Question 1

Calculate the frequency factor, A for the reaction below;

H + O 2 → OH + O
at 273K.
Question 2
Consider the isomerization of cyclopropane to propene which takes place at fairly high
temperatures in gas phase.

The hard sphere radius for cyclopropane is 2.2 Å. Using collision theory, calculate the pre-
exponential factor, A for the reaction above at 760 K.
Question 3
Hydrogen iodide, HI, decomposes in the gas phase to produce hydrogen, H2, and iodine, I2. The
value of the rate constant, k, for the reaction was measured at several different temperatures
and the data are shown here:

Temperature / K k / M-1s-1
555 6.23 × 10−7
575 2.42 × 10−6
645 1.44 × 10−4
700 2.01 × 10−3

What is the value of the activation energy (in kJ/mol) for this reaction?
Question 4
The rate constant for the rate of decomposition of N2O5 to NO and O2 in the gas phase is 1.66
L/mol/s at 650 K and 7.39 L/mol/s at 700 K:

2N2O5 (g) ⟶ 4NO (g) + 3O2 (g)

Assuming the kinetics of this reaction are consistent with the Arrhenius equation, calculate the
activation energy for this decomposition.

Ans: 113,000 J/mol

Question 5
The rate constant at 325 °C for the decomposition reaction
C4H8⟶2C2H4
is 6.1 × 10−8 s−1, and the activation energy is 261 kJ per mole of C4H8. Determine the frequency
factor for this reaction.

Ans: 3.75×1015 s−1

Question 6
The hydrolysis of sucrose to glucose and fructose,

C12H22O11 + H2O ⟶ C6H12O6 + C6H12O6

follows a first-order rate equation for the disappearance of sucrose:

Rate = k[C12H22O11]
(The products of the reaction, glucose and fructose, have the same molecular formulas but differ
in the arrangement of the atoms in their molecules.)

(a) In neutral solution, k = 2.1 × 10−11 s−1 at 27 °C and 8.5 × 10−11 s−1 at 37 °C. Determine the
activation energy, the frequency factor, and the rate constant for this equation at 47 °C. (assuming
the kinetics remain consistent with the Arrhenius equation at this temperature).

(b) When a solution of sucrose with an initial concentration of 0.150 M reaches equilibrium, the
concentration of sucrose is 1.65 × 10−7M. How long will it take for the solution to reach equilibrium
at 27 °C in the absence of a catalyst? Because the concentration of sucrose at equilibrium is so
low, assume that the reaction is irreversible.

(c) Why does assuming that the reaction is irreversible simplify the calculation in part (b)?
Answers: (a) Ea = 108 kJ, A = 2.0 × 108 s−1, k = 3.2 × 10−10 s−1
(b) 1.81 × 108 h or 7.6 × 106 day
(c) Assuming that the reaction is irreversible simplifies the calculation because we do not have
to account for any reactant that, having been converted to product, returns to the original state.

Question 7
The following reaction is an example of Michael addition reaction between β-nitrostyrene and
piperidine.

Reaction scheme:

Reaction rate equation:

𝑘𝑘1
𝑣𝑣 = 𝑘𝑘2 [𝛽𝛽–𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛𝑛][𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝𝑝]2 (1)
𝑘𝑘−1

a) What is the overall order of the reaction?

b) It is known that the first step of the reaction has established equilibrium, the second step is
catalysed by piperidine molecule and it is rate limiting. Both steps are elementary reactions.
Derive product rate equation (1). What is the observed rate constant?

c) Below are the given kinetic data of the reaction under investigation at different temperatures.
MeCN was used as the solvent together with a large excess of piperidine ([piperidine] > 0.01
M). Using Arrhenius equation approximately calculate Arrhenius parameter A and activation
energy Ea.

T/K 288 293 298 303 308

kobs / M-2 s-1 550 490 428 389 334

d) Usually, reaction rate is increased by increasing temperature. However, the reaction here is
slowing down with increasing temperature. Using the Transition State Theory explain this
phenomenon. (Hint: Use Eyring equation and draw conclusion from enthalpy and entropy of
activation)