December 04, 2014

16C. 1a) Calculate the vapor pressure of a spherical

droplet of water of radius 10 nm at 20C. The vapor
pressure of bulk water at that temperature is 2.3 kPa &
its density is 0.9982 g cm-3.
Ans. 2.6 kPa

16C. 1b) Calculate the vapor pressure of a spherical droplet

of water of radius 20 nm at 35C. The vapor pressure of bulk
water at that temperature is 5.632 kPa & its density is 994.0
kg m-3.

December 04, 2014

16C. 3a) Calculate the pressure differential of water across

the surface of a spherical droplet of radius 200 nm at 20C.
HINT: The surface tension of water is 7.27510-2 N m-1.
Ans. 728 kPa

16C. 3b) Calculate the pressure differential of ethanol across

the surface of a spherical droplet of radius 220mm at 20C.
HINT: The surface tension of ethanol at this temperature is
Ans. 204 x 10 kPa
22.39 mN m-1.
2

December 04, 2014

20A. 3a) The rate of formation of C in the reaction

2 A + B --> 2 C + 3 D
-3
-1
is 2.7 mol dm s . State the reaction rate, and the rates of
formation or consumption of A, B, and D.

20A. 3b) The rate of formation of B in the reaction

A + 3 B --> C + 2 D
-3
-1
is 2.7 mol dm s . State the reaction rate, and the rates of
formation or consumption of A, B, and D.

December 04, 2014

20A. 5a) The rate law for the reaction in Exercise 20A. 3(a)
was reported as d[C]/dt=kr[A][B][C]. Express the rate law in
terms of the reaction rate v; what are the units for kr in each
case when the concentrations are in moles per cubic
decimeter.

20A. 5b) The rate law for the reaction in Exercise 20A. 3(b)
was reported as d[C]/dt=kr[A][B][C]-1. Express the rate law in
terms of the reaction rate v; what are the units for kr in each
case when the concentrations are in moles per cubic
decimeter.

December 04, 2014

20B. 2a) The rate constant for the first-order decomposition
of N2O5 in the reaction 2 N2O5(g) --> 4 NO2(g) + O2(g) is kr=
3.38x10-5 s-1 at 25C. What is the half-life of N2O5? What will
be the pressure, initially 500 Torr, after (i) 50 s, (ii) 20 mins
after the initiation of the reaction?

20B. 2b) The rate constant for the first-order decomposition

of compound A in the reaction 2 A --> P is kr= 3.56x10-7 s-1
at 25C. What is the half-life of A? What will be the
pressure, initially 500 Torr, after (i) 50 s, (ii) 20 mins after
the initiation of the reaction?

December 04, 2014

20C. 1a) The equilibrium NH3 + H2O <==> NH4+ + OH- at
25C is subjected to a temperature which jump slightly
increased the concentration of NH4+ and OH-. The measured
relaxation time is 7.61 ns. The equilibrium constant for the
system is 1.78x10-5 at 25C, and the equilibrium constant of
NH4 is 0.15 mol dm-3. Calculate the rate constants for the
forward reverse steps.
Ans. 7.1x10 s , 1.28x10 dm mol s
5

-1

-1

20C. 1b) The equilibrium A <==> B + C is subjected to a

temperature which jump slightly increased the
concentrations of B and C. The measured relaxation time is
3 micros. The equilibrium constant for the system is 2x10-16
at 25C, and the equilibrium constant of B and C at 25C is
0.2 mmol dm-3. Calculate the rate constants for the forward
reverse steps.

December 04, 2014

20D. 2a) The rate of a chemical reaction is found to triple

when the temperature is raised from 24C to 49C.
Determine the activation energy.

20D. 2b) The rate of a chemical reaction is found to double

when the temperature is raised from 25C to 35C.
Determine the activation energy.

December 04, 2014

20E. 2a) The mechanism of a composite reaction consists of
a fast pre-equilibrium step with forward and reverse
activation energies of 25 kJ mol-1 and 38 kJ mol-1,
respectively, followed by an elementary step of activation 10
kJ mol-1. What is the activation energy of the composite
reaction?

20E. 2b) The mechanism of a composite reaction consists of

a fast pre-equilibrium step with forward and reverse
activation energies of 27 kJ mol-1 and 35 kJ mol-1,
respectively, followed by an elementary step of activation 15
kJ mol-1. What is the activation energy of the composite
reaction?

December 04, 2014

20F. 1a) The effective rate constant is for a gaseous reaction

which has a Lindemann-Hinshelwood mechanism is 2.5x10-4
s-1 at 1.30 kPa and 2.1x10-5 s-1 at 12 Pa. Calculate the rate
constant for the activation step in the mechanism.

20F. 1b) The effective rate constant is for a gaseous reaction

which has a Lindemann-Hinshelwood mechanism is 7x10-3 s-1
at 1.09 kPa and 2.2x10-4 s-1 at 25 Pa. Calculate the rate
constant for the activation step in the mechanism.

December 04, 2014

20G. 2a) Consider the quenching of an organic fluorescent

species with 0=6.0 ns by a d-metal ion with kQ=3.0x108 dm3
mol-1 s-1. Predict the concentration of quencher required to
decrease the fluorescence intensity of the organic species to
50 percent of the unquenched value.

20G. 2b) Consider the quenching of an organic fluorescent

species with 0=3.5 ns by a d-metal ion with kQ=2.5x109 dm3
mol-1 s-1. Predict the concentration of quencher required to
decrease the fluorescence intensity of the organic species to
75 percent of the unquenched value.

December 04, 2014

20H. 1a) Consider the acid-catalysed reaction

(1) AH + B <==ka/k'a==> BH+ + A- (both fast)
(2) A- + AH --kb--> product (slow)
Deduce the rate law.

20H. 1b) Consider the acid-catalysed reaction

(1) HA + H+ <==ka/k'a==> HAH+ (both fast)
(2) HAH+ + B --kb--> BH+ + AH (slow)
Deduce the rate law.