Is : 1527 - 1972

( Reallirmed 1996)
(Reaffirmed 1997)

Indian Standard
METHODS FOR
CHEMICAL ANALYSIS OF HIGH SILICA
REFRACTORY MATERIALS

( First Revision)

Fourlh Rrprint JANUARY 1990

HPCL, VISAKH Refinery.

Date 08-11-2013 Time 16:26:51
UDC 666.762.2:543

@ Copyright1973

BUREAU OFINDIAN STANDARDS

MANAK BHAVAN. 9 BAHADUR SHAH ZAFAK MARG
NJZWDELHI11OOUZ

Gr I February 1973
 lStl527-1972

hiian Stan&d
METHODS FOR
CHEMICAL ANALYSIS OF HIGH SILICA
REFRACTORY MATERIALS

(First Revision)
Methods of Chemical Analysis Sectional Committee, SMDC 2
Cboirmon w-*
DR R. K. Durr~ Hindgusapteel Ltd ( Durgapur Steel Plant),

Members
SHRI ii. C. BHAR~AVA India Government Mint, Bombay
SHRIJ. B~TTACHARJEB Ministry of Defence ( DC1 )

HPCL, VISAKH Refinery.

National Tat House. Calcutta

Date 08-11-2013 Time 16:26:51

SHRI A. K. BHA~ACHARYYA
SARI S. DAS GUF-TA( Alhnotc)
DR H. P. BHATTACHAR~A National Metalhtrgical LaboPatory ( CSIR ),
Jd=k=
Da U. N. BHIWW Indian Iron & Steel Co Ltd, Burnpur
SHRIA. C. bfVKHRRJKR ( dkdC)
DR V. M. BHVCHAR National Physical Laboratory ( CSIR ), New Delhi
,$‘dRl P. CHAKRA Indian Metals and Ferro Alloys Ltd, Koraput
DR B. N. CHAKRAVARTHI Hindustan Steel Ltd ( Bhilai Steel Plant ), Bhilai
SHRI Y. B. S. BISHNOI(Afirmotr)
SHRI A. K. CHATI-KRJRR Binani Metal Works Limited, Calcutta
CHEMIST AND M E I A t L u R Q xs T, Ministry of Railwaya
SOUTH CENTRAL RAILWAY,
SECUNDERABAD
A.w~sRcv=y;v~=T).

STANDARDS ORGAN&~,
CIV~ARANJAN ( A1tcmk)
JR A. N. CHOWVHVRY Geological Survey of India, Calcutta
B. N. BHATTAC~IARYA
SHRI (&em&)
&RI S. N. DASGVPTA Direczrte Gcoaal of Suppks & Dispos&, New

SHRI K. L. MIJR~~ ( Alfemafe)

DRR. DWITA The Eyre Smelting Private Ltd, Calcutta
SHRl S. ROY ( dkmuk)
SHRIC. S. GovRIs~~ANKA~ Directorate General, Ordnance Factoria ( Ministry
of De&x), Calcutta
SHRI J. W. GAWATHRK.~R ( Alfenta&)
( ~hmcd on pasr 2 )

BUREAU OF INDIAN STANDARDS

MANAK BHAVAN, 9 BAHADUR SHAH ZAFAR MARG
NEW DELHI 1loo02
I23 : 1527 - 1972

( cotltinliedfrom page1)
Members -
SHRIs. s. HONAVAR Italab Private Ltd. Bombay
SHRI J. C. DEY ( Altmalr I )
SHRI J. P. PATEL ( AftmuzleII )
SHRI D. P..JAIN Saru Smelting Priv8te Ltd, Mccrut
SRRI fi. N. CIUKRABOR~Y (~~) -
SHRI K. B. JAPE
De%%ra~u+~ R-
( Almu&)
SHRI S. L. N. ACHARYULU
SHRIG. L. JETHWANX Hindu&m Zittc Limited, Udtipur
DR A. K. MUKHERJEE Hinduscan Steel Ltd (Alloy Steel Plant), Durgapur
SHRI M. M. CHAKRAVARTY( A~MI~J )
SHRI K. RAMA~RISHNA Jzsscn& Co, BangJore
SHR~ A. SANOAMESWARARAO Fare Alloys Corporation Ltd, Sbreeratnnagar
SHRIG. RAJARAO ( Alfemafr )
DR B. C. SINHA’ Central Glass and Ccsamic Raearch Institute
( CSIR ), Calcutta
SHRI B. K. AGARWAL( Altw~te )
DR P. R. SUBBARAYAN National Chemical Laboratory ( C SIR ), Pooua
DR CH VENKATE~WARLU Bhahha Atomic Research Ccntre, Bombay

