Beruflich Dokumente
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2NH3(g) H = 92 kJ mol-1
(b)
State the conditions employed industrially in the manufacture of ammonia, and justify
them on physico-chemical grounds.
70 - 1000 atm (1)
high P moves equilibrium to right (1)
350 - 550 C (1)
low temperature moves equilibrium to right (1)
but rate too slow (1)
( use) iron or iron oxide catalyst (1)
if no other marks awarded high pressure and low temperature (1) if
both given
(5)
(c)
What effect does a catalyst have on the rate of achievement of the equilibrium and the
composition of the equilibrium mixture?
Faster give mark if mentioned in (b) (1)
no effect on equilibrium position (1)
(2)
(d)
(ii)
Use the enthalpies of formation, Hf, given below to evaluate H for the oxidation
of ammonia.
NO(g)
H2O(g)
NH3(g)
Hf / kJ mol-1
+90
-242
-46
= 4Hf(NO) + 6Hf(NH3)
= 4(90) + 6(-242) - 4(-46)
(-908) kJ mol-1 (3)
look for 4 6 4 gives (3)
if signs wrong (-I) on each occasion
correct answer with working (3)
if equation wrong mark consequentially.
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(iii)
Ammonia does not spontaneously catch fire in air or oxygen; use this fact and your
result from part (ii) to explain the difference between kinetic and thermodynamic
stability.
thermodynamic stability: products have higher energy than reactants
OR reverse for instability (1)
kinetic stability: (products more stable / lower energy than reactants)
/ ammonia thermodynamically unstable but (1)
(reaction slow due to) high E2 (1)
(7)
(Total 16 marks)
2.
2NH3(g) H = 92 kJ mol-1
3.
(a)
H = 92Kj mol1
Write an expression for the equilibrium constant, Kc, for this reaction and give
its units.
Kc
[ NH 3 ]2
[ N 2 ][ H 2 ]3
(ii)
When 3 mol of hydrogen and 1 mol of nitrogen were allowed to reach equilibrium
in a vessel of 1 dm3 capacity at 500C and 1000 atm pressure, the equilibrium
mixture contained 0.27 mol of N2, 0.81 mol of H2 and 1.46 mol of NH3.
Calculate Kc at this temperature.
Kc
(146
. )2
(0.27)(0.81) 3
(1)
(b)
(ii)
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increases (1)
energies / speed of molecules increased (1)
more have energy > EAct (1) or sufficient energy to react instead of EAct
reference to EAct or sufficient energy to react essential.
(6)
(Total 10 marks)
4.
Benzene and methylbenzene may be separated by fractional distillation. Sketch the general
form of the boiling point/composition diagram for such a mixture and use it to explain the basis
on which fractional distillation rests.
b.p. of methylbenzene
temperature
/C
b.p. of benzene
0
5.
(a)
(b)
(i)
Write an equation the enthalpy change for which would be the enthalpy of
formation of zinc sulphide, ZnS.
Zn(s) + S(s) ZnS(s) (1) allow 1/8S8
must have correct state symbols
(1)
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(ii)
= 441 kJ mol1
Use this, together with the data below, to calculate a value for the enthalpy of
formation of ZnS.
Data:
H
H
= 441 kJ mol1
= 297 kJ mol1
Zn
348
ZnO
ZnS
297
441
SO2
OR
ZnS + 1O2 ZnO + SO2
Hreact
441
Hf[ZnS]
(c)
One way of utilising he large quantities of sulphur dioxide formed in reaction such as that
in (b) is to convert it into sulphur trioxide thus:
2SO2 (g) + O2 (g)
2SO3 (g)
= 98 kJ mol1
Using your knowledge of Le Chateliers principle (which need not be stated), state and
explain the effect on the position of equilibrium of:
(i)
(ii)
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6.
One way of utilising he large quantities of sulphur dioxide formed in reaction such as that in (b)
is to convert it into sulphur trioxide thus:
2SO2 (g) + O2 (g)
2SO3 (g)
= 98 kJ mol1
Using your knowledge of Le Chateliers principle (which need not be stated), state and explain
the effect on the position of equilibrium of:
(i)
(ii)
7.
2HI(g)
Write an expression for Kp for this equilibrium, giving consideration to its units.
correct expression for Kp (1) no square brackets
atm 2
(b)
When 0.50 mol of I2 and 0.50 mol of H2 were mixed in a closed container at 723 K and 2
atm pressure, 0.11 mol of I2 were found to be present when equilibrium was established.
(i)
Calculate the partial pressures of I2 and 0.50 mol of H2 were mixed in a closed
container at 723 K and 2 atm pressure, 0.11 mol of I2 were found to be present
when equilibrium was established.
moles HI = 0.78 (1)
calculation of the mole fraction(s) (1)
calculation of the partial pressure(s) (1)
(3)
(ii)
(1.56) 2
(0.22) 2
(c)
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(ii)
What indicator would you use? Give the colour change at the end point.
starch (1)
blue/black to colourless (1)
not white or clear instead of colourless
(2)
(iii)
8.
