(Reaffirmed 2001)

IS:9386 - 1979

Indian Standard
METHODS FOR CHEMICAL
ANALYSIS OF ROCK PHOSPHATE

Methods of Chemical Analysis Sectional Committee, SMDC 2

Chairman Reprcscnfing
DR R. K. DUTTA Steel Authority of India Ltd (Durgapur Steel
Plant ), Durgapur

SHRI G. M. APPARAO Steelg;;gl;hority of India Ltd ( Bhilai Steel Plant ),

SHRI R. K. GUPTA ( Altcrnat~ )

SRRI P. K. BANERJEE Directorate General of Ordnance Factories ( Minis-
try of Defence ), Calcutta
SHRI H. C. BHARQAVA India_ Gpvcrnment Mint ( Ministry of Finance ),
UOmbay
SRRI J. BRATTAOHARJEE Ministry of Dcfence ( DGI )
SHRI M. Y. BOREER ( Akmtate )
DR V. M. BHUCHAR National Physical Laboratory ( CSIR ), New Delhi
DR S. K. BISWAS Hindustan Copper Ltd, Calcutta
SERI S. N. BOEIDAR Steel Authority of India Ltd ( Rourkela Steel Plant ).
Rourkcla
SHRI P. CHAKRA Indian Metals & Ferro Alloys Ltd, Koraput
DE M. M. CHAKRABORTY Indian Iron & Steel Co Ltd. I Burnour
1
SHIZI A. C. MUKHERJEE ( Alternate )
c IIEMlST & METALLURCXST, Ministry of Railways
SOUTH CENTRAL RAILWAY,
SECUNDERABAD
ASSISTANT DIRECTOR ( MET ),
RDSO, CHITTARANJAN ( Alternate )
CEIEF CHEMIST The Tata Iron & Steel Company Ltd, Jamshedpur
ASSISTANT CHIEF CHEMIST ( Alternate )
DR A. N. CHOWDHURY Geological Survey of India, Calcutta
SHRI B. N. BHATTAOHARYA( Alternate )
SHRI H. P. DEBEY National Test House, Calcutta
DR B. C. DUTTA Bharat Aluminium Company Ltd, New Delhi
SHRI K. P. MUKHERJRE ( Alternate )

( Continued on page 2 )

@ Copyright 1980
INDIAN STANDARDS INSTITUTION
This publxation is protected under the Indian Copyright Act ( XIV of 1957 ) and
rcproductlon in whole or in part bv any means except with written permission of the
publisher shall be deemrd to be an infringement of copyright under the said Act,
IS t9386 - 1979
( Continued,from pagr 1 )

Members Rcpressnting
SHBI S. N. HONAVAR Italab Private Ltd, Bombay
SHRI J. Cl. DEY ( Alternate I )
SHRI J. P. PATEL ( Alternate II )
SHRI D. P. JAIN Saru Smelting Pvt Ltd, Meerut
SHRI D. N. CH.~KRABO~~TY ( Alternate )
SHRI G. L. JETHWANI Hindustan Zinc Ltd, Udaipur
SHBI V. B. KHANNA Direcrorate General of Supplies & Disposals,
New Delhi
SHRI M. P. CHOWDIKTRY ( Alternats )
DR L. P. PANDEY National Metallurgical Laboratory ( CSIR ),
Jamshedpur
SHRI B. N. PRASAD SteelB.4;;f;rity of India Ltd ( Bokaro Steel Plant ),

DR J. RAJARAM Esscn & Co, Bangalore

SIIBI K. RAMAKRIS~NAN ( Alternate )
SHRI D. RAMAMOORTHY . Bharat Heavy Electricals Ltd, Tiruchirapalli
SHRI M. B. UNNI ( Alternate )
SHRI M. K. RAO Binani Metal Works Ltd, Calcutta
SHRI A. SANOAX~ESWARARAO Ferro Alloys Corporation Ltd, Shreeramnagar
SHRI G. RAJABAO ( Alternate )
DR B. C. SINHA Central Glass & Ceramic Research Institute
( CSIR ), Calcutta
SHRI R. SEN ( Altarnate )
DR P. SUBRAMANIAM Ministry of Defence ( R & D )
DR B. V. RAO ( Alternate )
DR CH. VENKATESWARLU Bhabha Atomic Research Centre, Bombay
DR C. S. P. IYER ( Aftcrnutc I )
SERI P. MURUQAIYAN ( Alternate II )
SHXI C. R. RAMA RAO, Director General, IS1 ( Ex-&cio Member )
Director ( Strut & Met )

