Chemical Kinetics and Energetics

(12)1, 6
One suggestion for the reduction of greenhouse gas emissions from coal-fired power stations
is to separate the CO
2
from the flue gases and pump it into the sea bed, where it can dissolve
in water under pressure.

()

()

()
During this process, hydrogen bonds are formed between CO
2
and H
2
O moledules.
What will be the signs of H and S for this equilibrium for the forward reaction?
H S
A - -
B - +
C + -
D + +

(12)1, 12
Lead is the final product formed by a series of changes in which the rate-determining step is
the radioactive decay of uranium-238. This radioactive decay is a first-order reaction with a
half-life of 4.5 x 10
9
years.
How long would it take for a rock sample, originally lead-free, to contain a molar proportion
of uranium to lead of 1:3?
A. 1.5 x 10
9
years
B. 2.25 x 10
9
years
C. 9.0 x 10
9
years
D. 13.5 x 10
9
years
(12)1, 13
The decomposition of hydrogen peroxide in aqueous solution is a first order process.
If 10% of the hydrogen peroxide in a solution of concentration 0.1moldm
-3
decomposes in 5
minutes at a certain temperature, what percentage of the hydrogen peroxide in a solution of
concentration 0.2moldm
-3
would decompose in 5 minutes at the same temperature?
A. 5%
B. 10%
C. 19%
D. 20%

(12)1, 14
The uncatalysed reaction between SO
2
and O
2
is slow.

The reaction is speeded up in the presence of the homogeneous catalyst NO, which
participates as follows.

Which reaction pathway diagram is most appropriate for describing the enthalpy changes
occurring during the catalysed reaction? In each case the reaction pathway for the
uncatalysed reaction is shown as a dashed line.


(11)1, 5
The standard enthalpy change of combustion of but-1-ene, C
4
H
8
(g), is x kJmol
-1
.
The standard enthalpy change of the reaction

()

() is y kJmol
-1
.
What is the standard enthalpy change of combustion of ethene, C
2
H
4
(g)?
A.

B.

C.

D.

(11)1, 6
The table shows the charge and radius of each of six ions.
Ion J
+
L
+
M
2+
X
-
Y
-
Z
2-

Radius /nm 0.14 0.18 0.15 0.14 0.18 0.15

The ionic solids JX, LY and MZ are of the same lattice type.
What is the correct order of their lattice energies, placing the most exothermic first?
A. JX, MZ, LY
B. LY, MZ, JX
C. MZ, JX, LY
D. MZ, LY, JX
(11)1, 7
At temperatures below 13C, shiny, ductile metallic tin, known as white tin, changes slowly
into a grey powder which is brittle.
Data for each form of tin are given in the table.
H
f

/kJmol
-1
S

/JK
-1
mol
-1

White 0 51.4
Grey -2.09 44.1

What is the expression for G

, in Jmol
-1
, for the formation of grey tin from white tin at 12C?
A. G

= -2.09 285(-7.3)
B. G

= -2.09 12(+7.3)
C. G

= -2090 12(+7.3)
D. G

= -2090 -285(-7.3)
(11)1, 12
The reaction between NO
2
and SO
2
is a key stage in the formation of acid rain.

()

() ()

()
The initial rate of this reaction was measured for different concentrations of reactants and the
following results obtained.
[NO
2
] /moldm
-3
[SO
2
] /moldm
-3
Relative rate
0.005 0.005 1.00
0.006 0.006 1.44
0.008 0.006 1.92

Which row gives the correct orders of reaction with respect to the two reactants?
Order with
respect to
[NO
2
]
Order with
respect to
[SO
2
]
A 1 0
B 1 1
C 2 0
D 2 1

(11)1, 13
The rate of the decomposition of the diazonium cation,

can be followed by measuring the time taken for the same volume of nitrogen to be produced
from a range of diazonium cation concentrations.
To find the order of the reaction with respect to the diazonium cation, which would be the
most suitable graph to plot using the data?
A. [C
6
H
5
N
2
+
] against time
B. [C
6
H
5
N
2
+
] against 1/time
C. Volume N
2
against time
D. Volume N
2
against 1/time

(11)1, 34
The kinetics of the zero order reaction were investigated under different conditions.
The table shows pairs of quantities that were plotted as graphs.
Which pairs gave the following graph?

y-axis x-axis
1 Rate Time
2 Rate constant Time
3 Rate constant Temperature

(10)1, 8
Which class of reaction always has an endothermic enthalpy change?
A. Atomisation
B. Combustion
C. Formation
D. Solution

(10)1, 9
The diagram shows the reaction pathway diagram for an uncatalysed reaction.

