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Published on: 02/06/2021
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Questions + Answers key
Take MCQ Chemistry Test1.
Derive an expression for Ostwald’s dilution law.
2.
Derive an expression for the hydrolysis constant and degree of hydrolysis of salt of strong acid and weak base.
3.
The Ka value for HCN is 10-9. What is the pH of 0.4M HCN solution?
4.
Calculate the pH of 1.5\(\times\)10-3 M solution of Ba(OH)2
5.
Calculate the pH of 0.1M CH3COOH solution. Dissociation constant of acetic acid is \(1.8\times10^{-5}\).
1.
(i) Ostwald's dilution law relates the dissociation constant of the weak acid (Ka) with its degree of dissociation (α) and the concentration (c).
where \(\alpha=\frac{\text { Number of moles dissociated }}{\text { Total number of moles }}\)
(ii) The dissociation of acetic acid can be represented as
\(\mathrm{CH}_{3} \mathrm{COOH} \rightleftharpoons \mathrm{H}^{+}+\mathrm{CH}_{3} \mathrm{COO}^{-}\)
The dissociation constant of acetic acid is,
\({ K }_{ a }=\frac { \left[ { H }^{ + } \right] \left[ { CH }_{ 3 }COO^{ - } \right] }{ \left[ { CH }_{ 3 }COOH \right] } \) ........(1)
| CH3COOH | H+ | CH3COO- | |
| Initial number of moles | 1 | - | - |
| Degree of dissociation of CH3COOH | α | - | - |
| Number of moles at equilibrium | 1-α | α | α |
| Equilibrium concentration | (1-α)C | αC | αC |
Substituting the equilibrium concentration in equation (1)
\({ K }_{ a }=\cfrac { \left( \alpha C \right) \left( \alpha C \right) }{ \left( 1-\alpha \right) C } \)
\({ K }_{ a }=\cfrac { { \alpha }^{ 2 }C }{ 1-\alpha } \) .......(2)
(iii) We know that weak acid dissociates only to a very small extent compared to one, a is so small and hence in the denominator (1 - α) ⋍1. The above expression (2) now becomes,
ka =a2C \(\Rightarrow { \alpha }^{ 2 }=\cfrac { { k }_{ a } }{ C } \) ; \(\alpha =\sqrt { \cfrac { { K }_{ a } }{ C } } \)
(iv) When dilution increases, the degree of dissociation of weak electrolyte also increases. This is called Ostwald's dilution law
Also \(;\left[\mathrm{H}^{+}\right]=\alpha \mathrm{C}\) and \(\left[\mathrm{H}^{+}\right]=\left(\sqrt{\frac{\mathrm{K}_{\mathrm{a}}}{\mathrm{C}}}\right) \mathrm{C}=\sqrt{\frac{\mathrm{K}_{\mathrm{a}} \mathrm{C}^{2}}{\mathrm{C}}}=\sqrt{\mathrm{K}_{\mathrm{a}} \cdot \mathrm{C}}\)
Similarly for a weak base
\(\begin{aligned} & \mathrm{K}_{\mathrm{b}}=\alpha^2 \mathrm{C} ; \quad \therefore \alpha=\sqrt{\frac{\mathrm{k}_{\mathrm{b}}}{\mathrm{C}}}, \\ \end{aligned}\)
\(\begin{aligned} & {\left[\mathrm{OH}^{-}\right] \alpha \mathrm{C}=\sqrt{\frac{\mathrm{K}_{\mathrm{b}}}{\mathrm{C}}} \times \mathrm{C}=\sqrt{\frac{\mathrm{K}_{\mathrm{b}} \mathrm{C}^2}{\mathrm{C}}}=\sqrt{\mathrm{K}_{\mathrm{b}} \mathrm{C}}} \end{aligned}\)
2.
(i) Let us consider the reactions between a strong acid, HCI, and a weak base, NH4OH, to produce a salt, NH4CI, and water.
HCI(aq) + NH4OH(aq) ⇌ NH4CI(aq) + H2O (I)
NH4CI(aq) ⟶ NH4+ +CI-(aq)
(ii) NH4+ is a strong conjugate acid of the weak base NH4OH and it has a tendency to react with OH- from water to produce unionised NH4OH
NH4+ (aq) + H2O(I) ⇌ NH4OH(aq) + H+(aq)
(iii) There is no such tendency shown by Cl- and therefore [H+] > [OH-]; the solution is acidic and the pH is less than 7.
