done in accordance with IS : 2-1960*.

1. SC;OPE

1.1 This standard prescribes the methods for the volumetric determination
of zinc by using (a) potassium ferrocyanide, and (b) ethylenediamine
tetraacetate ( EDTA ).

*Rules for rounding% numerical values ( raised ).

3
IS : 9252 - 1979

2. QUALITY OF REAGENTS

2.1 Unless specified otherwise, pure chemicals and distilled water ( see
IS : 1070-1977* ) shall be used in tests.
NOTX - ‘Pure chemicals ’ shall mean chemicals that do not contain impurities
which af&ct the results of analysis.

3. POTASSIUM FERROCYANIDE METHOD

3.1 Outline of the Method -The sample is decomposed with hydro-

chloric acid and nitric acid and hydrogen sulphide gas is passed to
precipitate cadmium and copper. Ammonium chloride, ammonium
hydroxide and bromine water are added to the filtrate to remove iron
and manganese. Hydrochloric aci’d is added to the solution which is
titrated with potassium ferrocyanide standard solution using uranyl salt
indicator.

3.2 Reagents

3.2.1 Concentrated Hydrochloric Acid - ( see IS : 265 - 1976t ).

3.2.2 Hydrochloric Acid - 1 : 1, 1 : 2, 1 : 5, and 1 : 50.

3.2.3 Nitric Acid - 1 : 1.

3.2.4 Sulphuric Acid - 1 : 2.

3.2.5 Ammonium Hydroxide

3.2.6 Hydrogen Sulphide Gas

3.2.7 Bromine Water

3.2.8 liydrogen Peroxide - 1 : 10.

3.2.9 Ammonium Chloride

3.2.10 Ammonium Persulphate

3.2.11 Ammonium Carbonate

3.2.12 Ammonium Chloride Wash Solution -Dissolve 20 g of ammonium

chloride in water, add 10 ml of ammonium hydroxide and dilute to
1 litre.
3.2.13 Litmus Paper

3.2.14 Hydrogen Sulphide Water - saturated.

*Specification for water for general laboratory use ( secondrevision ) .

TSpecification for hydrochloric acid ( second r&&n ).

4
 is : 9252 - 1979
3.2.15 Uranyl Salt Indicator - Dissolve 10 g of uranyl acetate or uranyl
nitrate in water and dilute to 100 ml.

3.2.16 Potassium Ferrocyanide Standard Solution - Dissolve 21.6 g of

potassium ferrocyanide in water, and dilute with water to 1 litre.
Standardize this solution as follows.

3.2.16.1 Weigh accurately 0.25 g of zinc into a 500-1111 conical flask.

Add 10 ml of hydrochloric acid to dissolve it completely. Then add
100 ml of water and 14 g of ammonium chloride and neutralize with
ammonium hydroxide using litmus paper and add 5 ml of hydrochloric
acid. Add 50 ml of hydrogen sulphide water ( saturated ) and dilute
with water to about 250 ml. Titrate zinc in accordance with 3.3.5 and
calculate the mass of zinc equivalent to 1 ml of potassium ferrocyanide
solution as follows:

where
m = mass in g of zinc equivalent to 1 ml of potassium
ferrocyanide solution,
1M = mass in g of zinc taken,
VI = volume in ml of potassium ferrocyanide solution consumed
in titration, and
vz = volume in ml of potassium ferrocyanide solution consumed
for the blank.

Store this standard solution in a brown bottle in a dark place and

restandardize prior to use.

3.3 Procedure
3.3.1 Weigh accurately 0’3 to 1 g of the sample into a 300-ml beaker.
Cover with a watch glass and moisten with small amount of water. Add
20 to 30 ml of hydrochloric acid and gently heat to volatilize sulphur
contained in sulphide as hydrogen sulphide gas. Add 10 ml of nitric
acid, continue the heating to decompose the sample completely and
evapomte to nearly dryness. After cooling, add 10 ml of hydrochloric
acid ( 1 : 1 ) to dissolve soluble salts and dilute with water to 3 percent
by volume of hydrochloric acid solution.

3.3.2 Heat the solution to 80 to 90°C and immediately pass hydrogen

sulphide gas for 20 to 30 minutes. After standing a while, filter, and wash
the filter paper with hydrochloric acid ( 1 : 50 ) saturated with hydrogen
sulphide gas. Collect the filtrate and.washings in a 500,-ml beaker and
reserve as the main solution.

5
IS 89252.1979

3.3.3 Place the original beaker under the funnel, add dropwise 9 ml of
hydrochloric acid ( 1 : 2 ) into the filter paper to dissolve the precipitate
and wash with about 100 nrl of warm water.

3.3.4 Heat the solution and pass hydrogen sulphide gas to precipitate
sulphides in the same way as prescribed in 3.3.2. Filter, wash and
combine the filtrate and washings with the main solution reserved in
3.3.2.

