Determination of Total Carbonate in Limestone, Rawmeal and Kiln feed:-

Preparation and Standardization of 0.4N HCl :-

Take one vial of 10N of AR Grade HCl (or 87.5 ml of approx 12N) and make it up to
2500 ml in distilled water.

Weigh accurately 0.5300 grams of Sodium Carbonate previously dried at a

temperature of 105-110 deg. C in a conical flask and add about 10-15 ml of distilled
water and warm it for dissolution. Add 1-2 drops of methyl orange indicator and titrate
against prepared HCl taken in a dosimat for a wine red end point. Note down the titre
volume.

Normality of HCl = 10

Vol. of Hcl consumed

Preparation and Standardization of 0.2N NaOH :-

Take one vial of 10N NaOH (or 40 grams of AR grade pellets) and make up to 5000
ml in distilled water. Standardize the prepared alkali against the standard HCl
solution.

Take 10 ml of the std HCl solution in a conical flask and add 2-3 drops of
Phenolphthalein indicator and titrate against the alkali taken in a dosimat till the
appearance of Pale pink color endpoint. Note down the volume of NaOH consumed

Normality of NaOH = Normality of HCl * 10

Vol. of NaOH consumed

Determination of % TC :-

Weigh accurately 0.5000 grams of sample in a conical flask and add 25 ml of 0.4N
HCl and wash the sides of the conical flask with distilled water and boil it to about 70-
80 deg. C for about one or two minutes and wash the sides of the conical flask with
distilled water and add 2-3 drops of Phenolphthalein Indicator and titrate when hot
against 0.2 N NaOH till the appearance of Pale pink color endpoint. Note down the
volume of NaOH consumed and calculate as follows.

% TC = Normality of HCl *10 *((25 – (volume of NaOH consumed * 0.5))

Standardization using Calcium Carbonate:-

Weigh accurately 0.4000 grams of sample (Purity of 99.5%) in a conical flask and
add 25 ml of 0.4N HCl and wash the sides of the conical flask with distilled water and
boil it to about 70-80 deg. C for about one or two minutes and wash the sides of the
conical flask with distilled water and add 2-3 drops of Phenolphthalein Indicator and
titrate when hot against 0.2 N NaOH till the appearance of Pale pink color endpoint.
Note down the volume of NaOH consumed and calculate as follows.

% TC (as CaCO3) = 99.5 (purity)

* 0.4 = 79.6 %
0.5

Factor: - If titre reading is 10.2 and the normality is 0.4 N HCl and 0.2N NaOH then
the factor is said to be 100 and

% TC = 100- (2 * volume of NaOH consumed)

Alternate Method of Standardization:-

Collect about 2-3 kilograms of Kiln feed sample and homogenize the sample. Then
the homogenized sample needs to be analyzed by about 4-5 competent chemists
and testers nearly five times each and the sample values with the minimum standard
deviation is taken as the Standard sample %TC (for eg.,79.4±0.2) and the sample
needs to be kept in an airtight container. This sample can also be used as a standard
sample instead of Calcium Carbonate by using the given below equation

% TC = 100 - 2 x V + Correction factor

The correction factor corresponds to the difference in TC content which could

either be in the +ve side or in the –ve side.

Determination of MgCO3 :-

After completion of % Total carbonate determination add 5 ml of excess NaOH in the

same conical flask and add 4-5 drops of Thymolphthalein till a purple violet color
appears and boil the solution. After boiling the contents cool it to room temperature
rapidly and back titrate till the disappearance of the violet color. Note down the
volume of HCl consumed

% MgCO3 = 8.43 * Normality of NaOH * [exc. NaOH – (2 * vol. of HCl consumed )]

% CaCO3 = % TC – (1.19 * MgCO3)

Reactions involved in Detmn of % TC :-

CaCO3 + 2 HCl CaCl2 + H2O + CO2

MgCO3 + 2 HCl MgCl2 + H2O +CO2

Unreacted
HCl + NaOH NaCl + H2O

MgCl2 + NaOH Mg( OH)2 + 2NaCl

Mg(OH)2 + HCl  MgCl2 + H2O