The reaction is then catalysed.
What are the changes in the rate constant and the reaction pathway diagram?

(10)1, 10
When steam condenses, 44kJmol
-1
of heat enthalpy is evolved.
What is the entropy change when 54g of steam condenses at 100C?
A. -354 JK
-1
mol
-1

B. -118 JK
-1
mol
-1

C. 118 JK
-1
mol
-1

D. 354 JK
-1
mol
-1

(10)1, 33
Solutes dissolve in solvents to form solutions. If a semi-permeable membrane, that allows
solvent molecules to pass through it, is placed between a pure solvent and a solution
containing a solute in that solvent, pure solvent only will go through the membrane into the
solution. This process is called osmosis.
In which processes will S be positive?
1. Dissolving the solute in a solvent
2. The evaporation of the solvent from the solution
3. The passage of the solvent through a semi-permeable membrane during osmosis
(10)1, 34
Hydrogen reacts with gaseous bromine to form hydrogen bromide,

()

() ()
and with gaseous iodine to form hydrogen iodide.

()

() ()
For the first reaction, the rate equation is

][

[]

For the second reaction, the rate equation is
[

][

]
What can be deduced from this information only?
1. For the hydrogen/bromine reaction, the formation of HBr slows down the rate of the
forward reaction.
2. Only the hydrogen/iodine reaction could be a single step reaction.
3. The mechanism of the hydrogen/bromine reaction involves free radicals.
(12)2, 2
Fossil fuels which are found in deposits beneath the ground have been formed from plants
and animals that lived up to 300 million years ago.
When fossil fuels are burned in internal combustion engines, CO
2
and H
2
O are the main
products, with NO and SO
2
also being formed.
a) [3]
i. Which class of compound, present in fossil fuels, produces CO
2
and H
2
O on
combustion?
ii. Briefly explain how NO is formed in an internal combustion engine.
iii. Suggest which class of compound, originally present in the living matter that
produced the fossil fuel, contained the sulphur that produces SO
2
on
combustion.
Most of the sulphur present in fossil fuels is removed at oil refineries. It is used to produce
SO
2
which is converted, in the Contact process, into SO
3
which is used for the manufacture of
sulfuric acid.
The Contact process involves the oxidation of SO
2
using a vanadium(V) oxide catalyst.

()

()

()---------- reaction 1
b) [4]
i. At 298K, H
f

(SO
2
) = -297 kJmol
-1
and H
f

(SO
3
) = -396kJmol
-1
.
Use these data to calculate H

for reaction 1.
State the units.
ii. For reaction 1, S

= -93.5JK
-1
mol
-1
at 298K.
Use this value and your answer to (i) to calculate G

for reaction 1 at 298K.

For any reaction, G

and the equilibrium constant, K

c
, are related according to the equation

.
c) [7]
i. Use this equation to calculate a value of K
c
for the oxidation of SO
2
at 298K.
ii. Suggest what is the significance of the magnitude of our answer in (i).
iii. Suggest why SO
2
and SO
3
is formed when sulphur is heated in air.
iv. Use your answer to (iii) to suggest why a catalyst is used industrially in the
Contact process. Explain your answer.

(12)3, 3
a) When heated, the carbonates of the Group II elements can lose carbon dioxide.

() ()

()

Under the influence of the metal cation, the carbonate ion is thought to break up as
follows.
O
-
O
-
O
M
2+
M
2+
O
2-
+
CO
2


The nitrates of the Group II elements also decompose on heating. [3]
i. Write an equation for the decomposition of Mg(NO
3
)
2
.
ii. State and explain the trend observed in the thermal stability of the Group II
nitrates.

b) Dinitrogen pentoxide, N
2
O
5
, exists as covalent molecules O
2
N-O-NO
2
in the gas
phase, but as the ionic [NO
2
+
NO
3
-
] in the solid or in solution. N
2
O
5
has been
suggested as a possible intermediate in the thermal decomposition of Group II nitrates
M(NO
3
)
2
. [7]

i. Using this information, and that provided in (a), suggest a mechanism for the
formation of N
2
O
5
from a Group II nitrate, M(NO
3
)
2
.

