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Question 4.1 From the rate expression for the following reactions, determine their
order of reaction and the dimensions of the rate constants.
(i) 3NO(g) → N2O (g) Rate = k[NO]2
(ii) H2O2 (aq) + 3I– (aq) + 2H+ → 2H2O (l) + 3 I− Rate = k[H2O2][I-]
(iii) CH3CHO (g) → CH4 (g) + CO(g) Rate = k [CH3CHO]3/2
(iv) C2H5Cl (g) → C2H4 (g) + HCl (g) Rate = k [C2H5Cl]
Question 4.2 For the reaction:
2A + B → A2B
the rate = k[A][B]2 with k = 2.0 × 10–6 mol–2 L2 s–1. Calculate the initial
rate of the reaction when [A] = 0.1 mol L–1, [B] = 0.2 mol L–1. Calculate
the rate of reaction after [A] is reduced to 0.06 mol L–1.
Question 4.3 The decomposition of NH3 on platinum surface is zero order reaction. What
are the rates of production of N2 and H2 if k = 2.5 × 10–4 mol–1 L s–1?
Question 4.4 The decomposition of dimethyl ether leads to the formation of CH4, H2
and CO and the reaction rate is given by
Rate = k [CH3OCH3]3/2
The rate of reaction is followed by increase in pressure in a closed
vessel, so the rate can also be expressed in terms of the partial pressure
of dimethyl ether, i.e.,
( ) 3 3
3/2
Rate = k pCH OCH
If the pressure is measured in bar and time in minutes, then what are
the units of rate and rate constants?
Question 4.5 Mention the factors that affect the rate of a chemical reaction.
Question 4.6 A reaction is second order with respect to a reactant. How is the rate of
reaction affected if the concentration of the reactant is
(i) doubled
(ii) reduced to half ?
Question 4.7 What is the effect of temperature on the rate constant of a reaction? How can
this temperature effect on rate constant be represented quantitatively?
Question 4.8 In a pseudo first order hydrolysis of ester in water, the following results were
obtained:
(i) Calculate the average rate of reaction between the time interval 30 to
60 seconds.
(ii) Calculate the pseudo first order rate constant for the hydrolysis of ester.
Question 4.9 A reaction is first order in A and second order in B.
(i) Write the differential rate equation.
(ii) How is the rate affected on increasing the concentration of B three times?
(iii) How is the rate affected when the concentrations of both A and B are
doubled?
Question 4.10 In a reaction between A and B, the initial rate of reaction (r0) was measured
for different initial concentrations of A and B as given below: What is the order of the reaction with respect to A and B?
Question 4.11 The following results have been obtained during the kinetic studies of the reaction:
2A + B → C + D Determine the rate law and the rate constant for the reaction.
Question 4.12 The reaction between A and B is first order with respect to A and zero order
with respect to B. Fill in the blanks in the following table:
Question 4.13 Calculate the half-life of a first order reaction from their rate constants
given below:
(i) 200 s–1
(ii) 2 min–1
(iii) 4 years–1
Question 4.14 The half-life for radioactive decay of 14C is 5730 years. An archaeological
artifact containing wood had only 80% of the 14C found in a living tree.
Estimate the age of the sample.
Question 4.15 The experimental data for decomposition of N2O5
[2N2O5 → 4NO2 + O2]
in gas phase at 318K are given below:
(i) Plot [N2O5] against t.
(ii) Find the half-life period for the reaction.
(iii) Draw a graph between log[N2O5] and t.
(iv) What is the rate law ?
(v) Calculate the rate constant.
(vi) Calculate the half-life period from k and compare it with (ii).
Question 4.16 The rate constant for a first order reaction is 60 s–1. How much time will
it take to reduce the initial concentration of the reactant to its 1/16th
value?
Question 4.17 During nuclear explosion, one of the products is 90Sr with half-life of
28.1 years. If 1μg of 90Sr was absorbed in the bones of a newly born
baby instead of calcium, how much of it will remain after 10 years and
60 years if it is not lost metabolically.
Question 4.18 For a first order reaction, show that time required for 99% completion
is twice the time required for the completion of 90% of reaction.
Question 4.19 A first order reaction takes 40 min for 30% decomposition. Calculate t1/2.
Question 4.20 For the decomposition of azoisopropane to hexane and nitrogen at 543
K, the following data are obtained. Calculate the rate constant.
Question 4.21 The following data were obtained during the first order thermal
decomposition of SO2Cl2 at a constant volume.
SO2Cl2 (g) → SO2 (g) + Cl2 (g)
Question 4.22 The rate constant for the decomposition of N2O5 at various temperatures
is given below: Draw a graph between ln k and 1/T and calculate the values of A and Ea.
Predict the rate constant at 30° and 50°C.
Question 4.23 The rate constant for the decomposition of hydrocarbons is 2.418 × 10–5s–1
at 546 K. If the energy of activation is 179.9 kJ/mol, what will be the value
of pre-exponential factor.
Question 4.24 Consider a certain reaction A → Products with k = 2.0 × 10–2s–1. Calculate
the concentration of A remaining after 100 s if the initial concentration
of A is 1.0 mol L–1.
Question 4.25 Sucrose decomposes in acid solution into glucose and fructose according
to the first order rate law, with t1/2 = 3.00 hours. What fraction of sample
of sucrose remains after 8 hours ?
Question 4.26 The decomposition of hydrocarbon follows the equation
k = ( 4.5 × 1011s–1) e-28000K/T
Calculate Ea.
Question 4.27 The rate constant for the first order decomposition of H2O2 is given by the
following equation:
log k = 14.34 – 1.25 × 104K/T
Calculate Ea for this reaction and at what temperature will its half-period
be 256 minutes?
Question 4.28 The decomposition of A into product has value of k as4.5 × 103 s–1 at 10°C
and energy of activation 60 kJ mol–1. At what temperature would k be
1.5 × 104s–1?
Question 4.29 The time required for 10% completion of a first order reaction at 298K is
equal to that required for its 25% completion at 308K. If the value of A is
4 × 1010s–1. Calculate k at 318K and Ea.
Question 4.30 The rate of a reaction quadruples when the temperature changes from
293 K to 313 K. Calculate the energy of activation of the reaction assuming
that it does not change with temperature.
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