Winter 1997 CH2 Mark Scheme

1
1. The equilibrium reaction
2SO
2
(g) + O
2
(g) SO
3
(g)
is used in the manufacture of sulphuric acid, using V
2
O
5+
as a catalyst
.
(a) (i) Given that the enthalpies of formation of SO
2
and SO
3
are 297 and 395 kJ mol
1

respectively, calculate the enthalpy of reaction, H, of the forward reaction,
assuming it goes to completion.
H = H
r
(prods) H (reags)
= (395 (2) (297 2) (1)
= 196 (kJ) (1)
(ie working (1) answer (1))
if incorrect sign because of incorrect working () only
if H = 98 kJ and H = H
f
(prods) H
1
(reags) or a correct cycle given then
()
(2)
(ii) State and explain what happens to the equilibrium position of this reaction as the
temperature is raised.
temp means yield / shifts to the left (1)
because equilibrium moves in endothermic direction (1)
mark consequentially on the answer to (a)(i)
(2)
(iii) The temperature used in practice for the industrial process is a balance between
economics and chemistry. Suggest three reasons which determine the choice of an
operating temperature of around 450 C.
low for good yield (1)
high for sensible rate (1)
role of catalyst / optimum temperature for catalyst (1)
compromise so that reasonable yield/time in terms of economic return or
some comment on yield rate and compromise required (1) (max 3) for (a)(iii)
(3)
(iv) What effect does the catalyst have on the position of equilibrium in this reaction?
none/no effect (on yield) (1)
(1)
(v) Sketch an enthalpy-level diagram for this reaction, showing on it the uncatalysed
and a possible catalysed route.
2 humps, not
necessarily this
way round
if 1 hump of lower energy for cat. ()
(1)
cat:
uncat (1)
correct relation
of H & H (1)
axes (1)
1 2
energy

levels labelled reactants and products (1)
consequential on answer given to part (a)(i)
if incorrect curve is drawn for answer given in (a)(i) then (max 3) for (a)(v)
(4)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
2

(b) (i) Write an expression for the equilibrium constant K
c
for the reaction;
( )
[ ]
[ ] [ ]
( ) K
SO
SO
2
3
2
2
2
2
0
1 =

square brackets essential
ignore any units
if p is used in front of brackets (0)
(1)
(ii) Explain with reference to your answer to (b)(i) the effect of increasing the
concentration of oxygen in the system at constant temperature.
yield increased (1)
[0
2
] raises denominator so numerator does too since K
c
constant or to keep
K
c
constant (1)
some explanation in terms of K
c
is required
(2)
(iii) A steel vessel of volume 2 dm
3
has introduced into it 0.2 mol of SO
3
, 0.04 mol of
SO
2
and 0.01 mol of O
2
. Show that this mixture is not at equilibrium and indicate
in which direction the system will move in order to achieve equilibrium at 700 K.
(K
3
at 450C is 1.7 10
6
mol
1
dm
3
).
[ ]
[ ] [ ]
( . )
( . ) ( . )
SO
SO
3
2
2
2
2
2
2
0
02
0 04 0 01
=

= 2.5 10
3
(1)
but K
c
at equilibrium is 1.7 10
6

the numbers are not the same it is not at equilibrium i.e. some comment
that 2.5 10
3
as not K
c
(1)
system / reaction mixture composition moves towards SO
3
(1)
or for K
c
to be achieved (1) concentration of SO
3
increases (1)
(3)
(Total 18 marks)

2. Consider the following series of reactions and answer the questions which follow.
NaOH (aq)
NaOH(aq)
ethanolic KOH
HCl(aq)
C H O
6 12 2
C H O
4 10 CH CO Na 3 2
+
C H 4 8
C H
4 10
2
H /Pt
C H Br
4 9
CH CO H
3 2
+
A B C
D E F
G
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
3

(a) (i) What type of reaction is represented by the conversion of E to F?
elimination (1)
ignore nucleophilic or electrophilic
(1)
(ii) The product F exists in two steroisomeric forms. Draw them, and state the feature
of the molecule which makes this isomerism possible.
H H H
CH CH
3 3
CH H
CH
3
3
C C C C allow stick for Hs
(1) (1)

restricted/no/stops rotation about C=C (1) this mark is conditional on two
correct cis/trans structures being given
(3)
(iii) Give a simple chemical test, stating what you would se, for the functional group
present in F.
bromine (water) (1)
yellow / brown / orange colourless (not clear) (1)
just decolourise without stating original colour ()
or any suitable equivalent:
eg potassium manganate(VII) purple brown/ colourless/green is OK
(2)
(iv) F is more reactive than G. Suggest in terms of the bonding of these compounds
why this is so.
alkenes have accessible / high electron density / description of and
bonding (1) or C=C has bond which is weaker than bond so alkenes react
(2)
if just alkene has a bond is given then (1) only
if double bonds add on and single bonds undergo substitution is
given then (1) only
(2)
(b) Compound E displays optical isomerism.
(i) State what this means.
rotates (plane of polarisation of) plane-polarised (monochromatic) light (not
bends/ twists) or non-superimposable mirror image (1)
if contains chiral carbon is given this must be explained or indicated on the
diagram for (1)
(1)
(ii) Sketch the optical isomers of E.
CH CH CH CH
H
H
C C Br Br
2 2 3 3
CH
3
CH
3

structure (1) correct mirror image (1)
must be 3D drawing for (2) if it is drawn flat (1) only
if a correct mirror image of an incorrect but chiral compound (1) the chiral
compound must be feasible to get this mark
(2)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
4

