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2012 J C2 Revision Package 2 Kinetics and Equilibria

Complied by Alvin Han 1


Kinetics

1. Hydrogen peroxide reacts with iodide ions in acidic solution as shown below.
H
2
O
2
(aq) + 2H
+
(aq) + 2I
-
(aq) 2H
2
O(l) + I
2
(aq)
In a series of experiments, the reaction was carried out with different concentrations of the 3
reagents and the following results were obtained.

i. Use the data to deduce the order of reaction with respect to each reagent. Explain
your answers and write a rate equation.


2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 2
ii. Two different mechanisms have been suggested for this reaction.

Which mechanism is consistent with your rate equation in (i)? Explain your
answer.






The decomposition of hydrogen peroxide is a first order reaction.

The uncatalysed reaction has an activation energy of 79 kJ mol
1
.
iii. Use the data provided to sketch a fully labeled reaction pathway diagram showing
all relevant energy changes.




2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 3
iv. Define the terms activation energy and rate constant.










v. How will the activation energy and the rate constant for the reaction be affected
by
(a) an increase in temperature?
(b) when a catalyst is used?
Explain your answers with the aid of the Boltzmann Distribution diagram if
necessary.


2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 4
2. Compound P is a sweet smelling substance extracted from a fern which grows in the
tropical region. Acid hydrolysis of compound P yields three products, compounds A,
B and C. Compound C was precipitated out as white solid and was filtered off the
reaction mixture. A series of tests were then performed on compound A and
compound B.
i. A gaseous sample of 0.146 g of compound A took up a volume of 80.1 cm
3

at a
temperature of 400 K and a pressure of 1.01 x 10
5
Pa. In addition, effervescence
of a colourless gas was observed when aqueous sodium carbonate is added to
compound A.
Use these data to calculate the M
r
of compound A and hence suggest a possible
structure.














2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 5
ii. Reacting compound A and compound B with phosphorus pentachloride, PCl
5
,
yield compound D and compound E respectively. Effervescence of white fume
was observed. Both compound D and E are then hydrolysed with aqueous sodium
hydroxide and the kinetics rate data are collected.
(a) The results for the hydrolysis of compound D are as shown.

Using the above data, deduce the order of reaction with respect to compound
D and OH
-
.

















(b) Hence, construct a rate equation and use it to calculate a value of the rate
constant, k
1
,

including its units, for the hydrolysis of compound D.


2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 6
iii. The results for the hydrolysis of compound E are shown in the form of graphical
representation. The overall concentration of aqueous NaOH remained virtually
constant at 0.120 mol dm
-3
.

(a) Use the graph above to determine the following:
I Use the half life method to deduce the order of reaction with respect to
compound E.




II Given that the same plot was obtained when the experiment was repeated
with 0.240 mol dm
-3

of aqueous sodium hydroxide, calculate the value of
the rate constant, k
2
, including its units, for the hydrolysis of compound E.



2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 7
iv. Using the initial rate data given in ii(a) and the graph above, calculate the ratio of
the initial rate of the hydrolysis of compound D to compound E. Hence, suggest
the functional group which is likely to be present in compound B. Explain clearly
your reasoning.





2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 8
3. Compounds E and F are structural isomers with a molecular formula of C
4
H
7
OCl.
Only isomer F is optically active. Neither E nor F reacts with sodium metal. When
heated with silver nitrate in excess ammonia, both E and F produced a silvery
deposit. On heating with dilute sodium hydroxide, E and F produced G and H
respectively both of which has a molecular formula of C
4
H
8
O
2
.
A number of experiments at a constant pressure of 101 kPa and temperature of 90
o
C
were performed in which the concentrations of E, F and sodium hydroxide were
varied. The results are shown below:

i. The rate equations when E and F react with NaOH are as shown below
Rate = k
1

[E][OH
-
]
x

Rate = k
2

[F][OH
-
]
y
Deduce the values of x and y

2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 9
ii. State and explain how the rate of reaction would change (if at all) when the
experiment was conducted at
(a) a pressure of 101 kPa and a temperature of 120
o
C
(b) a pressure of 121 kPa and a temperature of 90
o
C



2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 10
iii.
(a) Identify and draw the structural formulae of compounds E, F, G and H,
explaining the reactions described.
(b) Write the balanced equation when E reacts with silver nitrate in excess ammonia.