(a)
(i)
(ii)
[ NO 2 ] 2
(1) mol dm3 (1)
[ N 2 O4 ]
must be [ ] and unit consequential on expression given for Kc
if incorrect expression but correct units for this expression then award
the units mark
if give correct expression for Kp and correct units
then award the units mark
Kc =
N2O4
1x
2NO2
2x
[N2O4] =
(1 0.5)(1) mol
10 dm3 (1)
2 x 0.5 (1)
[NO2] =
= 0.1
10
Kc =
(0.1 mol dm 3 ) 2
(iii)
(iv)
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(b)
(d)
L.C.P. lower pressure favours side with the more molecules (1)
(i)
no change (1)
(ii)
no change (1)
(iii)
bond enthalpy of N2 is very high / high activation energy / the NN triple bond is strong /
the bonding in the nitrogen molecule is strong / mixture of N2 + O2 is kinetically stable (1)
reaction very slow at reasonable temperature/ endothermic reaction/ needs high
temperature/ or high cost low yield arguments (1)
2
[17]
9.
(a)
[ HI ] 2
(1)
[ H 2 ][ I 2 ]
(i)
Kc
(ii)
(iii)
(b)
(i)
(ii)
(c)
(iii)
(i)
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(ii)
(iii)
4
[25]
10.
(a)
(b)
(c)
(i)
(ii)
(d)
3
[12]
11.
(a)
(i)
2
(ii)
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(b)
(c)
(d)
(i)
(ii)
(iii)
(i)
[ HI ]2
KC = [ H ][ I ] (1) if ( ) or KP or use HCl (0)
2
2
(ii)
I2
a
ax
0.4
2HI
0
2x
3.0 (1)
(3 / 0.25) 2
(1) to gain this mark there must be some reference
(0.4 / 0.25)(0.4 / 0.25)
(e)
(i)
(ii)
rate = k[H2][I2]
1.5 105 = k[0.1/0.5][0.1/0.5] (1)
k = 3.75 104 (1)
moldm3s 1
units:
= mol1dm3s1 (1)
moldm 3 moldm 3
3
[17]
12.
(a)
(i)
(ii)
(0.9 / 0.235) 2
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(iii)
(b)
(c)
(i)
(ii)
No effect (1)
(conditional on some reasoning)
Since H=0 (K value independent of temperature) (1)
(iii)
[14]
13.
(a)
(b)
Kc =
(c)
(i)
(d)
[SO 3 ]2
[SO 2 ]2 [O 2 ] 1
or
1
mol dm 3
(ii)
(i)
(ii)
There needs to be some reference to an alternative route for the second mark. The
words lowers the activation energy do not score.
(e)
Read the candidates whole answer; if full marks cannot be given then look for the
individual points.
Award 1st mark for correct explanations of thermodynamic stability (or instability)
Award 2nd mark for correct explanation of kinetic stability.
Award the 3rd mark for applying these definitions to THIS system.
thermodynamic: products at lower energy level than reactants thus thermodynamically
unstable(1) can be argued the other way
Kinetic: large Ea or means very few molecules have enough energy to react (1) so reaction
is very slow or is kinetically stable (1)
3
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(f)
14.
(a)
(i)
(ii)
OR
(b)
(i)
(ii)
(1)
increase in temperature:
(position of ) equilibrium goes to the right (1)
as endothermic left to right (1)
on the addition of sodium propanaoate
the position of equilibrium goes to left (1)
higher concentration of / more propanoate ions
or
sodium propanoate produces propanoate ions (1)
14
start pH 2 to 4 (1)
12
(i)
at 25 cm3 (1)
10
(ii)
20
30
40
50
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(d)
(i)
(ii)
1
(1)
2
[19]
15.
(a)
Still reacting / rate of forward reaction and backward reaction equal / implication that
forward and backward reactions are still taking place (1)
But concentrations constant / no macroscopic changes (1)
(b)
(c)
Temp
(Increases)
Press
Increases/faster (1)
(i)
(ii)
Increases rate / more SO3 / only needs small pressure to ensure gas passes through
plant / high or reasonable yield obtained at 1 atms or at low pressure anyway (1)
and
references to economic cost against yield benefit
e.g increase in pressure would increase yield of product but the increase in yield
2
would not offset the cost of increasing the pressure (1)
(iii)
(d)
(e)
16.
(a)
(i)
(ii)
(b)
Kp = p(NO2)/p(N2O4) (1)
units are atm or any SI unit of pressure (1)
(2)
Kp = p(CO2) (1)
units are atm or any SI unit of pressure (1)
(2)
(i)
moles at start
change
but x = 0.81
equilibrium moles
mole fraction
partial pressure /atm
marking points
N2O4
1
x
NO2
0
+ 2x
1 0.81 = 0.19
0.19 /1.81 = 0.105
0.105 1.2 = 0.126
1.62
total moles = 1.81
1.62 /1.81 = 0.895
0.895 1.2 = 1.07
total moles = 1 + x
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(c)
(5)
(ii)
(1)
(i)
Kc =
(ii)
(iii)
[SO 3 ] initial
[SO 2 ] initial [O 2 ]initial
[SO 3 ] 2
[SO 2 ] 2 [O 2 ]
(1)
(1)
(0.20/2) 2
(1) = 50
(0.40/2) 2 .(0.010/2)
(3)
5
[15]
17.