(c) The reaction of E to give B is a nucleophilic substitution.
(i) What is meant by the term nucleophile?
species with lone pair () to donate ()
seeks positive centres () only
not seeks protons in nucleus or nucleus loving
not has a negative charge
(1)
(ii) Give the structural formula for B.
H C C C C H
H H H H
H H OH H
(1)

consequential alcohol on (b)(ii)
the structure must be sufficient to show butan-2-ol
CH
3
CH
2
CH(OH)CH
3
is OK
(1)
(iii) Give a simple chemical test for the functional group in B, and say what you
would see.
+PCI
5
(1) (steamy) (acid) fumes / white gas (1) if evolution of HCI given () if
PCI
5
(aq) then (0)
any other suitable test and result acceptable e.g.
sodium (1) Bubbles (1) if H
2
formed is given ()
or potassium dichromate (VI (1)green (1)
or potassium manganate(VII) (1)brown/colourless (1)
or add carboxylic acid and conc. sweet smell (1) if ester formed given then
()
sulphuric acid) (1)
or ZnCI
2
/HCI (1)white ppt (1)
or I
2
/NaOH or KI/NaCIO (1)yellow ppt (1) if forms CH
3

()
consequential on answer given to (c)(iii)
(2)
(d) The type of reaction exemplified by A B + C is important in the manufacture of soap.
(i) What type of reaction is this?
hydrolysis / saponification (1)
not substitution
(1)
(ii) A could be reacted with aqueous acid to give B and D. If the same quantity of A
was treated with aqueous acid, instead of aqueous alkali, how would the yield of B
differ? Explain your answer.
yield falls; () reaction with acid is an equilibrium ()
(1)
(e) Consider the reaction C D.
(i) Name D.
acetic/ethanoic acid (1)
(1)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
5

(ii) Identify the acid-base conjugate pair in this reaction.
CH
3
COOH / CH
3
COO

(1) CH
3
COONa given ()
if C and D given () only
(1)
(iii) Explain why the reaction occurs.
HCI/H
3O
+
is a stronger acid (1) than
ethanoic acid (1)
or
CH
3
COO

strong base (1) whereas
CI

weaker base (1)
(2)
(iv) A quantity of A was reacted with NaOH, acidified and the volatile acid D distilled
out. D was then added to a solution containing 0.0250 mol (an excess) of NaOH.
The excess NaOH from this reaction required 28.7 cm
3
of 0.100 mol dm
3
HCl for
complete reaction. What mass of a was reacted with NaOH in the first place?
NaOH left mol = =
28 7
1000
01 1 2 87 10
3
.
. ( ) .
NaOH used = 0.025 2.87 10
-3
(1) = 0.0221 mol
0.0221 mol of A
mass of A = 0.0221 116 (1) = 2.56/7 g (1)
(4)
(Total 25 marks)

3. This question is about the reaction between bromomethane and aqueous hydroxide ions
CH
3
Br + OH
(a) An increase in temperature increases the rate of this reaction.
Explain the increase by referring to the collision frequency and the collision energy of the
molecules.
collision frequency () as molecules move faster ()
collision energy () as mole have higher momentum/greater
kinetic energy ()
proportion of colls. energy > E
a
rises or
more successful/effective collisions (1)
(3)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
6

(b) By sketching the energy distribution of the molecules at a given temperature, T show how
the presence of a catalyst will increase the rate of the reaction.
no. of mols.
energy
E (cat)
a a E
if two graphs are
drawn then ( ) max 1

general form of graph (1) must be skewed to the left (no bell shapes)
E
a
shown (1)
E
a
cat (1) (this mark can still be awarded if speed on x-axis)
E
a
cat mark can not be awarded if it is to the LHS of the hump
(3)
(c) Define the following terms used in reaction kinetics.
(i) Overall order of reaction
sum of powers to which concentration terms are raised (in rate equation) (1)
sum of individual orders () only
(1)
(ii) Rate constant
(proportionality) constant in rate equation (1)
or defined K = Ae
E/RT

(1)
(d) In the reaction between bromomethane and aqueous hydroxide ions at constant
temperature the concentration of bromomethane at various times is given in the table.
time/min 0
0.100
10
0.074
20
0.057
30
0.043
40
0.033
50
0.025
60
0.019
70
0.014 [CH Br]/mol dm
3
3

graph of [CH
3
Br] vs t (2) ie correct points (1) correct line smooth curve (1)
if a plot of [CH
3
Br] vs 1/t (0)
or in [CH
3
Br] vs t (2)
penalise () if one or both of the axes are less than half the size of the grid
given show constant half-life using 2 values (2)
if one value of half-life is given and say it is 1st order (1) only
if just state constant half-life with no value used or state . 1st order (0)
(or constant t

from constant slope / straight line = 1st order if log plot used
(2))
(ii) Plot a graph to show that the reaction is first order with respect to bromomethane.
one (1)
(4)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
7

