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Question: 0.5 g of fuming sulphuric acid (H\(_2\)SO\(_4\)+SO\(_3\)), called oleum, is diluted with water. This...

0.5 g of fuming sulphuric acid (H2_2SO4_4+SO3_3), called oleum, is diluted with water. This solution is completely neutralised at 26.7 ml of 0.4 M NaOH. Find the percentage of free SO3_3 in the sample solution.
A. 20.73%
B. 43.80%
C. 79.27%
D. 60.74%

Explanation

Solution

Hint: This question is based on the mole concept. Find out the equivalence weight of molecules included in the composition of oleum. Then you can calculate the total number of equivalents, and then percentage can be calculated.

Complete step by step answer:
First, we know that oleum consists of sulphuric acid (H2_2SO4_4), and free SO3_3. The amount of fuming sulphuric acid used to perform the reaction is given i.e. 0.5 g.
So, let us consider the mass of SO3_3 in the given sample of oleum be x g.
Then, the mass of sulphuric acid will be equal to (0.5-x) g.
Now, if we calculate the equivalent weight of SO3_3, then the molecular weight of SO3_3 is 80. Thus, equivalent weight = 80/2 = 40
Similarly, for sulphuric acid, the molecular weight is 98. Then, equivalent weight = 98/2 = 49
Thus, no. of g equivalents for SO3_3 = x40\dfrac{x}{40};
No. of g equivalents for H2_2SO4_4= 0.5x49\dfrac{0.5-x}{49}
Therefore, total no. of g equivalents = x40\dfrac{x}{40} + 0.5x49\dfrac{0.5-x}{49}
According to the question, 26.7 ml of 0.4 N NaOH will have 0.41000\dfrac{0.4}{1000} ×\times 26.7 equivalents of NaOH.
Now, if we equalise the no. of g equivalents of oleum, and NaOH, at the equivalence point; then 0.41000\dfrac{0.4}{1000} ×\times 26.7= x40\dfrac{x}{40} + 0.5x49\dfrac{0.5-x}{49}.
By calculating we get x = 0.1036
Therefore, % of free SO3_3 = 0.10360.5\dfrac{0.1036}{0.5} ×\times 100= 20.72 %
Thus, % of free SO3_3 in the sample solution is 20.72%. The correct option is (A).

Note: Don’t get confused while calculating the percentage. Just move step by step as shown. The equivalents for the composition of oleum will be considered different in the terms of mass, as we have to calculate the percentage of SO3_3.