2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 11
iv. State and explain clearly the mechanism when F reacts with NaOH.










Equilibria

4. Sulphuryl chloride, SO
2
Cl
2
, is often used as a source of Cl
2
for various organic
reactions. Sulphuryl chloride is also a highly reactive gaseous compound. When
heated, it decomposes endothermically as follows:
SO
2
Cl
2
(g) SO
2
(g) + Cl
2
(g)
A 7:2 mole ratio of SO
2
Cl
2
and Cl
2
is placed in an evacuated vessel at 375 K and 6
atm. After 10 minutes, the mixture reached equilibrium and the partial pressure of
SO
2
is found to be 0.625 atm.
i. Write an expression for the equilibrium constant, K
p
, and calculate its value.
ii. Suggest, with a reason, how the position of equilibrium might alter when the
temperature is increased at the 20
th
minute.
Hence, draw labelled sketches on the same graph to show how the number of
moles of sulphuryl chloride and sulphur dioxide gas would change from the start
of the decomposition till the new equilibrium is reached.



2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 12
5. Hydrogen sulfide is a common contaminant in many of the worlds natural gas (NG)
wells. Hydrogen sulfide is removed by method that is similar to the steam reforming
of methane, one of which is represented by the equation below:
CH
4
(g) + 2H
2
S (g) CS
2
(g) + 4H
2
(g) H = + 250 kJ mol
-1
In a sealed 50 m
3
container at 800 C, methane and hydrogen sulfide were mixed in a
1:2 molar ratio. The pressure in the container increased from 7.5 atm to 10 atm.
i. Find the partial pressures of the four gases at equilibrium.
ii. Define the term K
p
using the above equilibrium as an example.
iii. Hence calculate the K
p
value at 800
o
C.
iv. Explain how the above equilibrium and K
p

are affected by
(a) decrease in temperature.
(b) allowing the sealed container to expand.















6. 8.00 g of potassium chromate is dissolved in acid to make a 100 cm
3

solution. A
dynamic equilibrium occurs, according to the equation below:
2CrO
4
2
(aq) + 2H
+
(aq) Cr
2
O
7
2
(aq) + H
2
O (l)
K
C
= 7.55 x 10
12

mol
3

dm
9
i. What do you understand by the term dynamic equilibrium?



2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 13
ii. Write the K
C
expression for the above equilibrium and calculate the pH at which
only one-fifth of the original amount of chromate ions remain.


























iii. Predict and explain the pH change when aqueous BaCl
2

is added to the above
mixture to precipitate BaCrO
4
.



2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 14
7. The key reaction in the contact process is as follows:
2SO
2
(g) + O
2
(g) 2SO
3
(g) H = -197 kJ mol
-1
V
2
O
5
is used as a catalyst for reaction.
i. Identify the type of catalyst V
2
O
5
is and explain how it works.









When a 2:1 ratio of sulfur dioxide and oxygen at a total initial pressure of 3 atm is
passed over V
2
O
5
, the catalyst in a fixed volume steel vessel at 430

C, the partial
pressure of sulfur trioxide at equilibrium is found to be 1.9 atm.

ii. Calculate the percentage conversion of SO
2
to SO
3
and the equilibrium constant,
K
p

at 430

C.


2012 J C2 Revision Package 2 Kinetics and Equilibria
Complied by Alvin Han 15
iii. According to Le Chateliers Principle, the reaction will be favoured by a low
temperature and a high pressure. Give one other reason (other than cost factor)
why a higher pressure is not applied?

















iv. Comment on the effect on the percentage conversion if another unreactive but
toxic gas was accidentally added to V
2
O
5
?