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Date 08-11-2013 Time 16:26:51
DR C. S. P. IYER ( Alfemafe I)
SHRIP. MURUQNYAN( Altema~c II )
SHRIR. K. SRIVASTAVA, I)mctor Gcnd, IS1 (ET+& Men&r)
Deputy Director (Strut & Met)
*m
SW S. L. BALI
Deputy Director ( Met ), IS1

Refractory Materials Analysis Panel, SMDC 2/P : 34

Conocnar
DR B. C. SINHA Central Glass and Ceramic Research Inrtitute
( CSIR ), Calcutta
Members
SHRI BHASKARRAO Kumardhubi Fircclay and Silica WorlrJ Ltd,
Kumardhubi
DR H. P. BXATTACXARYYA National Metallurgical Laboratory ( CSIR ),
Jamshedpur
DR A. N. CHOWDHURY Geological Survey of India. Calcutta
SHR~T. MOTILAL Bhilai Steel Plant ( Hindustan Steel Ltd ), Bhilai
SHRI H. F. K. NAD~O ( Ak~fe 1
SHRI T. K. S. RAO Bum & (20 Ltd, Raniganj, Dirt Burdwvl
SHRI A. SANGAMESWARA&o FCITOAlloys Gxporatioo Ltd, Shrceramnagar

2
 IS I 1527 - 1972

Indian Standard
METHODS FOR
CHEMICAL ANALYSIS OF HK;H SILICA
REFRACTORY MATERIALS

( First Revision )
0. FOREWORD
0.1 This Indian Standard ( First Revision ) was adopted by the Indian
Standards Institution on 25 October 1972, after the draft finalized by the
Methods of Chemical Analysis Sectional Committee had been approved by

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Date 08-11-2013 Time 16:26:51
the Structural and Metals Division Council.
0.2 This standard was earlier published in 1960. On the basis of the
experience gained during these years, it was felt that some of the methods
need modifications. While revising these methods actual investigations
have been carried out and due weightage has been given to the inter-
national practices followed in this field. The methods prescribed in this
standard may be used as referee methods and could 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
1.1 This standard covers the methods for determination of the loss on
ignition andof the oxides of silicon, aluminium, iron, titanium, calcium,
magnesium and the alkali metals in high silica materials ( over 94 percent
SiO, ). However these methods could be used for similar materials having
silica content of not less than 90 percent.

2. SAMPLING AND PREPARATION OF SAMPLE

2.1 The materials shall be sampled in accordance with the procedure laid
down in IS : 1528-1962t.
.
*Rules for roundingoff numericalvalues ( revised ) .
tMethods of sampling and physical tests for refractory materials

3
 IS : 1527- 1972

2.2 Laboratory Sample - The samples shall be crushed in any type of

crusher with hardened tool steel faces with due precautions to prevent
contamination of the sample with steel particles from the sampling equip-
ment during crushing and grinding. After quartering, 20 g of the sample
shall be carefully gone over with a magnet to remove extraneous iron
particles. It shall then be ground in an agate mortar so that it passes
completely through IS Sieve 15 ( aperture 149 microns, see IS : 460-1962* ).
2.3 Test Sample - It is prepared for the purpose of chemical analysis by
drying a sufficient quantity of the laboratory sample in a glass weighing
bottle in an air oven at 105 to 110°C.

3. QUALITY OF REAGENTS
3.1 Unless specified otherwise, pure chemicals and distilled water (see
IS : 1070-196Ot ) shall be used.
NOTE- ‘ Pure chemicals ’ shall mean chemicals that do not contain impurities which
affect the results of analysis.

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4. DETERMINATION OF LOSS ON IGNITION
4.1 Transfer one,gram of the test sample to a weighed platinum crucible
and introduce it into a muffle furnace and slowly raise the temperature to
950 to 1 000°C. After about 30 minutes, remove the crucible and cool in a
r zsiccator and weigh. Repeat the ignition, if necessary. Calculate the
loss of weight of the sample.
4.2 Calculation

Loss on ignition, percent = $X 100

where
A = loss of mass in g on ignition, and
B = mass in g of the sample taken.