Sccrctary

SHRI S. L. BALI
Deputy Director ( Met ), IS1

2
 lS:9386-1979

Indian Standard
METHODS FOR CHEMICAL
ANALYSIS OF ROCK PHOSPHATE

0. FOREWORD
0.1 This Indian Standard was adopted by the Indian Standards
Institution on 27 June 1979, after the draft finalized by the Methods of
Chemical Analysis Sectional Committee had been approved by the
Structural and Metals Division Council.
0.2 In order to determine correctly the main constituents of rock
phosphate, standard methods of analysis have been laid down in this
standard. These methods may also be used for routine analysis.

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

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

1. SCOPE
I.1 This standard covers the methods for determination of phosphorus
pentoxide, calcium oxide, fluorine and carbon dioxide in rock phosphate.

2. SAMPLING
2.1 The samples shall be drawn in accordance with IS : 1817-1961t.

3. QUALITY OF REAGENTS

3.1 Unless otherwise specified, pure chemicals and distilled water (JCC .
IS : 1070-1977:) shall be employed in the test.
NOTE - ‘ Pure chemicals ’ shall mean chemicals that do not contain impurities
which affect the results of analysis.

4. DETERMINATION OF PHOSPHORUS PENTOXIDE

4.1 Outline of the Method - Phosphorus is directly precipitated as

magnesium-ammonium-phosphate in presence of ammonium citrate,
ignited and weighed as magnesium pyrophosphate.

*Rules for rounding off numerical valurs f revised ).

tMethods of sampling non-ferrous metals for chemical analysis.
SSpecification for water for general laboratory use ( second rcvirion).

3
IS : 9386 - 1979

4.2 Reagents

4.2.1 Concentrated Hydrochloric Acid -r d = 1.16 ( conforming to IS :

265-1962* ).

4.2.2 Concentrated Nitric Acid - rd = 1.42 ( conforming to IS : 26 4-

196nt ).
4.2.3 Ammonium Citrnte - solid.

4.2.4 Magnesia Mixture - Prepare magnesia mixture as follows:

Dissolve 400 g of magnesium chloride (MgC12. 6HtO ) and 300 g

of ammonium chloride in 1500 ml of warm water. When solution
is complete, add ammonium hydroxide until the solution is alkaline
to litmus. Allow to stand for about one hour. filter, and add
hydrochloric acid ( 1 : 1 ) to the filtrate until the solution is acid to
litmus. If properly prepared, the volume of the solution is almost
2 litres.
4.2.5 Concentrated Ammonium Hydroxide - r d = 0’89.

4.2.6 Dilute Ammonium Hydroxide - 1 : 20 ( v/v ).

4.2.7 Dilute Hydrochloric Acid - 20 percent.

4.2.8 Citric Acid - solid.

4.3 Procedure

4.3.1 Transfer 0’5 g of a sample that has been dried at 105°C to a

500-ml Erlenmeyer flask, and add 15 ml of concentrated hydrochloric
acid and 3 ml of concentrated nitric acid. Place a small cover glass over
the mouth of the flask,. and boil gently for 30 minutes. Rinse and
remove the’ cover glass, and add 30 g of ammonium citrate, 10 ml of
concentrated hydrochloric acid, and 100 ml of magnesia mixture.
Neutralize the solution with concentrated ammonium hydroxide. using
litmus paper as indicator, and add 3 ml of concentrated ammonium
hydroxide in excess. Dilute the solution to 225 to 250 ml with water,
add a few glass beads, stopper the flask tightly, shake vigorously for
about one-ar.d-a-half hours, and allow to stand overnight. Filter through
a paper of close texture, and wash the flask and paper once with a small
quantity of dilute ammonium hydroxide. Discard the filtrate.
4.3.2 Dissolve any magnesium ammonium phosphate remaining in the
flask in about 50 ml of warm dilute hydrochloric acid and then pour the
solution through the paper to dissolve the phosphate that was transferred
to the filter and to separate any insoluble residue that may have remained

“Specification for hvdrochloric acid ( raised ).

tSpecification for n’itric acid (first rruision ).

4
 IS : 9386 - 1979

after the acid attack. Wash the paper and flask with more of the same
acid, and add 0’3 g of citric acid and 1 ml of magnesia mixture to the
solution, which should have a volume of about 100 ml. While stirring,
slowly add concentrated ammonium hydroxide until the solution is
alkaline to litmus, and then add 5 ml in excess. Stir occasionally during
one-and-a-half hours, and allow to stand for 4 hours or overnight.

