E.R.

Procedures for Chemical Analysis of Ordinary Portland Cement

1.0 REPRODUCIBILITY OF RESULTS

1.1 Blank determinations shall be made on the reagents for each Constituent in the cement
and the corrections shall be applied where necessary. In all cases check determination
shall be made and repeated if satisfactory checks are not obtained. The difference
between check determinations shall not exceed 0.2 percent for silica and alumina, and 0.1
percent for other constituents.

The difference between check determinations by EDTA method shall not exceed 0.2
percent for calcium oxide and magnesia, 0.15 percent for alumina and 0.1 percent for
ferric oxide.

2.0 Reagents and Special Solutions

Unless specified otherwise pure chemical of analytical reagent grade shall be employed
in tests, and distilled water shall be used where the use of water as a reagent is intended.
The following reagents and special solutions of analytical reagent grades are required.

2.1 Hydrochloric acid- sp gr 1.16

2.2 Nitric acid – sp gr 1.42
2.3 Sulphuric acid – sp gr 1.84
2.4 Phosphoric acid- sp gr 1.7
2.5 Hydrofluoric acid – 40 percent.
2.6 Ammonium Hydroxide – sp gr 0.90
2.7 Acetic acid – glacial.
2.8 Diethylamine- liquid.
2.9 Sulphosalicylic acid - solid
2.10 Potassium periodate – solid.
2.11 Dilute solutions of Reagents- prepare the following dilute solutions by diluting the
reagent with distilled water.
2.12 Hydrochloric acid – 1;1,1:3, 1:10 and 1:99 (by volume).
2.13 Nitric acid – 1:4 , 1:33 (by volume).
2.14 Ammonium hydroxide – 1: 1 and 1:6 (by volume).
2.15 Sulphuric acid – 1:3 (by volume)
2.16 Phosphoric acid – 1:3 (by volume)
2.17 Sodium hydroxide solution -4 N (approximately) Dissolve 80 g of sodium hydroxide in
500 ml volumetric flask and make up to the mark with distilled water.
2.18 Glycerol – 1:1 (by volume).
2.19 Triethanolamine – 1:1 (by volume).
2.20 Ammonium acetate -50percent solution. Weigh 500 grms of Ammonium acetate and
make up the volume to 1000ml with distilled water.
2.21 Barium Chloride Solution- Dissolve 100 g of barium chloride BaCl2.2H2O) in one litre
of water.

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2.22 Bismuth nitrate Solution – Weight about 4 g of bismuth nitrate

entahydrate[Bi(NO3)3.5H2O] in 500 ml beaker. Add 20 ml of acetic acid. Stir and dilute with
about 40 ml water. Filter and transfer the solution to one litre volumetric flask and make up the
volume to the mark with distilled water

2.23 Buffer solution – pH 10- Dissolve 70 g of ammonium chloride in 570 ml of ammonium

hydroxide (sp gr 0.90) and make up to one litre with distilled water.
2.24 Standard Zinc Solution – 0.01 M. Disolve accurately weighed 0.6537g of granulated zinc
in a minimum quantity of dilute hydrochloric acid (1:1). Make up to the mark with
distilled water in one litre volumetric flask.
2.25 Standard EDTA Solution- 0.01 m. Dissolve 3.7224 g of disodium ethylenediamine tetra
acetate dehydrate in 400 ml hot water and make up the volume in one litre flask. Take 10
ml of standard zinc solution in an Erlenmeyer flask. Add 20 ml buffer solution of pH 10
and warm to 50 to 60 Dec. C Add 50 mg Eriochrome Black-T indicator and titrate with
EDTA. Till the colour changes from wine red to clear blue. Note the volume of EDTA used
(V). Calculate the molarity of EDTA as follows:

Molarity of EDTA = 0.01 x 10

V

Adjust the molarity to 0.01 M, if required.

2.26 Eriochrome black-T – Grind 100 mg of indicator with 10 g of sodium chloride till
homogeneous mixture is obtained and store in an airtight polyethylene bottle

2.27 Xylenol Orange- Grind 100 mg of indicator with 10 g of potassium nitrate till a
homogeneous mixture is obtained and store in an airtight ontainer.