5. D$;;~EF;NATION OF SILICA BY THE GRAVIMETRIC

5.1 outline of the Method - The sample is decomposed by fusion with

sodium carbonate and extracted with acid. Silica is then determined by
dehydration and baking followed by hydrofluorization as usual. The
residual silica is determined photometrically.

*+&cation for test sieves ( revised ).

tspecification for water, distilIed quality ( revised).

k
 IS : 1527 - 1972

5.2 Reagents
5.2.1 Sodium Carbonate - anhydrous.
5-2.2 Dilute Hydrochloric Acid - 1 : 1, 1 : 3 and 1 : 19 ( V/V ).

502.3 Dilute Sulflhuric Acid- 1 : 1 ( v/v ).

5.2.4 Hydrojuorfc Acid - 40 percent.
5.2.5 Potassium Pyrosul&hate - Solid.
502.6 EDTA Solution ( 0,025 M Appoximately ) - Dissolve 9.31 g
of disodium salt of ethylene-diamine tetraacetic acid, dihydrate
( C~,HuN&‘,Cs, 2HsC ) in water and dilute to 1 litre.
5.2.7 Phenolphthalein Sob&on - Dissolve 1 g of phenolphthalein in 100 ml
of rectified spirit.
5.2.8 Dilute Ammonia Solution - 1 : 3 ( v/v).
5.2.9 Ferric Ammonium Sulphate Solution ( l-12 mg Fe/ml ) - Dissolve

HPCL, VISAKH Refinery.

482 g of ferric ammonium sulphate [ NH,Fe ( SO, )s, 121&O ] in water

Date 08-11-2013 Time 16:26:51

containing 80 ml of dilute hydrochloric acid ( 1 : 1 ) and dilute to 500 ml
in a volumetric flask.
5.2.10 Ammonium Molybdate Solution -Dissolve 100 g of ammonium
lolybdate in water containing a few drops of dilute ammonia ( 1 : 3 ),
liter if necessary and dilute to 1 litre.
5.2.11 Oxalic Acid Solution - Dissolve 100 g of oxalic acid in water and
dilute to 1 litre.
5.2.12 Ascorbic Acid Solution ( 10 percent ) - Dissolve 10 g of the acid in
100 ml water and filter if necessary. Preserve in an amber-coloured bottle.
The solution, thus preserved, could be used up to 5 days.
5.2.13 Standard Silica Solution ( 0.04 mg/ml )
a) First prepare a stock solution with 0.4 g/l; for this purpose fuse
0.200 g of pure silica ( 99.8 percent ) in 5 g of sodium carbonate
in a platinum crucible. Dissolve in 300 ml of water, containing
8 to 10 g of sodium hydroxide, using a polvthene beaker. Cool
and dilute with water in a volumetric flask’to 500 ml. Store in
a polythene bottle.
b) Prepare immediately before use a standard solution containing
0.04 mg/ml by diluting the above stock solution appropriately.
5.3 Procedure
5.3.1 Decomposition oJ the Sample - Weigh accurately about 0.5 g of the
finely ground test sample ( see 2.3 ) into loo-ml platinum dish. Add 3 g
of sodium carbonate; after mixing intimately, cover the dish with lid and
5
IS : 1527- 1972

heat over a Meker burner slowly, increasing the temperature with caution
until the mixture fuses. Keep at this temperature for 10 minutes and
finally heat till a clear melt is obtained. Remove from the burner and
Cool.
5.3.1.1 Add about 30 ml of dilute hydrochloric acid ( 1 : 1 ) and
O-5 ml of dilute sulphuric acid. Allow the covered dish to stand on a
steam bath until disintegration of \he melt is complete. Crush any large
flakes with a flattened end of a glass rod.
5.3.2 GravimetricDetermination of Insoluble Silica
5.3.2.1 Evaporate the solution in the dish to dryness and allow the
dish to remain on a steam bath. ( The evaporation may be facilitated by
occasional use of a glass rod to break up the crust of salt that covers the
liquid and tends to prevent further evaporation ). Transfer the dish to an
air oven maintained between 105 to 110°C and bake it for one hour.
Cool the dish and its contents slightly, then add 20 ml of the dilute
hydrochloric acid ( 1 : 1 ). After about one minute, add 30 ml of hot