3.3.5 Heat the solution to evaporate to about 50 ml and add a small

amount of bromine water or hydrogen peroxide water. Heat the
solution to oxidize iron, etc, and add 5 g of ammonium chloride.
Add, under stirring, 15 ml of ammonium hydroxide to precipitate iron,
etc, followed by 10 to 20 ml of bromine water or 0.5 g of ammonium
persulphate, ancl boil the solution for a few minutes covered with a watch
glass.

3.3.6 After standmg a while, filter the solution into a 500-ml conical
flask, and was!~ the filter paper several times with ammonium chloride
wash solution. Reserve the filtrate and washings as the main solution.
Wash the precipitate with water into the original beaker, add 10 ml of
hydrochloric acid ( 1 : 1 ) and heat to dissolve the precipitate.

3.3.7 Add 3 g of anuuonium chloride and repeat the procedure as in

3.3.5 with the addition to ammonium hydroxide and bromine water or
ammonium persulphate to precipitate iron, etc. Filter the precipitate
through the original filter paper, and wash with ammonium chloride wasik
solution. Combine the filtrate and washings lvith the main solution.
Boil the solution for a. few minutes to decompose the excess of bromine or
ammonium persuiphate present and adjust the volume of the solution to
about 200 ml.
3.3.8 Add dropwise hydrochloric acid to neutralize the solution against
litmus paper. Add additional 5 ml of the acid, followed by 50 ml of
hydrogen sulphide water ( saturated ) and titrate the solution with
potassium ferrocyanide solution using uranyl salt as the external indicator
keeping the solution temperature at 75 to 80°C. In the titration, add
potassium ferrocyanide solution in small increments at first and shake
t.lre flask every time. The precipitate produced will gradually become
fine as the titration proceeds and becomes milky at the approach of the
end point. Add 1 or 2 drops of the standard solution and shake the flask
after each addition. Take one drop of the solution with a gIass rod on
a porcelain plate and mix with the external indicator placed on the
plate. Continue the titration until the mixed solution changes colour
from yellowish green to pale brown. Titrate three times to arrive at the
exact volume of potassium ferrocyanide solution required. Run the
blank for all reagents under the same condition and calculate the zinc

6
 IS : 9252 - 1979

3.4 Calculation
m x ( v1- v2_> x 1()(-J
Zinc ( as Zn ), percent by mass =
M

where
m -- equivalent in g of zinc to 1 ml of potassium ferrocyanide
solution,

VI = volume in ml of potassium ferrocyanide solution consumed

in titration,
Vz = volume in ml of potassium ferrocyanide solution for the
blank, and
M = mass in g of the sample taken in the test solution.

4. EDTA METHOD

4.1 Principle of the Method - The sample is decomposed with hydro-

chloric acid and nitric acid and zinc is retained on a strongly basic anion
exchange resin. The resin column is washed with dilute hydrochloric
acid and then zinc is eluted with dilute ammonium hydroxide containing
ammonium chloride. The @H value of the eluate is adjusted to about
5.5 and titrated with EDTA standard solution using xylenol orange
indicator.

4.2 Apparatus
4.2.1 Ion-Exchange Resin Column .- Ion exchange resin column shall be
as shown in Fig. 1. The resin, to be filled in the tube, shall be of
strongly basic .anion exchange resin of grain size 215 to 150 micron IS
sieve ( see IS : 460-1962+ ). Fill about 20 g of the resin with water into
the tube and pour 100 ml of ammonium hydroxide ( 7 : 100 ) at a rate
of 5 ml per minute, followed by about 50 ml of water at the same rate.
Wash the column with 100 ml of hydrochloric acid ( 1 : 5 ) and finally
with 50 ml of water. Repeat this procedure.

When the resin is used again, only one washing cycle is necessary.

4.3 Reagents
4.3.1 Concentrated Hydrochloric Acid - ( see IS : 265 - 1976t ),

4.3.2 Hydrochloric Acid - 1 : 5.

4.3.3 Nitric Acid - 1 : 1.

*Specification for test sieves ( rsvisad ).

*Specification for hydrochloric acid ( second revihon ).
IS I 9252- 1979

4.3.4 Sulphuric Acid - 1 : 1 and 1 : 10.

4.3.5 Acetic Acid - 1 : 1.
4.3.6 Ascorbic Acid - Hydrochloric Acid Solution - Dissolve 0.25 g of
ascorbic acid in hydrochloric acid ( 1 : 5 ) and dilute to 100 ml.
l

RESIN COLlJMN
LENGTli 200

All dimensions in millimetres.

