(Chemical Kinetics and Chemical Bonding)

Suggested Answers
1 (a) (i) Comparing Expt 1 and 2:
Increasing [propanone] by four times causes rate to increase by four times.
Reaction is first order with respect to propanone.

Comparing Expt 1 and 4:

Increasing [H+] by two times causes the rate to increase by two times.
Reaction is first order with respect to H+.

Comparing Expt 3 and 4:

Increasing [iodine] by 8 times did not cause the rate to increase.
Reaction is zero order with respect to I2.

Since the concentration of the intermediate is directly affected by the

concentration of propanone and the concentration of intermediate is directly
affected by the concentration of H+. Thus, the rate equation of the slow step
which is first order with respective to the intermediate, will also be first order
with H+ and propanone.

This is shown in the slow step of the reaction. Thus, the mechanism is
plausible.

(ii) Rate = k[H+][propanone]

(iii) Using experiment 1:

0.001 = k(0.01)(0.01)
k = 10 mol-1 dm3 min-1

(b) (i) Energy

Ea (slow step) Ea (step 3)

OH

H2C C CH3
Ea (step 1)

+
OH

H3C C CH3
O ΔHr

O IH 2 C C CH3

H3 C C CH
+H 3
+
+ HI

Reaction Coordinate

Note: Only need to indicate Ea of the slow step and the ∆Hr. I have included
the other Ea so that you can see that step 2 has the highest Ea.
∆Hr = +22 kJ mol-1 (step taken: bond broken – bond formed)

(ii) H+ acts as a homogenous catalyst.

Kwok YL
 (Chemical Kinetics and Chemical Bonding)

Number of molecules

At temperature, T

Energy
0 Ea(catalysed) Ea(uncatalysed)

ƒ H+ provides an alternative reaction pathway with a lower energy barrier.

ƒ Therefore, there will be more reactant molecules which possess the
minimum energy for the reaction to occur.
ƒ Hence, the number of effective collision increase and hence rate of
reaction increases.

(c) (i) From the Data Booklet: Br–Br, Cl–Cl, and I–I

ƒ The bond strength is in the order of Cl–Cl being the strongest and I–I
being the weakest.
ƒ This is because as we move from Cl to I, the atomic radius increase.
Since formation of covalent bond is due to overlapping atomic orbital.
ƒ Hence, the overlapping of atomic orbitals between two I atoms is less
effective than the overlapping of atomic orbital between two Cl atoms,
since the former is larger than the latter.

(ii) Melting point trend: Cl2 < Br2,< I2

ƒ Are all simple discrete molecules. Melting these substances would

require the breaking of van der waals’ forces of interaction between
them.
ƒ Since, I2 has the largest electron cloud size, it is the most polarisable
and hence its induced dipole moment is the largest. Therefore, its id-id
interaction is the strongest, thus it has the highest melting point.
ƒ Cl2 has the smallest electron cloud size and it is thus the least
polarisable and hence its induced dipole moment is the smallest.
Therefore, its id-id interaction is the weakest, thus the lowest melting
point.

(d) ƒ Rate of iodination of propanone occurs as fast as the rate of chlorination of

propanone.
ƒ As the reaction occurs in a multiple steps reaction, the rate of the reaction is
dependent on the activation energy of the slow step.
ƒ This is because that the breaking of the halogen-halogen bond does not happen
in the rate determination step. The activation energy for the slow step for
iodination of propanone and the chlorination of propanone is the same.
ƒ Thus rate of reaction remains the same despite I–I being weaker than the Cl–
Cl.

Kwok YL