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Date 08-11-2013 Time 16:26:51
water and stir the mixture for a few moments until solution of soluble salts
appears to be complete. Cover the dish and allow the mixture to digest
on a steam bath for 10 minutes without stirring. Filter through No. 42
filter paper and rinse the dish with dilute hydrochloric acid ( I : 19 ),
scrubbing the basin with a rubber-tipped glass rod. Wash the precipitate
five times with hot dilute hydrochloric acid ( 1 : 19) and then with hot
water until free from chlorides. Transfer the filtrate and washings to a
500-ml volumetric flask and make up to the mark (solution S).
5.i.2.2’ Transfer both paper and precipitate to an ignited and weighed
platinum crucible. Ignite at a low temperature until the precipitate is
free from carbonaceous matter and then heat in the furnace at 1050°C to
constant weight ( one hour being normally sufficient ). Cool and weigh.
Moisten the contents of the cold crucible with water, add five drops of
dilute sulphuric acid and 10 ml of hydrofluoric acid. Evaporate to dr+
ness on a hot plate or sand bath in a fume cupboard, taking care to avoid
spurting.
5.3.2.3 Heat the crucible and residue, cautiously at first, over a gas
flame until the disappearance of white fumes and finally for five minutes
in the furnace at 105O”C, cool and weigh. If the residue weighs more
than 10 mg, repeat the treatment with dilute sulphuric and hydrofluoric
acids.
5.3.3 Molybdenum Blue Method
5.3.3.1 Transfer 20 ml aliquot of the solution S ( 5.3.2.1) to a lOO-ml
measuring flask. Add 5 ml of EDTA solution, a drop of phenolphthalein
solution and then dilute ammonia solution dropwise until the colour
changes to red. Add 5 ml of ferric ammonium sulphate solution and

6
 IS : 1527 - 1972

dilute to about 40 ml with water. (The PH of the sol&on should be

1 to 1.5 ).
5.3.3.2 Add 5 ml of the ammonium molybdate solution and allow to
stand for 10 minutes. Then add 5 ml of oxalic acid solution followed
immediately by 5 ml of ascorbic acid solution and dilute the volume to
100 ml. Allow the solution to stand for 30 minutes for development of
full colour.
5.3.3.3 Transfer a suitable portion of the coloured solution to an
absorption cell and take photometric reading using light band centred
approximately at 810 nm against a referend test blank solution prepared
in the same way without the sample.
NOTE-Test blank solution-It is preparedby taking all reagents and solutions except
the sample in accordance with the general procedure for the determination of residual
silica. However, fusion may be omitted to avoid undue attack on platinum crucible.
5.3.3.4 Calibration curve - Transfer 0, 1, 2! 3 and 4 ml of standard
silica solution to lOO-ml volumetric flasks. Dilute each to 10 ml with

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Date 08-11-2013 Time 16:26:51
water. Add a drop of phenolphthalein solution an! acidify with a few
drops of dilute hydrochloric acid ( 1 : 3 ), Carry out the entire stages of
procedure as described in 5.3.3.1 ( except the addition of 10 ml of solu-
tion S) and 5.3.3.2 using the same quantities of reagents and record the
photometric readings of all these solutions against the blank ( ‘ 0 ’ ml ).
5.3.3.5 Convert the photometric reading of the test solution’ to milli-
grams of silica by means of the calibration curve and calculate the silica
content in grame in 500 ml of solution S ( 5.3.2.1 1I*

5.4 Calculation
(B---C’++
Silica, percent = x 100
A
where
B = mass in g of dish and contents before hydrofluoric acid
treatment,
C = mass in g of dish and residue after hydrofluoric acid treat-
ment,
D = mass in g of silica present in 500 ml of solution S, and
A = mass in g of sample.

