CHEM1070B: Principles of Modern Chemistry

Assignment 4
Answer all the questions using the empty space provided. (80 marks in total)

1. Write equilibrium constant expressions (K) for the following reactions:

a) HC2H3O2 + H2O H3O+ + C2H3O2¯

b) HC2H3O2 + CH3OH H2O + C2H3O2CH3

(4 marks)
Ka = [H3O+][C2H3O2¯ ] / [HC2H3O2]
K = [H2O][C2H3O2CH3] / [HC2H3O2][CH3OH] (only in dilute aqueous solution, the [H2O] can
be omitted)
(2 marks each)

2. Write the formulas for the conjugate bases of the following acids:
a) HCN
b) HCO3¯
c) N2H5+
(3 marks)
a) CN ¯ b) CO32- c) N2H4
(1 mark each)

3. Write the formulas for the conjugate acids of the following bases:
a) HCO3¯
b) C5H5N
c) N2H5+
(3 marks)
a) H2CO3 b) C5H5NH+ c) N2H62+
(1 mark each)

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4. Calculate the hydronium ion concentration and the percent dissociation of an acid
with Ka = 1.0 x 10-6 in
a) 0.10 M solution
b) 0.0010 M solution
c) Explain precisely the di erence between the terms higher hydronium ion
concentration and greater percent dissociation, as applied to weak acid solution.
(10 marks)

HA + H2O → H3O+ + A¯ Ka = [H3O+][A¯ ] / [HA] = 1.0 x 10-6 (2 marks)

Initial Produced Used up Equilibrium

[H3O+] 0 x - x

[A¯ ] 0 x - x

[HA] 0.10 - x 0.10 - x ≃ 0.10

(3 marks)
a) x2/(0.10) = 1.0 x 10-6; x = 3.2 x 10-4; % ionisation = [x/(0.10)] x 100% = 0.32 % (2
marks)
b) x2/(0.0010) = 1.0 x 10-6; x = 3.2 x 10-5; % ionisation = [x/(0.0010)] x 100% = 3.2 % (2
marks)
c) Despite the lower hydronium ion concentration, the weak acid is ionised to a greater
percent in part (b), where it is more dilute. (1 marks)

5. Calculate the percent ionisation of 1.00 M solution of hydrocyanic acid, HCN.

(4 marks)
HCN H+ + CN ¯ ; Ka = [H+][CN ¯ ] / [HCN] (1 mark)

Let x = [H+] = [CN ¯ ], then [HCN] = 1.00 - x, and x will be very small (1 mark)
Ka = x2 / 1.00 = 6.2 x 10-10 (1 mark); x = 2.5 x 10-5 ; % ionisation = [2.5 x 10-5 / (1.00)] x
100 % = 0.0025 % (1 mark)

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6. A solution is prepared with 0.0200 M NaC2H3O2 and 0.0500 M HC2H3O2;
a) What is the hydronium ion concentration (Ka = 1.8 x 10-5)?
b) Determine the pH of the solution.
(6 marks)
Ka = [C2H3O2¯ ][H3O+] / [HC2H3O2] = 1.8 x 10-5 (1 mark)
Initial Produced Used up Equilibrium

[C2H3O2¯ ] 0.0200 x - 0.0200 + x ≈ 0.0200

[H3O+ ] 0.0000 x - x

[HC2H3O2] 0.0500 - x 0.0500 - x ≈ 0.0500

(3 marks)
(0.0200)(x) / (0.0500) = 1.8 x 10-5; x = 4.5 x 10-5 = [H3O+ ] (1 mark)
b) pH = -log [H3O+ ] = 4.35 (1 mark)