(iii) If the concentration of the hydroxide ion doubles, all other factors remaining
constant, the rate of the reaction doubles. What is the order of reaction with respect
of the hydroxide ion?
rate = k [CH
3
Br] [OH
-
] (1) consequential on answer to (d)(ii)
(1)
(iv) Hence write a rate equation for this reaction.
C Br
HO
H
H
H H H

HO C Br
H
HO C
H
H+ Br
H

C C may be shown as Br Br
+

arrows must not come from the charge
drawing of the lone pair is not essential
intermediate must be ve
if (d)(iii) is correct but a correct S
N
1 mechanism is given here
(1) max for (d)(iv)
if in (d)(iii) rate = k [CH
3
Br) ie 1st order is given but a correct S
N
1 mechanism is given here (3) for (d)(iv)
if (d)(iii) is incorrect but a correct S
N
2 mechanism is given here
(1) max for (d)(iv)
if no answer to (d)(iii) and a correct S
N
1 or S
N
2 mechanism is given here
then (1) max for (d)(iv)
(1)
(v) Based on the kinetic information obtained above write the mechanism for the
reaction between CH
3
Br and aqueous OH

ions.
(3)
(Total 17 marks)

4. (a) This question is about the reaction between bromomethane and aqueous hydroxide ions
CH
3
Br + OH
An increase in temperature increases the rate of this reaction.
Explain the increase by referring to the collision frequency and the collision energy of
the molecules.
collision frequency () as molecules move faster ()
collision energy () as mole have higher momentum/greater
kinetic energy ()
proportion of colls. energy > E
a
rises or
more successful/effective collisions (1)
(3)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
8

(b) By sketching the energy distribution of the molecules at a given temperature, T show how
the presence of a catalyst will increase the rate of the reaction.
no. of mols.
energy
E (cat)
a a E
if two graphs are
drawn then ( ) max 1

general form of graph (1) must be skewed to the left (no bell shapes)
E
a
shown (1)
E
a
cat (1) (this mark can still be awarded if speed on x-axis)
E
a
cat mark can not be awarded if it is to the LHS of the hump
(3)
(Total 6 marks)

5. Define the following terms used in reaction kinetics.
(a) Overall order of reaction
sum of powers to which concentration terms are raised (in rate equation) (1)
sum of individual orders () only
(1)
(b) Rate constant
(proportionality) constant in rate equation (1)
or defined k = Ae
E/RT

(1)
(Total 2 marks)

6. In the reaction between bromomethane and aqueous hydroxide ions at constant temperature the
concentration of bromomethane at various times is given in the table.
time/min 0
0.100
10
0.074
20
0.057
30
0.043
40
0.033
50
0.025
60
0.019
70
0.014 [CH Br]/mol dm
3
3

graph of [CH
3
Br] vs t (2) ie correct points (1) correct line smooth curve (1)
if a plot of [CH
3
Br] vs 1/t (0)
or in [CH
3
Br] vs t (2)
penalise () if one or both of the axes are less than half the size of the grid
given show constant half-life using 2 values (2)
if one value of half-life is given and say it is 1st order (1) only
if just state constant half-life with no value used or state . 1st order (0)
(or constant t

from constant slope / straight line = 1st order if log plot used (2))
(b) Plot a graph to show that the reaction is first order with respect to bromomethane.
one (1)
(4)
www.xtremepapers.net
www.XtremePapers.net
Winter 1997 CH2 Mark Scheme
9

(c) If the concentration of the hydroxide ion doubles, all other factors remaining constant, the
rate of the reaction doubles. What is the order of reaction with respect of the hydroxide
ion?
rate = k [CH
3
Br] [OH
-
] (1)
(1)
(d) Hence write a rate equation for this reaction.
C Br
HO
H
H
H H H

HO C Br
H
HO C
H
H+ Br
H

C C may be shown as Br Br
+

arrows must not come from the charge
drawing of the lone pair is not essential
intermediate must be ve
if (c) is correct but a correct S
N
1 mechanism is given here
(1) max for (d)
if in (c) rate = k [CH
3
Br) ie 1st order is given but a correct S
N
1 mechanism is given here (3) for (d)
if (c) is incorrect but a correct S
N
2 mechanism is given here
(1) max for (d)
if no answer to (c) and a correct S
N
1 or S
N
2 mechanism is given here
then (1) max for (d)
(1)
(e) Based on the kinetic information obtained above write the mechanism for the reaction
between CH
3
Br and aqueous OH

ions.
(3)
(Total 9 marks)


www.xtremepapers.net
www.XtremePapers.net