6. DETERMINATION OF ALUMINA BY EDTA METHOD

6.1 Outline of the Method - Aluminium ( also iron and titanium when
present ) is complexed quantitatively with EDTA by boiling with an excess
of the reagent. The excess EDTA is back titrated with standard zinc

7
Is : 1527- 1972

solution at about PH 5.2 using xylenol orange indicator. The aluminium

EDTA complex ( also titanium-EDTA complex, if present ) on boiling with
ammonium fluoride liberates EDTA which when titrated with standard
zinc solution gives the amount of aluminium present in the solution, Due
correction for titania is also carried out.
6.2 Reagents
6.2.1 Dilute Sulphuric Acid- 1 : 1 ( v/v). Add 100 ml of concentrated
sulphuric acid (sp gr 1.84) cautiously with stirring to 100 ml of water and
cool.
6.2.2 Hydrojluoric Acid - 40 percent.
6.2.3 Sodium Carbonate - solid.
6.2.4 Dilute Hydrochloric Acid - 1 : 1 ( v/v).
6.2.5 EDTA Solution ( O-025 M ) - See 5.2.6.
6.2.6 Methyl Orange - Dissolve @05 g of methyl orange in 100 ml of

HPCL, VISAKH Refinery.

water.

Date 08-11-2013 Time 16:26:51

6.2.7 Dilute Ammonia ( 1 : 5 ) - Dilute 25 ml of concentrated ammonia
( sy gr 0.90 ) to 150 ml.
6.2.8 Acetate Bu& (PH 5.2 ) - Dissolve’ 21.5 g of sodium acetate
( CHsCOONa, 3HsO ) in 300 ml of water containing 2 ml ofglacial acetic
acid and dilute to 1 litre.
6.2.9 Standard Aluminium Solution ( 1.0 mg Al,Os/ml ) - Weigh O-529 3 g
of aluminium metal ( 99.9 percent purity ) into a beaker containing 40 ml
of dilute hydrochloric acid ( 1 : 1 ) and small drops of mercury. Heat the
beaker over a water bath. Transfer the solution to a 1 OOO-mlvolumetric
flask and make up to the mark.
NOTE - Mercury will not dissolve and may be removed while transferring the solu-
tion to 1 OOO-ml volumetric flask.

6.2.10 Standard zinc Solution ( 0.025 M ) - Dissolve 5.484 5 g of zinc

acetate [ Zn ( CHsCOO )a, 2HsO] in 50 ml of water, 0.5 ml of glacial
acetic acid and 25 ml of acetate buffer ’ 6.2.8 ) and dilute tcJ 1 litre
in a measuring flask. Find out the equiva i ent A&O, in g per ml from
the procedure given in 6.3.2 taking 20 ml of standard aluminium solution
(6.2.9).
6.2.11 Xylenol Orange - Dissolve 0.1 g of xylenol orange in 100 ml of
water containing two drops of dilute hydrochloric acid ( 1 : 1 ).
6.2.12 Ammonium Fluoride (20 percent) - Dissolve 20 g of ammonium
fluoride in 100 ml of water. Add 3 drops of xylenol orange ( 6.2.11)‘ and
then dilute hydrochloric acid ( 1 : 9 ) dropwise till the colour changes to
yellow,

8
 IS : 1527- 1972

6.3 Procedure
6.3.1 Solution of the Sample - Weigh accurately about 2 g of the finely
ground test sample ( Jee 2.3) in a platinum dish. Moisten the sample
with 5 ml of water. Add 3 ml of the dilute sulphuric acid and 20 ml of
the hydrofluoric acid and evaporate slowly to dryness on the sand bath. or
hot plate in a fume cupboard, taking care to avoid spurting. Repeat
the process with 10 ml of hyd,rofluoric acid. Cool, add 2 ml of the dilute
sulphuric acid and evaporate as before, Heat the dry residue cautiously
until fumes of sulphur trioxide cease to be evolved. Raise the temperature
to 1000°C and ignite for five minutes. Cool and fuse the residue with
about 3 g of sodium carbonate. Dissolve the residue in 30 to 40 ml dilute
hydrochloric acid, cool and dilute to 250 ml in a calibrated flask, Reserve
the solution for determination of iron, titania and aluminii.
6.3.2 Transfer. 100 ml aliquot of the solution to a 500.ml conical flask.
Add sufficient EDTA solution to provide an excess of at least 5 mi over the
expected amount of alumina and iron ( 1 ml of 0.025 M EDTA = 1.25 mg
Al,O, approximately ). Add 2 to 3 drops of methyl orange and then dilute
ammonia dropwise until the colour. changes from red to yellow. Add 5 ml