4.3.3 Collect the precipitate on a g-cm paper of close texture, wash

with cool dilute ammonium hydroxide and transfer the paper and
precipitate to a weighed silica or porcelain crucible. Char the paper
without flaming, burn off the carbon below 900°C and finally ignite to a
constant mass, preferably in a muffle, at 1 050 to 1 100°C.
4.3.4 Make a blank determination using the same procedure and same
quantities of reagents but without the sample.

4.4 Calculation
( A - I3 ) x 63.78
Phosphorus pentoxide, percent =
C

where
A = mass in g of the magnesium pyrophosphate precipitate,
B = correction for the blank, and
c I mass in g of the sample taken.

5. DETERMINATION OF CALCIUM OXIDE BY THE OXALATE

( VOLUMETRIC ) METHOD
5.1 Outline of the Method - Calcium is precipitated as oxalate,
filtered, washed, dissolved in hydrochloric acid and reprecipitated. This
precipitate is filtered, washed, dissolved in sulphuric acid and titrated
with standard potassium permanganate solution.

5.2 Reagents

5.2.1 Concentrated Hydrochloric Acid - See 4.2.1.

5.2.2 Concentrated JVitric Acid - See 4.2.2.

5.2.3 Hydro~7uoric Acid - 40 percent.

5.2.4 Sodium Carbonate ( AR ) - solid.

5.2.5 Dilute Hydrochloric Acid - 1 : 1 ( v/v ).

5.2.6 Ammonium Chloride - solid.

5.2.7 Dilute Acetic Acid - 1 : 1 ( v/v ).

5
IS :9386- 1979
5.2.8 Ammonium Oxalate - solid.

5.2.9 Oxalic Acid Solution - 1 g/l ( m[v ).

5.2.10 Dilute Sulphuric Acid - 1 : 4 ( v/v ).

5.2.11 Standurd Potassium Permanganatc Solution (0’1 N) - Dissolve 3.2 g

of potassium permanganate in 1 litre of water. Let stand in the dark
overnight. Fiiter, without washing, through glass wool. Avoid contact
with rubber or other organic material. Store m a dark-coloured glass-
stoppered bottle. Standardize against standard sodium oxalate ( AR ).

5.3 Procedure
5.3.1 Transfer 0’3 g of the sample that has been dried at 105 & 5°C to
a 400-ml tall form beaker. Dissolve, by boiling gently with 20 ml of
concentrated hydrochloric acid and 10 ml of concentrated nitric acid,
until the volume is reduced to about 10 ml. Covering the beaker by a
watch-glass throughout the process of dissolution, add 20 ml of concent-
rated nitric acid, and again evaporate to a small volume. Wash the
lower surface of the watch-glass into the beaker with hot water, dilute
the contents of the beaker with about 20 ml of hot water, filter and
wash collecting the filtrate and washings in a 250-ml measuring or
volumetric flask. Preserve the filter and washings.

5.3.2 Dry the residue and burn off the filter paper by ignition in a
platinum crucible. Moisten the coo!ed residue with a few drops of
concentrated nitric acid, and add about 10 ml of hydrofluoric acid.
Evaporate continuously just to dryness, ignite and fuse the residue with
about 2 to 3 g of sodium carbonate. Extract the melt in about 25-30 ml
of dilute hydrochloric acid in a beaker, evaporate to dryness and bake.
Extract the baked mass with about 10 ml of concentrated hydrochloric
acid, dilute, ,boil, filter and wash collecting the filtrate and washings in
the same volumetric flask wherein the first filtrate along with washings
has been preserved ( .ree 5.3.1 ). Cool the combined filtrates and make
up to the mark.
5.3.3 Pipette out exactly 100 ml from the solution in the volumetric
flask under 5.3.2 into a 400-ml beaker. Add sufficient ammonium
chloride ( about 15 g ) to hold magnesium in solution in presence of
ammonium oxalate. Add 20 ml of dilute acetic acid, heat to boiling and
add with stirring about 2 g of ammonium oxalate. Roil :;nd allow the
precipitate to settle for 1 to 2 hours, cool and filter the solution through
a close texture paper. Wash the precipitate with hot wattr until ft,ee
from oxalate.