7. How many moles of sodium hydroxide can be added to 1.00 L of a solution 0.100 M in
NH3 and 0.100 M in NH4Cl without changing the pOH by more than 1.00 unit? Assume
no changes in volume.
(10 marks)
Kb = 1.8 x 10-5, so pKb = 4.75 and [NH4+] / [NH3] = 1.00 (1 mark)
pOH = pKb + log [NH4+] / [NH3] = 4.75 + 0.00 = 4.75 (1 mark)
The original pOH = 4.75 and cannot be less than 3.75. (1 mark)
pOH = 3.75 = 4.75 + log [NH4+] / [NH3]; log NH4+] / [NH3] = -1.00; so [NH4+] / [NH3] = 0.10
(2 marks)
Initially, [NH4+] + [NH3] = 0.200; although the reaction with OH ¯ converts NH4+ into NH3,
the sum of these two concentrations remains 0.200. (1 mark)
[NH4+] + [NH3] = 0.200 M; and [NH4+] = 0.10 [NH3] (1 mark)
So 0.10[NH3] + [NH3] = 0.200 M and [NH3] = 0.182 M (1 mark)
Hence, [NH4+] = 0.018 M (1 mark)
Assume no change in volume, 0.100 - 0.018 = 0.082 mol of NaOH can be added without
changing the pOH by more than 1.00 unit. (1 mark)

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8. A galvanic cell was operated under almost ideally reversible conditions at a current of
10-16 A.
a) At this current, how long would it take to deliver 1 mol electrons?

(1 mol e¯ )(96500 Cmol-1)(1s / 10-16 C) = 9.65 x 1020 s (2 mark)

(9.65 x 1020 s)(1/3600 s)(1 day/24 hr)(1 year/365 days) = 3.06 x 1013 years (1 mark)

b) How many electrons would be delivered by the cell to a pulsed measuring circuit in
10 ms of operation?

10 ms = (10 x 10-3 s)(1 mol e¯ / 9.65 x 1020 s)(6.02 x 1023 e¯ / 1 mol e¯) = 6 e¯ (2 marks)

(5 marks)

9. A constant current was passed through a solution of AuCl4¯ ions between gold
electrodes. After a period of 10.0 min, the cathode increased in mass by 1.314 g. How
many charge, q, was passed? What was the current, I ?
(5 marks)
AuCl4¯ + 3e¯ → Au + 4Cl ¯ (1 mark)
No. of moles of Au = 1.314 g / 197 gmol-1 = 6.67 x 10-3 mol (1 mark)
q = (6.67 x 10-3 mol) x 3 = 2.00 x 10-2 F (1 mark)
I = q / t = (2.00 x 10-2)(96500)/(600) (1 mark) = 3.22 A (1 mark)

10. What mass of bismuth metal is deposited electrolytically from bismuth(III) solution in
30.0 min by a current of 40.0 A?
(3 marks)
Equation (1 mark)
(30 min)(60 smin-1)(40 Cs-1)(1 mol e¯ / 96500 C)(1 molBi / 3 mol e¯ )(209 g Bi / mol Bi)
= 52.0 g Bi

11. An electrolytic cell contains a solution of CuSO4 and an anode of impure copper. How
many kg of copper will be re ned (deposited on the cathode) by 150 A maintained for
12 h?
(2 marks)
Cu2+ + 2e¯ → Cu (1 mark)
(12 h) (3600 s/hr)(150 C/s)(1 mol e¯ / 96500 C)(1 mol Cu / 2 mol e¯ )(63.5 g Cu / mol Cu) /
1000
= 2.1 kg Cu (1 mark)

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 12. Calculate the free energy change per mol copper(II) ion formed in a cell consisting of a
copper/copper(II) ion half cell suitably connected to a silver/silver(I) ion half cell of
su cient size that the ions is not changed from 1.00 M.
(5 marks)

Ag+ + e¯ → Ag Eº = 0.80 V (1 mark)

Cu2+ + 2e¯ → Cu Eº = 0.34 V (1 mark)
Cu + 2Ag+ → 2Ag + Cu2+ Eº = 0.46 V (1 mark)

∆Gº = -EºnF = -(0.46 V)(2 mol e¯ )(96500 C/mol e¯ ) = - 88800 J = -89 kJ (2 mark)

13. Given the following standard reduction potentials:

Sn4+ + 2e¯ → Sn2+ Eº = 0.13 V
Ag+ + e¯ → Ag Eº = 0.80 V
a) Calculate the potential of the cell
Pt⏐Sn2+ (1.0 M, aq), Sn4+ (1.0 M)⏐⏐Ag+ (1.0 M)⏐Ag.