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Date 08-11-2013 Time 16:26:51
of acetate buKer and about 25 ml water and heat to boiling for 5 minutes.
Cool, add 5 ml of buffer solution and titrate with standard zinc solution
using 5 to 6 drops of xylenol orange indicator. The end point is indicated
by a clear change from yellow to deep orange colour. Add 10 ml of
ammonium fluoride solution and heat to boiling for 5 minutes. Cool, add
5 ml of buffer solution and titrate the liberated EDTA with standard zinc
solution.
NOTE- If titania content is well above O-5 percent, it may effect the sharpness of the
end point.,
6.4 Calculation
Alumina, percent = L;x x 100 - 0.637 8 D

where
A = volume in ml of standard zinc required for the titration
of liberated EDTA,
B = equivalent Al,Os in g per ml of standard zinc solution,
G = mass in g of the sample represented by 100 ml of solution
taken, and
D = percent of TiO, present in the sample. The value is
obtained from, photometric determination ( see 8.4 ).
7. DETERMINATION OF IRON BY THE ORTHO-PHENAN-
‘FHROLINE (PHOTOMETRIC ) METHOD
7.1 Outline of the Method-The orange-red complex produced in
acid solution of the sample (flH 4 to 6 ) by the addition ofO-phenanthroline
is determined photometrically at approximately 510 nm.
IS t 1527 - 1972

7.2 Reagents
7.2.1 Turtaric Acid Solution - 10 percent ( m/v).
7.2.2 Hydroxylamine Hydrochloride Solution ( 10 g/l ) - Dissolve 1 g of the
reagent in water. Transfer the solution to loo-ml volumetric flask, Dilute
to the mark and mix well.
7.2.3 Ortho-Phenanthroline Solution ( One Percent ) - Dissolve one gram of
the 0-phenanthroline monohydrate in 90 ml of water with gentle heating
and constant stirring. Cool and dilute to 100 ml.
7.2.4 Acetate Buffer - Dissolve 21.5 g of sodium acetate ( CH,COONa,
3H,O ) in 300 ml of water containing 2 ml of glacial acetic acid and
dilute to 1 litre.
7.2.5 Standard Iron Solution ( 1 ml = 0.02 mg Fe ) - Dissolve 0.2 g of
pure iron in concentrated hydrochloric acid. Dilute the solution to 100 ml.
Take the solution in a I-litre volumetric flask, dilute to the mark and mix
well. Transfer 100 ml of this solution to l-litre measuring flask and dilute
to the mark with water. Mix well.

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7.3 Procedure
7.3.1 Transfer a 5 ml aliquot of the solution preserved under 6.3.1 to a
100~ml measuring flask. Add 2 ml of tartaric acid solution, and 2 ml of
the hydroxylamine hydrochloride solution. Stir well. To this, add 5 ml
of the ortho-phenanthroline solution and 10 ml of acetate buffer solution.
Allow to stand for 15 minutes and dilute to 100 ml. Shake well.
7.3.2 TranSfer a suitable portion of the solution to an absorption cell
and take photometric reading using a light band centred approximately at
510 nm against a reference test blank solution.
7.3.3 Calibration Curve - Transfer 0, 1,2, 4, 8 and 10 ml of the standard
iron solution in lOO-ml volumetric flasks, using same quantities of reagents.
Carry out the entire stages of procedures as described under 7.3.1 and 7.3.2
and record the photometric readings of all the standard solutions against
the blank.
7.4 Calculation -Convert the photometric reading of the sample to
milligrams of iron by means of a calibration curve and calculate the ‘per-
centage of iron as follows:

Ferric oxide, percent = ; x 0,142 9

where
A = mass in mg of iron found in aliquot, and
B = mass in g of the sample represented by the aliquot taken,

10
 IS : 1527 - 1972

8. DETERMINATION OF TITANIA BY THE PHOTOMETRIC

METHOD
8.1 Outline of the Method - The yellow coloured complex produced in
acid solution of the sample by the addition of hydrogen peroxide is deter-
mined photometrically at approximately 410 nm.

8.2 Reagents
8.2.1 Dilute Sulphuric Acid - 1 : 1 ( v/v ).
8.2.2 Phosphoric Acid - Add 400 ml of phosphoric acid ( sp gr I.75 ) to
500 ml of iater, cool and dilute to 1 litre.
8.2.3 Hydrogen Peroxide - 20 volumes.
8.2.4 Standard Tiitania Solution - Fuse 0.5 g of dried TiO, with 5 g of
potassium pyrosulphate and dissolve by heating at a low temperature to
avoid hydrolysis in 200 ml of water containing 20 ml of concentrated

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Date 08-11-2013 Time 16:26:51
sulphuric acid ( sp gr 1.84 ) . Cool and dilute to 1 litre in a measuring
flask ( 1 ml = 0.5 mg TiO, ).

