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Q8.35:
In the estimation of sulphur by Carius method, 0.468 g of an organic sulphur compound afforded 0.668 g of barium sulphate. Find out the percentage of sulphur in the given compound.

Solution :

Step 1: Chemical Principles and Stoichiometric Basis

The Carius method for the estimation of sulphur relies on the quantitative conversion of organic sulphur into inorganic sulphate ions ($SO_4^{2-}$). These ions are subsequently precipitated as barium sulphate ($BaSO_4$) by the addition of barium chloride ($BaCl_2$).

The chemical relationship is defined by the stoichiometry of the precipitation reaction:
$SO_4^{2-} (aq) + Ba^{2+} (aq) \rightarrow BaSO_4 (s)$

From the molar masses, we observe that $1$ mole of $BaSO_4$ contains $1$ mole of sulphur ($S$).

Step 2: Calculation of Molar Masses

Using the standard atomic masses ($S = 32.06 \, g/mol$, $Ba = 137.33 \, g/mol$, $O = 16.00 \, g/mol$):

  • Molar mass of $S = 32.06 \, g/mol$
  • Molar mass of $BaSO_4 = 137.33 + 32.06 + (4 \times 16.00) = 233.39 \, g/mol$

Step 3: Determining the Mass of Sulphur in the Precipitate

Since $233.39 \, g$ of $BaSO_4$ contains $32.06 \, g$ of sulphur, we use the mass-proportion formula [Per Law of Definite Proportions]:

Mass of sulphur $= \left( \frac{\text{Atomic mass of S}}{\text{Molar mass of } BaSO_4} \right) \times \text{Mass of } BaSO_4$

Mass of sulphur $= \left( \frac{32.06}{233.39} \right) \times 0.668 \, g$

Mass of sulphur $\approx 0.13745 \times 0.668 \approx 0.091817 \, g$

Step 4: Calculation of Percentage Composition

The percentage of sulphur in the original organic compound is calculated as follows:

$\% S = \left( \frac{\text{Mass of sulphur}}{\text{Mass of organic compound}} \right) \times 100$

$\% S = \left( \frac{0.091817}{0.468} \right) \times 100$

$\% S \approx 19.619 \%$

Data Summary Table

Parameter Value
Mass of organic compound $0.468 \, g$
Mass of $BaSO_4$ $0.668 \, g$
Calculated Mass of $S$ $0.0918 \, g$
Percentage of $S$ $19.62 \%$
Organic S Carius Method BaSO4 ppt

Final Solution: The percentage of sulphur in the given compound is $19.62\%$.


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