5.3.4 Dissolve the precipitate on the filter in about 50 ml of hot dilute

hydrochloric acid. Wash the filter thoroughly with hot water until the
filter is free from acid and collect the washings also in the same beaker

6
 IS : 9386 - 1979

in which calcium was first precipitated. Reduce the bulk to about 100 ml
by evaporation and reprecipitate calcium as oxalate as under 5.3.3.

5.3.5 Filter the precipitate and wash first with water containing oxalic
acid or ammonium oxalate and then with water until the final washings
are free from oxalate or oxalic acid.

5.3.6 Wash the precipitate of calcium oxalate into the same braker in
which precipitation was first carried out and treat the filter with about
25 ml of warm ( 70 to 80°C ) dilute sulphuric acid for dissolving
adhering precipitate of calcium oxalate. Wash the filter free from acid
by means of hot water. Collect the washings also in the same beaker
into which the precipitate was transferred. Add about 25 ml more of
dilute sulphuric acid and raise the temperature of contents to about 70°C.
When the precipitate has dissolved, titrate with standard potassium
permanganate solution until a permanent pale pink colour persists in
solution.

5.4 Calculation
A x B x 0 028 x loo
Calcium oxide, percent =
c

where

A = volume in ml of the standard potassium permanganate

solution,
B = normality of the standard potassium permanganate
solution, and
C = mass in g of the sample represented by the aliquot taken.

6. DETERMJNATION OF FLUORINE BY DISTILLATION

METHOD
6.1 Outline of the Method - Fluorine is separated as hydrofluosilicic
acid by distillation with perchloric acid and determined by titration
against standard thorium nitrate solution using sodium alizarine
sulphonate as indicator.

6.2 Apparatus
6.2.1 The distillation apparatus ( see Fig. 1 ) consists of a 250-ml
distillation flask ( A ), side arm of which is connected to a condenser
( B ). The neck of the flask is fitted with a two-holed rubber stopper
carrying a thermometer ( C) and 4 mm glass tube ( D ) connects the
flask to a steam generator ( E ) which is equipped with two discharges,
one tube ( F) to release steam and the other ( D ) to deliver steam into
the distillation flask ( A ). The distillate is collected in a Erlenmeyer
flask ( G ).

7
 500 ml
Fm. 1 ‘APPARATUS FOR DISTILLATION
OF FLUORINE

6.3 Reagents

6.3.1 Perchloric Acid - 70 percent.

6.3.2 Sodium Alizarine Sulphonate Indicator - Dissolve 0.050 g of alizarine

sulphonate in 100 ml of water, and store in a dropping bottle.

6.3.3 Sodium Hydroxide Solution - Dissolve 20 g of sodium hydroxide

pellets in water, cool and dilute to one litre. Mix well.
6.3.4 Dilute Hydrochloric Acid - Dilute 19.6 ml of concentrated
hydrochloric acid ( rd = 1’16 ) to 1000 ml with water. Mix well.

8
 IS : 9386 - 1979

6.3.5 Buffer Solution - Dissolve 9’40 g of monochloracetic acid in

100 ml of water. Add 50 ml of sodium hydroxide ( 1-O N ). Check the
J’IH by PH meter. The PH should be 3.0 f 0.1.

6.3.6 Standard Thorium Nitrate Solution ( 0.025 M ) - Dissolve 13’8OG g

of thorium nitrate ‘Th ( NOa )d 4Hz0, in water and make up to one
litre. Mix well. Standardize against standard sodium fluoride solution
( see 6.3.7 ) and c:nrv out all the stages of procedure given in 6.4.3.
Preferably a calibration curve may be prepared showing volume of
thorium nitrate titre against quantity of sodium fluoride.

6.3.7 Standard Sodium Fluoride Solution ( I ml = 1 mg of F) - Dissolve

2.211 g of sodium fluoride ( AR ), previously dried at 120°C to constant
mass, in one litre of water in a volumetric flask.

6.4 Procedure

6.4.1 Transfer 0’5 g of an accurately weighed sample to a 250-ml

distillation flask containing 0.5 g of sodium silicate and a few glass beads.
Add 10 ml of perchloric acid. ( Phosphoric acid may be used along
with perchloric acid as it may help release of fluorine for the complex. )

6.4.2 Place a 1 OOO-ml flask under the condenser. Connect the

apparatus as shown in Fig. 1, distillation flask ( A) to the condenser and
distil the solution until the boiling point reaches 140°C. While this is
being done heat the water in the steam generator ( E ) to boiling but do
not allow the steam to get in the flask ( A ). When the temperature
reaches 14O”C, admit steam into the flask ( A ). Maintain the tempera-
ture at 140 i 2°C by adjusting the steam flow and heating of the flask
( A ). Distil at such a rate that no fumes or mist escape from the
volumetric flask. Continue distillation until nearly 250 ml are collected
in a loo-ml flask.1