8.3 Procedure
8.3.1 Transfer 50 ml aliquot of the solution from 6.3.1 to a loo-ml
measuring flask. Add 5 ml of dilute sulphuric acid, 10 ml of the phospho-
ric acid and 10 ml of hydrogen peroxide. Dilute the solution to 100 ml.
8.3.2 Transfer a suitable portion of the solution to an absorption ceil
and take a photometric reading using a light band centred approximately
at 410 nm against a .reference test blank solution.
8.3.3 Calibration Curue - Transfer 0, 1, 2, 4 and 6 ml of the standard
titanium solution to lOO-ml volumetric flasks, using the same quantity of
reagents, carry out the entire stages of procedure as in 8.3.1 and 8.3.2 and
record the photometric readings of all the standard solutions against the
blank.
8.4 Calculation -Convert the phototietric reading of the sample to
milligrams of titania by means of calibration curve and calculate the
percentage of TiO, as follows:
A
Titania, percent = .li- x -&

where
A = mass in mg of titania determined in the aliquot solution,
and
B = mass in g of sample represented by the aliquot taken,

II
IS : 1527 - 1972

9. DETERMINATION OF CALCIUM OXIDE AND MAGNESIUM

OXIDE BY THE EDTA METHOD
9.1 Oailine of the Method - In an aliquot of the sample solution, R,O,
group e’lements are masked by triethanolamine, and calcium and mag-
nesium are titrated with EDTA solution at pH 10 using eriochrome black
T indicator. In another aliquot magnesium is precipitated out at #H 12
in presence of triethanolamine and calcium is titrated with EDTA using
Patton and Reader ( P & R ) indicator. Subtracting the titre value of
calcium from that of calcium and magnesium, the titre vaiue for mag-
nesium is obtained.

9.2 Reagents
9.2.1 Concentrated .Nitric Acid - sp gr 1.42 (conforming to IS: 264-
1968* ).
9.2.2 Perchloric Acid - 70 percent.
9.2.3 HydroJIuoric Acid - 40 percent.
9.2.4 Concentrated Hydrochloric Acid - sp gr 1.16 ( conforming to IS : 265-

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Date 08-11-2013 Time 16:26:51
1962t ).
9.2.5 Triethanolamine SnZuti& - 30 percent ( v/v). Dilute 60 ml of
triethanolamine to 200 ml.
9.2.6 Sodium Hydroxide Solution ( 5N Approximately ) - Dissolve 100 g of
sodium hydroxide in water, cool and dilute to 500 ml and store in a
polythene bottle.
9.2.7 P & R Indicator - Mix by grinding togjether 0.1 g of P & R indi-
cator and 30 g of sodium chloride. About 0.2 g of the mixture is required
for each titration.
9.2.8 Standard ED IA Solution ( 0.01 M ) - Dissolve 3.72 g of disodiub salt
of ethylenediamine tetra acetic acid dihydrate in warm water, filter if neces-
sary, cool and dilute to one litre. Store in a polythene bottle. Standardize
against- the standard calcium solution (see 9.2.9 ) using P $i R indicator
and against the standard magnesium solution ( SPY9.2.10) using ‘Mixed’
indicator.
9.2.9 Standard Calcium Solution - Dissolve 1.7848 g of calcium carbonate
dried at 150°C in a slight excess of hydrochloric acid, boil to expel carbon
dioxide, cool and dilute to 1 litre ( 1 ml L- 1 mg CaO ).
9.2.10 Standard Magnesium Solution - M7ash a piece of magnesirmi in
dilute hydrochloric acid to remove any oxide film, then with water and

*Specification for nitric acid (Jirst rev&m ).