2.28 Patton-Reeders Indicator – Grind 100 mg of indicator with 10 g of sodium or potassium

sulphate till a homogeneous mixture is obtained and store in an airtight bottle.

2.29 Thymol Phthalexone indicator- Grind 100 mg of thymol phthalexone indicator with 10 g
of potassium nitrate till a homogeneous mixture is obtained and store in an airtight
container.

2.30 Thymol Blue – 0.1 percent solution in ethyl alcohol (W/V).

2.31 Standard Sodium Chloride solution – 0.01N : Dissolve 0.2923g of sodium Chloride dried
at 105±2 deg C in distilled water and make up to 500ml.
2.32 Standard silver nitrate solution – 0.01N : Dissolve 1.6987 g of silver nitrate dried at
105±2 deg C in distilled water and make up to 1000ml. The solution should be covered
with carbon paper.
2.33 Standard Ammonium thiocyanate solution – 0.01N : Dissolve 0.7612g of ammonium
thiocyanate in distilled water and make up to 1000ml.
2.34 Potassium chromate solution (5%) - Dissolve 5.0g of potassium chromate in 100 ml
distilled water.

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2.35 Ferric alum indicator – Cold Saturated solution of ferric ammonium sulphate in water
(about 4%) to which a few drops of 6N nitric acid has been added.
2.36 Take 25ml of standard sodium chloride in to 250ml titration flask and add 1ml of
potassium chromate indicator solution, Titrate slowly with silver nitrate solution with
constant stirring until the red colour formed begins to disappear more slowly. continue
addition of silver nitrate solution drop were until faint red brown colour persists
throughout the solution.

Normality of silver nitrate (N 2 ) =

N1 V1
2
N1 = Normality of Sodium Chloride
V1 = Volume of Sodium Chloride
V2 = Volume of Silver nitrate

2.37 Take 25ml of standardised silver nitrate solution into a 250ml titration flask, add 5ml of
6N nitric acid and 1 ml of Ferric alum indicator solution. Titrate with ammonium
thiocyanate solution - at first white precipitate appears rendering the liquid a milky
appearance and as each drop of thiocyanate falls in it, produces reddish brown cloud
which quickly disappears on shaking. Add ammonium thiocyanate dropwise faint brown
colour persists on shaking.

Normality of ammonium thiocyanate (N 3 ) = N2 V2

V3
N 2 = Normality of Silver nitrate
V2 = Volume of silver nitrate
V3 = Volume of ammonium thiocyanate

3.0 Loss on Ignition

3.1 Weigh empty platinum crucible (W1 ).

3.2 Transfer about 1.0 g sample to platinum crucible and weigh (W2).

3.3 Heat crucible with sample in a muffle furnace at 900-1000oC to constant weight (W3).

(W3 - W2 ) x 100
3.4 LOI (%) =
(W2 - W1 )

E. RAMESH
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4.0 Silica

4.1 Transfer about 0.5 g of accurately weighed sample in a 250 ml beaker. Add 10 ml of
water followed by 5-10 ml of concentrated hydrochloric acid and digest with gentle heat
to dissolve the sample. Evaporate to dryness on steam bath.
4.2 Treat residue with 10-20 ml of hot dil hydrochloric acid (1:1) and treat with equal
volume of hot water. Digest on water bath for 5-10 minutes and filter through Whatmann
filter no. 40.

4.3 Wash silica thoroughly with hot water and reserve the residue.

4.4 Re-evaporate the filtrate to dryness followed by oven baking at 105-110oC for 1 hour.

4.5 Extract residue in 10-15 ml of dil HCl (1:1) followed by digestion on water bath and
dilution with equal volume of hot water.

4.6 Filter through Whatmann no. 40, wash thoroughly with hot water and reserve filtrate and
washings for determination of combined alumina and ferric oxide.

4.7 Weigh empty platinum crucible (W1) and transfer both filter papers (under 4.3 & 4.6) on
it.

4.8 Dry & char paper without enflaming, burn carbon at low temperature and finally ignite at
1050-1100oC to obtain constant weight (W2).