Eº = - 0.13 + 0.80 = 0.67 V

b) Write equations for both half-cell reactions and the overall reaction.

Sn2+ + 2Ag+ → Sn4+ + 2Ag

c) Calculate the value of ∆Gº for the reaction.

∆Gº = -nFEº = -(2)(96500)(0.67) = -1.3 x 105 J (2 marks)

d) In what way would an increase in the concentration of silver ion a ect the potential
of the cell?

The potential would be increased. (1 mark)

(5 marks)

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14. A reaction between substances A and B is represented stoichiometrically by A + B →
C. Observations on the rate of this reaction are obtained in three separate experiments
as follows:

Initial Concentrations
Duration of Final Concentration,
[A]0, M [B]0, M Experiment, ∆t, hr [A]f, M

1 0.1000 1.0 0.50 0.0975

2 0.1000 2.0 0.50 0.0900

3 0.0500 1.0 2.00 0.0450

What is the order with respect to each reactant, and what is the value of the rate
constant?
(10 marks)

[A]0, M [B]0, M ∆[A], M ∆t, h - ∆[A]/∆t, Mh-1

1 0.1000 1.0 -0.0025 0.50 0.0050

2 0.1000 2.0 -0.0100 0.50 0.0200

3 0.0500 1.0 -0.0050 2.00 0.0025

(3 marks)
Compare (1) and (2), [A] is the same in both, [B] is twice as great in (2), the rate in (2) is
four times than that in (1), the reaction must be second order in B. (2 marks)
Compare (1) and (3), [B] is the same in both, [A] is twice as great in (1), the rate in (3) is
twice than that in (1), the reaction must be rst order in A. (2 marks)
Rate = k[A][B]2 (1 mark)
k = (0.0050) / (0.1000-0.0025)(1.0)2 = 0.051 L2mol-2h-1 = 1.4 x 10-5 L2mol-2s-1 (2 marks)

15. The hydrolysis of methyl acetate in alkaline solution,

CH3COOCH3 + OH ¯ → CH3COO ¯ + CH3OH
Followed rate = k[CH3COOCH3][OH ¯ ], with k equal to 0.137 Lmol-1s-1 at 25 ºC. A
reaction mixture was prepared to have initial concentrations of methyl acetate and OH¯
of 0.050 M each. How long would it take for 5.0% of the methyl acetate to be
hydrolysed at 25 ºC?
(2 marks)

Initial rate = (0.137)(0.050)2 = 3.4 x 10-4 Ms-1; (1 mark)

assume the initial rate does not drop, (0.050)(0.050 M) / 3.4 x 10-4 Ms-1 = 7.4 s (1 mark)

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16. A reaction A + B → products, is rst order with respect to each reactant, with k = 5.0 x
10-3 M-1s-1. Calculate the concentration of A remaining after 100 s if the initial
concentration of A was 0.100 M and that of B was 6.00 M. State any approximation
made in obtaining your result.
(3 marks)

Since the concentration of B is 6.00 M, and throughout the reaction the B concentration
cannot possibly fall below 5.9 M. Concentration of B is treated as constant, the rate
expression will be
Rate = 6.00k[A] (1 mark)
Treating 6.00k as a new constant rate k’
log[A] = log[A0] - 6.00kt/2.30 or using “ln” (1 mark)
log[A] = -1.00 - [(3.0 x 10-2)(100)/2.30] = -1.00 - 1.304 = -2.30
[A] = 5.0 x 10-3 M (1 mark)

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