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Published on: 09/10/2019
Ionic Equilibrium
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1.
Calculate the pH of 0.1M CH3COOH solution. Dissociation constant of acetic acid is \(1.8\times10^{-5}\).
2.
Define pH.
3.
Define ionic product of water. Give its value at room temperature.
4.
Explain common ion effect with an example.
5.
Find the pH of a buffer solution containing 0.20 mole per litre sodium acetate and 0.18 mole per litre acetic acid. Ka for acetic acid is \(1.8\times10^{-5}\).
6.
Derive an expression for the hydrolysis constant and degree of hydrolysis of salt of strong acid and weak base.
7.
Calculate the extent of hydrolysis and the pH of 0.1 M ammonium acetate Given that \(K_{a}=K_{b}=1.8\times10^{-5}\)
8.
The Ka value for HCN is 10-9. What is the pH of 0.4M HCN solution?
9.
50ml of 0.05M HNO3 is added to 50ml of 0.025M KOH. Calculate the pH of the resultant solution.
10.
Calculate the pH of 1.5\(\times\)10-3 M solution of Ba(OH)2
1.
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
2.
(i) pH = -log10 [H3O+]
(ii) The pH of a solution is defined as the negative logarithm of base 10 of the molar concentration of the hydronium ions present in the solution.
3.
(i) \(\mathrm{K}_{\mathrm{w}}=\left[\mathrm{H}_{3} \mathrm{O}^{+}\right]\left[\mathrm{OH}^{-}\right]=1 \times 10^{-14}\left(25^{\circ} \mathrm{C}\right)\)
(ii) Ionic product of water is defined as the product of the concentration of hydronium and hydroxide ions of pure water. Its value at 25oC is \(1 \times 10^{-14} \mathrm{~mol}^{2} \mathrm{dm}^{-2}\)
4.
(i) The dissociation of a weak acid (CH3COOH) is suppressed in the presence of a salt (CH3COONa) containing an ion common to the weak electrolyte. It is called the common ion effect.
(ii) Consider the dissociation of a weak acid, acetic acid whose ionisation is incomplete.
CH3COOH(aq) ⇌ H+(aq) + CH3COO-(aq)
(iii) If the salt sodium acetate with common ion CH3COO- is added to the above equilibrium, it dissociates completely increasing.
CH3COONa(aq)⟶Na+(aq) + CH3COO-(aq)
(iv) Hence, the overall concentration of CH3COO- is increased, and the acid dissociation equilibrium is disturbed.
(v) So, in order to maintain the equilibrium, the excess CH3COO- ions combines with H+ ions to produce much more unionized CH3COOH i.e, the equilibrium will shift towards the left. In other words, the dissociation of CH3COOH is suppressed.
5.
\(pH=pK_{a}+\log[\frac{salt}{acid}]\)
Given that Ka = \(1.8\times10^{-5}\)
\(\therefore pK_{a}=-\log(1.8\times10^{-5})\)
= 5 - log 1.8
= 5 - 0.26
= 4.74
\(\therefore pH=4.74+\log\frac{0.20}{0.18}\)
= 4.74 + log(10/9)
= 4.74 + log10 - log9
= 4.74 + 1 - 0.95
= 5.74 - 0.95
= 4.79
6.
(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+]
7.
\(h=\sqrt{K_{h}}=\sqrt{\frac{K_{w}}{K_{a}K_{b}}}=\sqrt{\frac{1\times10^{-14}}{1.8\times10^{-5}\times{1.8\times10^{-5}}}}\)
\(= \frac{1 \times10^{-7}}{1.8\times10^{-5}}\)
=\(0.7453\times10^{-2}\)
\(pH=\frac{1}{2}pK_{w}+\frac{1}{2}pK_{a}-\frac{1}{2}pK_{b}\)
Given that \(K_{a}=K_{b}=1.8\times10^{-5}\)
if Ka = Kb, then, pKa = pKb
\(\therefore pH= \frac{1}{2}pK_{w}=\frac{1}{2}(14)=7\)
pH = 7
8.
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
9.
\(\mathrm{M} =\frac{\mathrm{V}_{1} \mathrm{M}_{1}-\mathrm{V}_{2} \mathrm{M}_{2}}{\mathrm{~V}_{1}+\mathrm{V}_{2}} \)
\(=\frac{(50 \times 0.05)-(50 \times 0.025)}{50+50} \)
\(\text { Molarity }=\frac{\text { Number of millimoles }}{\mathrm{V}_{\mathrm{m} l}}\)
\(=\frac{2.5-1.25}{100}=\frac{1.25}{100}=0.0125 \mathrm{M} \)
\(\mathrm{pH} =-\log _{10}\left[\mathrm{H}^{+}\right] \)
\(=-\log _{10} 0.0125 \)
Normality = Molarity \(\times\) basicity
\(=-\log _{10}\left(1.25 \times 10^{-2}\right) \)
\(=-\left[\log _{10} 1.25-2 \log _{10} 10\right] \)
\(=2-\log _{10} 1.25=2-0.0969 \)
pH = 1.9031
10.
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
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