4.9 Moisten residue with distilled water, add 2-3 drops concentrated sulphuric acid followed
by 10ml HF and evaporate to dryness. Heat residue left at 1050-1100oC for 5 minutes,
cool and weigh (W3).

(W3 - W2 ) x 100
4.10 SiO2 (%) = weight of sample

4.11 use residue with 0.5 g of potassium persulphate or pyroshlphate to red heat, extract fused
mass in dil hydrochloric acid and mix with filtrate under 4.6 for determination of
combined oxides.

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5.0 Ferric Oxide

5.1 Make up filtrate given under 4.11 to 250ml in a volumetric flask.

5.2 Take 25ml aliquot under 5.2.1. add 1:6 NH4OH till turbidity appears. Clear turbidity
with minimum dil. Hydrochloric acid (1:10)
5.3 Add few drops in excess of acid to adjust pH 1 to 1.5 and shake well.
5.4 Add 100mg of sulphosalicylic acid and filtrate with 0.01m EDTA a colorless or pale
yellow solution.
5.5 Fe2O3% = 0.7985 x V
5.6 W
V = Volume of EDTA used in ml.
W = Weight of Sample in g.

6.0. Alumina

6.1 Take 25ml of solution given under 5.2.1. and titrate iron at pH 1-1.5 with EDTA using
sulphosalicylic acid indicator as given in 5.0
6.2 Add 15ml of standard EDTA solution, 1ml of phosphoric acid (1:3) and 5ml of sulphuric
acid (1:3).
6.3 Further add one drop of thymol blue followed by addition of ammonium acetate solution
by stirring until the colour changes from ret to yellow.
6.4 Add 25ml of ammonium acetate in excess to obtain pH 6. Heat the solution to boiling and
cool.
6.5 Add 50mg of xylenol orange indicator and titrate with bismuth nitrate solution slowly
with stirring until the colour of solution changes fro yellow to red. Add 2 to 3 ml of
bismuth nitrate solution in excess.
6.6 Titrate with 0.01M EDTA to a sharp yellow end point.
6.7 Al2 O 3 (%) = 0.5098 x V
W
V = V1 – V2 – (V3 x E)
V = Volume of EDTA for alumina in ml
V1 = Total Volume of EDTA used in ml
V2 = Volume of EDTA used for Iron (5.0) in ml
V3 = Total Volume of bismuth nitrate used in ml
W = Weight of sample in grams

6.8 Obtain equivalence of bismuth nitrate as follows :

Transfer 100ml of bismuth nitrate in a 500ml titration flask. Add 100ml of distilled water
a few drops of thymol blue indicator and ammonium acetate solution until the co lour of
solution changes from red to yellow. Add 50mg xylenol Orange indicator. The colour of
solution changes from red to yellow. Titrate with 0.01M EDTA solution until the colour
changes from red to yellow.

E= V4
100
V4 = Volume of EDTA used in ml.

E. RAMESH
E.R.

7.0. Calcium Oxide

7.1 Take 10ml of solution given under 5.2.1

7.2 Add 5ml of glycerol (1:1) with constant stirring, 5ml of diethylamine amine followed by
addition of 10ml of 4N sodium hydroxide solution.
7.3 Shake well to adjust pH of 12 or slightly more.
7.4 Add 50ml of distilled water and 50mg of Patton & Reeders indicator.
7.5 Titrate with 0.01M EDTA to a sharp change in colour from wine red to clear blue (see
7.7)
7.6 CaO % = 0.05608 x 25 x V
W
7.7 Manganes interferes with estimation of CaO and the procedure is modified as follows:
Warm 10ml of solution (under 1) on a hot plate and add dropwise ammonium hydroxide
(1:1) with constant shaking till a turbidity appears filter through whatman 41 and wash
the filter paper 2-3 times with distilled water. Add 2-3 drops of nitric acid and 50mg of
potassium perioda keep the flask on water bath until pink colour developes. Shake and
allow to cool to room temperature. Add 5 ml of glycerol (1:1) with constant
stirring,follows by addition of 5ml of diethylamine and 20ml of 4N NaOH to adjust pH to
12 or more. Add approx. 50ml distilled water, 100mg Patton & Reeders indicator and
titrate with 0.01M EDTA to a sharp change in colour from violet to blue. Calculate
Calcium Oxide as given under 7.6 above.

