CHEM 120

CHUKA UNIVERSITY

UNIVERSITY EXAMINATIONS

FIRST YEAR EXAMINATION FOR THE AWARD OF DEGREE OF BACHELOR OF

SCIENCE AND BACHELOR OF EDUCATION (SCIENCE)

CHEM 120: PHYSICAL CHEMISTRY I

STREAMS: BSC (CHEM, MATHS, BIOL, BIOCHEM, INDUSTRIAL. CHEM,

BIOMED) TIME: 2 HOURS

DAY/DATE: FRIDAY 18/12/2020 8.30 A.M. – 10.30 A.M.

INSTRUCTIONS: Answer question ONE and any other TWO questions

QUESTION ONE (30 MARKS)

(a) (i) State the Avogadro’s law (1 mark)

(ii) State what can you deduce from the fact that at STP 22.4 dm3 of carbon dioxide
contain more than 6.02 x1023 molecules (2 marks)
(iii) On reacting potassium chromate (VII) (potassium chlorate), KClO4, with
fluorosulphonic acid FSO3H a gas X is evolved. A 0.245 g of X are found to occupy
112cm3 at 293 k and at pressure of 5.20 x 104 Pa. Calculate the relative molecular
mass of X. {(K = 39.098, Cl = 34.45, O = 15.999 g/mol) R =8.314 JK-1 mol-1}
(2 marks)
(iv) Describe how the syringe method can be used to determine the relative molecular
mass of a gas and vapour (volatile liquids) (5 marks)

(b) (i) Write short notes on the order of reaction and rate constants (3 marks)

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(ii) The progress of the reaction below can be followed by using the fact that
compound A reacts with acidified potassium iodide, liberating iodine whereas
compound B does not.

A series of experiments was carried out to determine the initial rate of reaction for
various concentrations of compound A. The following data were obtained.

Concentration of compound A (mol dm-3) Initial rate (mol dm-3s-1)

0.060 3.12 × 10-4
0.120 6.23 × 10-4
0.180 9.38 × 10-4
0.240 12.5 × 10-4

From the data in the table, deduce the order of reaction with respect to compound A.
Explain your reasoning (1 mark)

(iii) In an investigation of the recombination of X atoms to give X2 molecules in the

gas phase in the presence of argon, that is the reaction X + X + Ar → X2 + Ar the
following data were obtained.

With the concentration of argon fixed at 1.0×10-3 mol dm-3

Concentration [X] (mol dm-3) 𝑑[𝑋2 ]

Initial rate (mol dm-3 s-1)
𝑑𝑡
1.0×10-5 8.70 × 10-4
2.0×10-5 3.48 × 10-3
4.0×10-5 1.39 × 10-2

With the concentration of X fixed at 1.0×10-5 mol dm-3

Initial concentration [Ar] (mol dm-3) 𝑑[𝑋2 ]
Initial rate (mol dm-3 s-1)
𝑑𝑡
1.0×10-3 8.70 × 10-4
5.0×10-3 4.35 × 10-3
1.0×10-2 8.69 × 10-3

Find the order of reaction with respect to [X] and [Ar], hence determine the overall
velocity constant for the formation of X2 molecules (3 marks)

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(c) Draw the various types of curves showing variation of the rate with temperature
(5 marks)
(d) At certain temperature, equilibrium constant for the reaction CO + H 2O ⇌ CO2 + H2 is
5.0. If the reaction started with initial partial pressures of CO and steam as 1 atmosphere
and 10 atmospheres, calculate the partial pressure of all the gases when the equilibrium
state is reached. (5 marks)
(e) A 2.5 M solution of a weak monobasic acid has the same pH as 0.017M HCl. Assuming
that the HCl is completely ionized;
(i) calculate the pH of these solutions (1 mark)
(ii) determine the degree of ionization of the weak acid in its 2.5M solution (2 marks)

QUESTION TWO (20 MARKS)

a) The rate constant for the reaction H2 (g) + I2 (g) → 2HI (g) is 5.4 ×10-4 m-1s-1 at 326oC. At
410oC the rate constant was found to be 2.8 ×10-2 m-1s-1 calculate the
(i) Activation energy (R = 8.314 JK-1 mol-1) (3 marks)
(ii) High temperature limiting rate constant for this reaction. (2 marks)

b) Briefly explain why the study of the effect of temperature on rates is important (3 marks)

c) The table below gives values for the velocity constant k, of the reaction between
potassium hydroxide and bromoethane in ethanol at a series of temperature, T