(iv) The Kh and Kb are related by
\(\mathrm{K}_{\mathrm{h}} \cdot \mathrm{K}_{\mathrm{b}}=\mathrm{K}_{\mathrm{w}}\)
(Or)
\(\mathrm{K}_{\mathrm{h}}=\frac{\mathrm{K}_{\mathrm{w}}}{\mathrm{K}_{\mathrm{b}}}\)
Degree of hydrolysis (h)
\(\underset{(1-h)}{\mathrm{NH}_{4}^{+}(\mathrm{aq})}+\mathrm{H}_{2} \mathrm{O}_{(j)} \rightleftharpoons \underset{h} {\mathrm{NH}_{4} \mathrm{OH}_{(\mathrm{aq})}} +\mathrm{H}^{+} \underset{h}{(\mathrm{aq})}\\ \)
\(\mathrm{K}_{\mathrm{h}} =\frac{\left[\mathrm{NH}_{4} \mathrm{OH}\right]\left[\mathrm{H}^{+}\right]}{\left[\mathrm{NH}_{4}^{+}\right]} \\ \)
\(=\frac{\mathrm{hc} \times \mathrm{h}}{(1-\mathrm{h}) \mathrm{c}} \)
\(K_{h}=\frac{h^{2} c}{(1-h)} \)
\(\text{If } \mathrm{h}<<1 ; \mathrm{K}_{\mathrm{h}} \simeq \mathrm{h}^{2} \mathrm{c} \)
\(h^{2}=\frac{K_{h}}{c}\)
\(h=\sqrt{\frac{K_{h}}{c}} \ (or) \ h=\sqrt{\frac{K_{w}}{K_{b} \cdot C}} \quad\left(\because K_{h}=\frac{K_{w}}{K_{b}}\right)\)
Also; \(\left[\mathrm{H}^{+}\right]=\sqrt{\mathrm{K}_{\mathrm{h}} \cdot \mathrm{C}} \) (or) \(\left[\mathrm{H}^{+}\right]=\sqrt{\frac{\mathrm{K}_{\mathrm{w}} \cdot \mathrm{C}}{\mathrm{K}_{\mathrm{b}}}}\)
pH = -log [H+]
3.
HCN is a weak acid
\({\left[\mathrm{H}^{+}\right] } =\sqrt{\mathrm{K}_{\mathrm{a}} \cdot \mathrm{C}} \)
\(=\sqrt{10^{-9} \times 0.4} \)
\(=\sqrt{4 \times 10^{-10}} \)
\(=2 \times 10^{-5} \)
\(\mathrm{pH} =-\log _{10}\left[\mathrm{H}^{+}\right] \)
\(=-\log _{10}\left(2 \times 10^{-5}\right) \)
\(=-\left[\log _{10} 2-5 \log 10\right] \)
\(=5-\log 2\)
= 5-0.3010 = 4.6990
4.
Considering Ba(OH)2 to be a strong base:
\(\text { Normality } =\text { Molarity } \times \text { Acidity } \)
\(=1.5 \times 10^{-3} \times 2\)
\({\left[\mathrm{OH}^{-}\right] } =3 \times 10^{-3} \)
\(\mathrm{pOH} =-\log _{10}[\mathrm{OH}^-] \)
\(=-\log _{10}\left(3 \times 10^{-3}\right) \)
\(=-\left[\log _{10} 3+3 \log 10\right] \)
= 3-log 3
= 3-0.4771
= 2.5229
\(\mathrm{pH} =14-\mathrm{pOH} \)
= 14-2.5229
pH = 11.4771 = 11.48
5.
pH=-log[H+]
For weak acids,
\(= \sqrt{k_a \times C}\)
=\(\sqrt{1.8\times10^{-5}\times0.1}\)
=\(1.34 \times10^{-3}\) M
\(pH=-\log(1.34\times10^{-3})\)
= 3-log1.34
= 3-0.1271
= 2.8729 \(\simeq\) 2.87
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