8.0. Magnesium Oxide

8.1. Take 10ml of solution given under 5.2.1.

8.2. Add 5ml of triethonolamine with constant shaking and 20ml of buffer solution pH 10.
8.3. Add 50mg of thymolphthalaxone indicator and approx 50ml distilled water.
8.4. Titrate with 0.01M EDTA to a sharp change the colour from blue to clear pink.
8.5. This titration gives volume of EDTA corresponding to calcium and magnesium oxide in
the solution. Subtract volume of EDTA used in filtration of calcium oxide to obtain
volume of EDTA for titration of magnesium oxide in the solution.
8.6. MgO(%) = 0.04032 x 25 x (V1 -V)
W
V1 = Volume of EDTA used in this titration in ml.
V = Volume of EDTA used for CaO in ml.
W = Weight of Sample in g.

E. RAMESH
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9.0. Sulphur Trioxide

9.1. To about 1 g accurately weighed sample add 25 ml of water, 5 ml of hydrochloric acid

and digest on water bath.

9.2. Dilute to 50 ml with hot water, filter through Whatmann 40 filter paper and wash
thoroughly with hot water.

9.3. Set aside filter paper containing residue for determination of insoluble residue.

9.4. Dilute filtrate to 250 ml, heat to boiling and precipitate barium sulphate by drop wise
addition of 10 ml of hot barium chloride solution (10%).

9.5. Allow the precipitate to settle for 4 hours on water bath or preferably overnight.

9.6. Filter precipitate through Whatmann no 42 and wash thoroughly with hot water.

9.7. Transfer precipitate to a weighed platinum crucible (W 1 ), dry and char paper without
enflaming at low temperature. Ignite crucible at 850-900o C to constant weight (W2 ).

(W2 - W1 ) x 34.3
9.8. SO 3 (%) =
weight of sample

10.0. Insoluble Residue

10.1. Digest filter paper containing residue under 3 (sulphur trioxide) in 30 ml of hot water and
30 ml of hot 2 N sodium carbonate solution for 10 minutes maintaining constant volume
at water bath.

10.2. Filter through Whatmann 40 filter paper, wash with hot (1:99) hydrochloric acid to
remove excess alkali; and finally with hot water until chloride free.

10.3. Transfer residue to a weighted platinum crucible (W 1 ) dry and char paper without
enflaming at low temperature. Ignite residue at 950-1000o C to constant weight (W2 )

(W2 - W1 ) x 100
10.4. Insoluble Residue (%) =
weight of sample

E. RAMESH
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11.0. Chloride – Volhard’s Method

11.1. Weigh 2.0g of cement sample in a beaker.
11.2. Moisten with 10ml of distilled water to prevent lumping and add 10ml of 6N nitric acid.
11.3. Digest with gentle heat and agitation until the sample is completely dissolved.
11.4. Dilute with 25ml of hot water and filter through medium textured filter into a 250ml
titration flask. Wash thoroughly with hot water.
11.5. add 10ml of standard silver nitrate solution to the titration flask. Further add 1ml ferric
alum indicator and 2ml nitrobenzene.
11.6. Titrate the excess silver nitrate with drop wise addition of standard ammonium
thiocyanate with constant and vigorous stirring until a permanent faint reddish brown
colouration appears in the solution.
11.7. Note volume of ammonium thiocyanate used from the volume of silver nitrate added
subtract the volume of silver nitrate solution that is equivalent to volume of standard
thiocyanate used. This given volume of silver nitrate solution corresponding to chloride
solution.
11.8. Cl % = 0.03546 x N x V x 100
W
N = Normality of silver nitrate solution
V = Volume of silver nitrate corresponding to chloride.
W = Weight of sample in g.

E. RAMESH