N
2
O
5
decomposes on heating in a first order reaction to give NO
2
and O
2
. The
mechanism of this thermal decomposition is thought to involve three steps.
There is an initial homolytic breaking of an N-O bond to give NO
2
and
NO
3
radicals.
This is followed by the dimerization of the NO
3
radical to give N
2
O
6
,
which contains a O-O- peroxide bond.
The third step involves the dissociation of this dimer via further N-O bond
cleavage to form the products.

ii. Write a balanced equation for the thermal decomposition of N
2
O
5
.


iii. Use the information given above to draw out the full mechanism for the
thermal decomposition of N
2
O
5
. You are advised to use structural formulae for
all species, such as
N
O O
O H
2
N
O
O H
2
for N
2
O
5
, so that it is clear which
bonds are broken and which are formed. Indicate any unpaired electrons by a
dot ().

iv. Suggest which of the steps you have drawn is the slowest step. Explain your
reasoning.


c) When benzene is added to a solution of N
2
O
5
in CCl
4
, an excellent yield of
nitrobenzene is obtained in the absence of any added catalyst. [3]

i. Suggest the other product formed during this reaction.

ii. Suggest a mechanism for this reaction, showing all charges and using curly
arrows to show the movements of electron pairs.

The following table lists some H
f

values.
Compound H
f

/kJmol
-1

NO
2
(g) +33.2
N
2
O
5
(g) +5.0

The enthalpy change for the dissociation of N
2
O
5
(g) is given below.
Reaction 1:

()

()

(), H

= +92.5kJmol
-1


d) Use the data above to calculate [3]
i. H
f

of NO
3
(g),
ii. H

for reaction 2.

Reaction 2:

()

()

()

e) By considering the entropy and enthalpy changes during reaction 1 and reaction 2,
suggest how the standard Gibbs free energy change of the two reactions will compare
in sign and in magnitude.
Hence predict which reaction will be the more spontaneous. Explain your reasoning.
[4]

(11)3, 4
a) Briefly describe what is meant by the secondary, tertiary and quaternary structures of
proteins. [6]

b) Once the primary structures of the polypeptide chains of haemoglobin have been
formed from their constituent amino acids, and in the presence of haem groups, the
chains spontaneously coalesce into a haemoglobin molecule.

By considering the chemical interactions involved at each step, suggest what the signs
of G, H and S would be for the overall process. Explain your reasoning. [3]
(10)2, 3
Nitrogen monoxide, NO, is a by-product of the combustion of hydrocarbon fuels in internal
combustion engines.
a) NO is considered to be involved in the formation of acid rain.
State one other undesirable consequence of the presence of NO in the atmosphere. [1]
Nitrogen monoxide is readily converted into nitrogen dioxide.
()

()

()
In order to determine the rate equation for this reaction, an investigation was carried out at a
constant temperature and with the same partial pressure of oxygen,

, for each experiment.

The following results were obtained.
Initial rate /Nm
-2
s
-1
16.2 47.2 78.8 124 172

/Nm
-2
0.30 0.50 0.66 0.82 0.95
(

/N
2
m
-4
0.09 0.25 0.44 0.67 0.90

b) To determine the order of reaction with respect to

, use these data to plot a

suitable graph. [3]

c) What is the order of reaction with respect to

? Explain your answer. [2]

d) The partial pressure of oxygen was halved and a new series of experiments carried out
at the same temperature. When a similar graph was plotted, the gradient at each point
was half that obtained from the first graph.

What is the order of reaction with respect to

? Explain your answer. [2]

e) [2]
i. Construct the rate equation for the reaction between NO and O
2
.
ii. What are the units of the rate constant for this reaction?
(10)2, 4
Data concerning the elements of Group II of the Periodic Table, at 298K, are given in the
table. Further data may be found in the Data Booklet. No calculation is required.
Mg Ca Sr Ba
H
hydration
of M
2+
/kJmol
-1
-1980 -1650 -1480 -1365
S
hydration
of M
2+
/Jmol
-1
K
-1
-293 -238 -222 -188
G
hydration
of M
2+
/kJmol
-1
-1895 -1582 -1415 -1310
Solubility of sulphate/mol per 100g water 1.8 x 10
-1
4.7 x 10
-3
7.1 x 10
-5
9.4 x 10
-7


a) When a salt such as a Group II sulphate dissolves in water, the lattice energy must be
overcome. [2]
i. How will the magnitude of the lattice energy of Group II sulfates change
from MgSO
4
to BaSO
4
?
ii. Suggest a reason for this trend.

b) When the sulfate has dissolved, the anions and cations are each surrounded by a
number of water molecules. The formation of these hydrated ions is an exothermic
process. [4]
i. Draw simple diagrams to show how a water molecule can be attached to a
magnesium cation, and to a sulfate anion. Label each diagram to show the type
of interaction involved.

ii. Suggest why H
hydration
of M
2+
becomes less negative from Mg
2+
to Ba
2+
.