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Question: A plot given shows P – T curves (where P is the pressure and T is the temperature) for two solvents ...

A plot given shows P – T curves (where P is the pressure and T is the temperature) for two solvents X and Y, and isomolar solutions of NaCl in these solvents. NaCl completely dissociates in both the solvents. In addition to an equal number of moles of non-volatile solute S in equal amount (in Kg) of these solvents, the elevation of the boiling point of solvent X is three times that of solvent. Solute S is known to undergo dimerization in these solvents. If the degree of dimerization is 0.7 in solvent Y, the degree of dimerization in solvent X is:

Explanation

Solution

The elevation in the boiling point is equal to the product of ionization of solute, molality, and molal elevation constant. The formula is ΔTb=i x m x Kb\Delta {{T}_{b}}=i\text{ x m x }{{\text{K}}_{b}}. The value of i can be calculated by the reaction 2(S)S22(S)\to {{S}_{2}}.

Complete answer: In the graph, there are four lines in which the first 2 lines are used for solvent X and the last two lines are used for solvent Y.
Line 2 is at 362 K and line 1 is at 360 K, so we can calculate the elevation in the boiling point as:
ΔTb(X)=362360=2\Delta {{T}_{b(X)}}=362-360=2
Line 4 is at 368 K and line 3 is at 367 K, so we can calculate the elevation in the boiling point as:
ΔTb(Y)=368367=1\Delta {{T}_{b(Y)}}=368-367=1
According to the formula, we can write for X and Y as:
ΔTb(X)=i x mNaCl x Kb(X)\Delta {{T}_{b(X)}}=i\text{ x }{{\text{m}}_{NaCl}}\text{ x }{{\text{K}}_{b(X)}}
ΔTb(Y)=i x mNaCl x Kb(Y)\Delta {{T}_{b(Y)}}=i\text{ x }{{\text{m}}_{NaCl}}\text{ x }{{\text{K}}_{b(Y)}}
When we divide the above equations, we get:
Kb(X)Kb(Y)=2\dfrac{{{K}_{b(X)}}}{{{K}_{b(Y)}}}=2
Since the dimerization takes place, we can write the equation as:
2(S)S22(S)\to {{S}_{2}}
After the equilibrium is attained, the concentration of S will be 1α1-\alpha and the value of S2{{S}_{2}} will be α2\dfrac{\alpha }{2}
So, the value of i, will be:
i=(1α2)i=(1-\dfrac{\alpha }{2})
Now, putting these values in the elevation in boiling point equation, we get:
ΔTb(X)=(1α12) x mNaCl x Kb(X)\Delta {{T}_{b(X)}}=(1-\dfrac{{{\alpha }_{1}}}{2})\text{ x }{{\text{m}}_{NaCl}}\text{ x }{{\text{K}}_{b(X)}}
ΔTb(Y)=(1α22) x mNaCl x Kb(Y)\Delta {{T}_{b(Y)}}=(1-\dfrac{{{\alpha }_{2}}}{2})\text{ x }{{\text{m}}_{NaCl}}\text{ x }{{\text{K}}_{b(Y)}}
In the question, it is given that:
ΔTb(X)=3 x ΔTb(Y)\Delta {{T}_{b(X)}}=3\text{ x }\Delta {{T}_{b(Y)}}
Combining, all these we can write:
(1α12) x Kb(X)=3 x (1α22) x Kb(X)(1-\dfrac{{{\alpha }_{1}}}{2})\text{ x }{{\text{K}}_{b(X)}}=3\text{ x }(1-\dfrac{{{\alpha }_{2}}}{2})\text{ x }{{\text{K}}_{b(X)}}
2 x (1α12)=3 x (1α22)2\text{ x }(1-\dfrac{{{\alpha }_{1}}}{2})=3\text{ x }(1-\dfrac{{{\alpha }_{2}}}{2})
a2{{a}_{2}} = 0.7 and a1{{a}_{1}} = 0.05.
The degree of dimerization of solvent X is 0.05.

Note: Don’t get confused between the formulas ΔTb=i x m x Kb\Delta {{T}_{b}}=i\text{ x m x }{{\text{K}}_{b}} and ΔTb= m x Kb\Delta {{T}_{b}}=\text{ m x }{{\text{K}}_{b}}, the former is used when there is any electrolyte or ionic compound is present in the solution and the latter is used when covalent compound is present.