FIG. 1 ION EXCHANGE RESIN COLUMN

4.3.7 Ammoniacal I&ent - Dissolve 20 g of ammonium chloride in 1 litre

of ammonium hydroxide ( 7 : 100 ).
4.3.8 Buffer Solution - Dissolve 250 g of ammonium acetate in water,
add 25 ml of glacial acetic acid and dilute with water to 1 litre. Adjust
the pH value to about 5.5 by means of a PH meter.
4.3.9 Ammonium Fluoride Solution - 5 percent ( m/v >.
4.3.10 Sodium Thiosulphate Solution - 10 percent ( m/u ).

8
 IS : 9252 - 1979

4.3.11 Xylenol Orange Indicator Solution - Dissolve 9.1 g of xylenol

orange in 100 ml of water or 100 ml of 50 percent ethyl alcohol ( o/u).

4.3.12 Sodium Diethyl Dithiocarbamatr

4.3.13 Eriochrome Black 7 Indicaior Solution - Dissolve 0.5 g of

eriochrome black T in 100 ml of ethyl alcohol and add 4 g of hydroxyla-
mine hydrochloride.

4.3.14 <in Standard Solution - 0.05 hl. Weigh accurately 3.269 g of

zinc into a 500-ml conical flask and add 20 ml of hydrochloric acid to
dissolve it. Heat the solution and dilute with water to exactly 1 litre.
Standardize this solution with EDTA standard solution ( O-05 M ) as
follows.
4.3.14.1 T’o 10 ml of EDTA standard solution add 180 ml of
ammoniacal cluent and a few drops of Eriochrome black T indicator
solution and titrate with the zinc solution until the colour changes from
blue to violet.

4.3.15 &V%l Sfundard Solution - 0.5 M. Dissolve 18’610 g of disodium

ethylenediamine tetraacetate dihydrate in water and dilute to 1 litre.
One millilitrc of this solution is equivalent to about 3.269 mg of zinc.
Standardize this solution as follows.
4.3.15.1 Weigh accurately 0’15 g of zinc into a 500-1~1 conical flask
and add 10 ml of hydrochloric acid to dissolve it. Add 180 ml of
ammoniacal eluent, neutralize with acetic acid ( 1 : 1 ) and proceed as
prescribed in 4.4.3. Calculate the mass of zinc equivalent to 1 ml of
EDTA solution as follows:
L%l
m=&=-&
where
m = mass of zinc equivalent to 1 ml of EDTA solution,
M = mass in g of zinc taken,
1’1 = volume in ml of EDTA solution consumed in titration
for sample, and
li, = volume in ml of EDTA solution consumed in titration
for the blank.

4.3.15.2 For the sample containing small amount of zinc, EDTA

solution ( 0.01 M ) shall be prepared.

4.4 Procedure
4.4.1 Weigh accurately 0.3 to 1 g of the sample into a 250-ml beaker.
Cover with a watch glass and moisten with a small amount of water.

9
1s : 9252 - 1979

Add 20 to 30 ml of hydrochloric acid and gently heat to volatilize

sulphur contained in sulphide as hydrogen sulphide gas. Then add 10 ml
of nitric acid, continue heating to decompose the sample completely.
Add 10 ml of sulphuric acid ( 1 : 1 ) and heat to evolve white fumes.
After cooling add 50 ml of water, heat to dissolve soluble salts and allow
to cool to room temperature. Filter the precipitate and wash several
times with cold sulphuric acid ( 1 : 10 ). Collect the filtrate and wash-
ings in a 250-1111 beaker and pour into the dropping funnel of the
apparatus. Add 16 ml of hydrochloric acid and water to make to 100 ml
and mix well.

4.4.2 Pour the solution on to the column at a rate of about 6 ml per

minute and allow the zinc to be adsorbed in the column. After comple-
tion of the pouring, add 100 ml of llydrochloric acid followed by 100 ml
of ascorbic acid-hydrochloric acid solution and finally 100 ml of hydro-
chloric acid to wash the column, adding about 7 ml of each solution per
minute.

4.4.3 Add 180 ml of the ammoniacal elucnt at a rate of about 6 ml per

minute to elute the zinc from the column and collect the effluent in a
500-ml beaker. Neutralize the solution with acetic acid and add 20 ml
of buffer solution to adjust the pH value to 5.0 to 5.5. Then add 2.5 ml
of ammonium fluoride solution 5 percent ( m/u ), 5 ml of sodium
thiosulphate solution [ 10 percent ( r/z/v ) ] and a few drops of xylenol
orange indicator solution and titrate with EDTA solution until the
solution changes colour from pink to yellow.

4.5 Calculation

4.5.1 Calculate the zinc content as follows:

ni \; ( VI - Vz )
Zinc ( as Zn ), percent by mass = -- - N - x 100

where
m = mass in g of zinc equivalent to 1 ml of EDTA solution,

VI = volume in ml of EDTA solution consumed in titration for

sample,
Vz = volume in ml of EDTA solution consumed for the blank,
and

&I == mass in g of the sample taken.

10