tSpecification for hydrochloric acid (rcukf ).
 IS t 1527 - 1972

dry it with ethanol followed by ether. Dissolve 0’603 2 g of the metal in

a slight excess of dilute hydrochloric acid, cool and dilute to 1 litre in a
calibrated flask ( 1 ml = 1 mg MgO ).
9.2.11 Ammonia-ammbnium Chloride Bu$r Solution ( ~JH = 10 ) - Dissolve
57.5 g of ammonium chloride in 250 ml of water, and 570 ml of ammonia
( sp gr = 0.88 ) and dilute to 1 litre and mix thoroughly.
9.2.12 Eriochrome Black T Indicator Solution - Dissolve 0.4 g of the sodium
sait of eriochrome black T in a mixture of 20 ml of ethanol and 30 ml of
triethanolamine. This solution is stable for at least 3 months when kept
in a tightly closed plastic dropping bottle.
9.3 Procedure
9.3.1 Solution of the Sample -Weigh accurately about 1 g of the test
sample (see 2.3 ) into a platinum dish. Add 5 ml of concentrated nitric
acid, 5 ml of perchloric acid and about 10 ml of hydrofluoric acid. Cover
the dish with a lid. Allow the reaction to proceed for at least 15 minutes,
then remove the lid and evaporate the mixture to dryness on a sand bath

HPCL, VISAKH Refinery.

Date 08-11-2013 Time 16:26:51
in a fume cupboard, taking care to avoid spurting. Cool, add 5 ml of
perchloric acid, rinse the lid and sides of the dish with water and again
evaporate carefully to dryness. To the cool, dry residue, add 2 ml of
concentrated hydrochloric acid and about 15 ml of deionized water.
Digest on a steam bath for 10 minutes, cool, filter if necessary and dilute
the solution with deionized water to 250 ml in a calibrated flask. Reserve
the solution for determination of calcium and magnesium oxides as well as
alkali metals in a polythene bottle.
g-3.111 Determination of calcium - Pipette 50 ml ( = 0.2 g ) of the
solution into a 250-ml conical flask. Add 10 ml triethanolamine solution,
5 ml of sodium hydroxide solution dropwise while shaking the solution,
and then add 0.2 g of P & R indicator. Titrate immediateIy with a
standard EDTA solution from 10 ml semi-micro burette until the colour
changes from pink to blue. .
NOTE- If sharp end point is not ‘obtained, 2 ml of potassium cyanide ( 10 percent
m/u ) may be added after the addition of triethanolamine in 9.3.1.1 and 9.3.2.

9.3.1.2 Calculation
Calcium oxide, perceht = AXBX
c-- 100

where
A E volume in ml of standard EDTA solution required for
titration,
B = (=a0 equivalent in g/ml of the standard EDTA solution,
and
C i= mass in g of the sample represented by the aliquo: sample
solution taken.

13
 .., _ . .. . “. ^___. _ .___ _ .

ISt1527-1972

9.3.2 Determination of Magnesium Oxide - Pipette out 50 ml ( E 0.2 g ) oc

solution reserved in 9.3.1into a 250-ml conical flask. Add 10 ml of
triethanolamine solution. Add 15 ml of *ammonia-ammonium chloride
buffer solution. Add 4 to 5 drops of eriochrome black T indicator solu-
tion and imm,ediately titrate with the standard EDTA solution from a
lo-ml semi-microburette until the colour changes from wine red to blue. .
9.3.2.1 Calculation

Magnesium Oxide, percent = tA--)

--D- Cx.100

where
A = volume in ml of standard EDTA solution required for
titration of total calcium and magnesium obtained in
9.3.2,
B = titre value for calcium,
C= MgO equivalent in g/ml of the standard EDTA solution,

HPCL, VISAKH Refinery.

Date 08-11-2013 Time 16:26:51
and
D = mass in g of the sample represented by the aliquot taken.

10. DETERMINATION OF ALKALI METALS

10.1From the solution reserved in 9.3.1alkali metals are determined by
using a flame photometer.
10.2 Determine the alkali metal contents on aliquots of solution by com-
parison with solutions containing-known amount of potassium and sodium
using a suitable flame photometer. The procedure should be appropriate
for the type of flame photometer and should be confirmed by determination
on standard samples of solutions. The standard solutions should be of
similar composition as far as possible to the sample solution being analysed.
10.3 The alkali metal contents are calculated as oxides by reference to
previously prepared calibration graphs.
1 IO.4 A procedural blank should also be carried out and necessary correc-
tion made in t.he final calculation.
NOTE- Wherever required, only deionized water shall be used.

14
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