6.4.3 Transfer to a 240-ml volumetric flask. Make the volume up to

the mark and mix well. Pipette out 50-ml aliquot into a 250-ml beaker.
Add 50 ml of water, 10 drops of sodium alizarine sulphonate indicator
solution and mix. Add sodium hydroxide solution slowly with stirring
till the solution becomes pink. Add dilute hydrochloric acid drop by
drop with stirring till the pink colour is just discharged leaving the
solution just acid. Add two millilitres of buffer solution and titrate
with standard thorium nitrate solution with constant stirring, till a
permanent pink end point is reached. The colour intensity at the end
point should be kept in mind and the titration should be stopped exactly
at the same colour intensity for both the standard thorium nitrate
solution ( see 6.3.6 ) and the test solution titration.

9
IS:9386 - 1979

6.5 Calculation

Fluorine, percent = AX
7 BX 100

where

A = volume in ml of standard thorium nitrate solution,

B = fluorine equivalent of the standard thorium nitrate
solution in g/ml, and
C = mass in g of the sample represented by the aliquot taken.

7. DETERMINATION OF CARBON DIOXIDE

7.1 Outline of the Method - A known mass of the sample is made to

react with an acid and the liberated carbon dioxide freed from impurities
is absorbed in previously weighed soda asbestos bulbs and weighed.
From the difference in masses the percentage of carbon dioxide is
calculated.

7.2 Apparatus - The assembly of apparatus is shown in Fig. 2. In

order to obtain better pressure for drawing gases through the train, all
joints should be mercury sealed.

7.3 Reagents

7.3.1 Dilute Hydrochloric Acid - 1 : 1 ( v/v ).

7.3.2 Concentrated Sulphuric Acid - rd = 1.84 ( conforming to IS : 266-

1961* ).

7.3.3 Ascarite or Soda Asbestos - solid.

7.3.4 Magnesium Perchlorate - solid.

7.3.5 Pumice Impregnated with Copper Sulphate - Anhydrous. Crush

pumice to approximately 5 mm size, sift free from dust, and transfer
60 g to a casserole. Cover with a concentrated solution of 30 to 35 g of
copper sulphate, evaporate to dryness while constantly stirring, and then
heat for 3 to 4 hours at 150 to 160°C in an air-bath. Cool in a desiccator
and preserve in a glass-stoppered bottle.

7.4 Procedure - Transfer 1 g of an accurately weighed sample to the

flask A and cover it with water. Insert the stopper carrying the separatory
funnel ( B ) and a condenser ( C ). Connect the latter with ( D ), ( E )
and ( F ). Pass air that is free from carbon dioxide through the system
until it is judged that all carbon dioxide has been removed. Close the

*Spcc,ification for sulphuric acid ( revised ).

10
 IS:9386- 1979

stop-cock in the separatory funnel, and insert the weighed absorption

bulbs ( G ) and ( H ) in the train ; H’ acts as a guard tube. Halffill the
separatory funnel with dilute hydrochloric acid, replace the stopper
carrying the air, and see that there is free passage for gases through the
train. Open the stop-cock in the separatory funnel and run acid into the
flask slowly if there is much carbon dioxide, and rapidly if there is but
little. When effervescence diminishes in the former case, at once in the
latter, start a flow of water in the condenser and heat the flask slowly so
as to secure steady but quiet ebullition. When it is judged that carbon
dioxide has been boiled out of the solution, remove the flame, increase
the current of air and sweep out all carbon dioxide. Disconnect the
weighed bulbs, close the inlet and outlet tubes, and place them on the
balance case. When cool, open the stopper momentarily and weigh.

7.5 Calculation

Carbon dioxide, percent (A

= -G- -% 100

where
A 3 mass in g of the bulbs after the test,
B = mass in g of the bulbs before the test, and
C = mass in g of the sample taken.

11
 CONCENTRATED
SULPHURIC ACID IMPREGNATED
WITH COPPER
SULPHATE OR EQUIVALEN
(0.7 TO 1.2mm)
OR EQUIVALENT

NOTE -Tubes are compactly arranged along the edge of 150 x 230 mm board which is supported 130 mm from the
table top upon a tripod base.

FIQ. 2 ABSORPTIONTRAIN FOR CARBON DIOXIDE