K (dm3mol-1 s-1) T (k)

0.182 305.0
0.466 313.0
1.35 323.1
3.31 332.7
10.2 343.6
22.6 353.0

Calculate the value for the activation energy of the reaction (R = 8.31 JK -1 mol-1)
(5 marks)

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d) The following data are for the reaction

A + B ⇌ Products

(i) Determine the order with respect to A and B (4 marks)

(ii) Calculate the rate constant (2 marks)
(iii) Determine the reaction rate when the concentrations of A and B are 0.2M and 0.35M
respectively. (1 mark)

QUESTION THREE (20 MARKS)

a) This question concerns the following reversible process
2SO2 (g) + O2 (g) ⇌ 2SO3 (g) ∆Ho = -98 KJ mol-1
Explain the effect on the position of equilibrium on;
(i) Increasing the pressure at constant temperature (1 marks)
(ii) Increasing the temperature at constant pressure (11/2 mark)
(iii) Bearing in mind your answer for part (i), how do your account for the fact that
industrially a temperature of about 800K, a pressure of 1 or 2 atm and a catalyst are
used. (2 marks)
(iv) At 800K, the equilibrium partial pressures in atmospheres are; P SO2 = 0.1, PO2 = 0.7
and PSO2 = 0.8. Calculate KP (11/2 mark)

b) Consider the reaction PCl5 (g) ⇌ PCl3 (g) + Cl2 (g). For such a system of total volume,
dm3 and a total pressure of 202.6 kPa, at equilibrium the percentage dissociation of PCl5
(g) at temperatures of 200oC and 300oC are 48.5 and 97.0 respectively.
(i) Calculate the value for Kp at 200oC (4 marks)

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(ii) Calculate the percentage dissociation of PCl5 that would result if the pressure of the
system was reduced to 135.1 kPa. {Temperature remains constant} (2 marks)
(iii) How is the value obtained in (ii) explained in terms of Le chatelier’s principle?
(1 mark)
c) State the law of Gay-Lussac and show how it is related to Avogadro’s principle (3 marks)

d) The reaction, 2N2O5 → 4NO2 + O2, is forming NO2 at the rate of 0.0076 mol/L/sec at
some time. Calculate;
(i) The rate of appearance of O2 at this time (2 marks)
(ii) The rate of disappearance of N2O5 at this time (2 marks)

QUESTION FOUR (20 MARKS)

a) Distinguish between electrolytic cell and electrochemical cell with aid of suitable
diagrams (4 marks)
b) Will Ce3+ (a=1) ions reduce chlorine to Cl (a=1) ions at 298 K according to the reaction
1
Ce3+ (a=1) + 2 Cl2 (p = 1 atm) ⇌ Ce4+ (a=1) + Cl (a=1)

Given that
o
Ece 3+
4+ /Ce /Pt = 1.82 V

o
E𝐶𝑙  /Cl2/Pt = 1.3595 V (4 marks)

c) Using the thermochemical data given below at 298 K,

2OF2 (g) → O2 (g) + 2F2 (g) ∆Ho = -49.4 KJ
2ClF (g) + O2 (g) → Cl2O (g) + OF2 (g) ∆Ho = +205.6 KJ
1 3
ClF3 (g) + O2 (g) → 2 Cl2O (g) + 2 OF2 (g) ∆Ho = +266.7 KJ

Calculate the change in enthalpy (∆Ho) for the following reaction

ClF (g) + F2 (g) → ClF3 (g) ∆Ho = ? (3 marks)

d) The first proton of sulphuric acid is completely ionized but the second proton is only
partially dissociated with an acidity constant Ka2 of 1.2 ×10-2. Calculate the pH of the
solution. (4 marks)

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e) The hydrogen sulphate ion, HSO4, is a moderately strong Bronsted acid with a Ka of
1.0×10−2
i. Write the equilibrium expression for this acid (1 mark)
ii. Calculate the value of {H+} in 0.010M HSO4 (Furnished by the salt, NaHSO4).
(3 marks)
iii. Calculate the percentage ionization of HSO4 into H+ and SO42 in 0.010M HSO4
(1 mark)

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