(a)
(i)
(i)
(ii)
(ii)
(i)
(ii)
(c)
(iii)
[15]
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18.
(a)
(b)
(i)
Dynamic:
reaction occurring in both directions / rate of forward reaction
and reverse reactions equal (1)
Equilibrium:
constant concentrations / no change in macroscopic properties (1)
(ii)
all substances in same phase / are all in the gaseous state (1)
(i)
(i)
(ii)
(ii)
(c)
(d)
(i)
(ii)
3
1
2
[14]
19.
(a)
(b)
(c)
(i)
(ii)
Kp
(iii)
(i)
No change (1)
(ii)
KP increase (1)
(iii)
No change (1)
(i)
Kp
(ii)
(iii)
not [ ]
1
p(CH 4 ) (1)
1
1
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(iv)
1
[12]
20.
(a)
(b)
(i)
12.25 100%
(1) = 95% (1)
(12.25 0.1 0.5)
(ii)
(c)
(i)
(ii)
If water is added to acid heat generated boils and liquid spits out (1)
if acid added to water the large volume of water absorbs the heat
generated (and the mixture does not boil) (1)
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(d)
(i)
(ii)
1
[18]
21.
(a)
(b)
(i)
(ii)
(i)
(ii)
Fraction
of
molecules
E a cat
E a uncat
(c)
(i)
Energy
Axis labels (1)
Starts at or near origin (not on y or x axis) skewed distribution
that is reasonably asymptotic to the x-axis (1)
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(ii)
4
[12]
22.
(a)
(i)
(ii)
(b)
(c)
(d)
0.2
30
= 3.33 103
0.1
1.8
60
60
3
1.67 10
0.03 (1)
(0.03) 2
Kc =
= 4860or 4.86 104 (1)
(3.33 10 3 ) 2 1.67 10 3
mol1 dm3 (1)
(i)
Kc decreases (1)
(ii)
(i)
no effect (1)
(ii)
no effect (1)
(i)
(ii)
(iii)
(iv)
2
[14]
23.
(a)
(b)
(i)
www.edexcel-cie.com
(ii)
(c)
(i)
H
H
H
C
H
(ii)
(iii)
OH OH OH OH
Penalise C-HO once
Or CH2(OH)CH(OH)CH(OH)CH2OH (1) for adding two OH groups across
one double bond, and (1) for adding it across both.
Consequential on structure in (c)(i)
2
1 mark per double bond max 2
[11]
24.
(a)
Kc =
[CO 2 ][ H 2 ] 4
CH 4 H 2 O2
(1)
Starting amounts:
CH 4 10g / 16 g mol
0.625 mol
(1)
3.0 mol
H 2 O 54 g / 18g mol 1
Equilibrium amounts:
CH4 = 0.625 2.0 = 0. 1 25 mol (1)
H2O = 3.0 2.0 = 2.0 mol (1)
CO2 = 0.0 + 2.0 = 0.500 mol (1)
H2 = 2.0 mol (given)
Equilibrium concentrations:
above values 4 dm3 (1)
(mark consequently)
[CH4] = 0.03125 mol dm-3
[H2O] = 0.500 mol dm-3
[CO2] = 0.125 mol dm-3
[H2] = 0.50 mol dm-3
Kc
[CO 2 ] eq [ H 2 ] eq
[CH 4 ] eq [H 2 O] eq
(c)
0.125 0.50 4
0.03125 0.500 2
H = (-394) [(-76) + (2 242)] (2) 1 mark for 2, 1 mark for signs and values
= + 166 (1) kJ mol1
166 scores zero
A catalyst (of nickel) is used because the reaction, even at 750C, is too slow /
to speed up the reaction (1)
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even though the reaction goes from 3 to 5 gas moles / more gas moles of
right of equation (1)
but a moderately high pressure is needed to push the gases through the
7
plant (1)
Ignore any reference to rate
Pressure could score up to 3 but max 6 for T and P combined.
Do not give all 7 marks unless the candidate has expressed their ideas clearly
[18]
25.
(a)
(i)
(ii)
The heat (energy) / enthalpy change when 1 mol of gaseous atoms (1)
NOT energy on its own
is formed from the element (1)
(iii)
Sr2+ (g)
2Cl (g)
2Cl(g)
Sr +(g)
Sr(g)
Hf
Sr(s) + Cl 2 (g)
SrCl 2 (s)
Cycle marks:
1 mark for cycle showing all balanced species
1 mark for all state symbols correct
Allow Sr(g) Sr2+(g) as a single stage
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Calculation marks:
Hf = sum of other terms and / or
829 = +164 +550 +1064 + 2 x ( +122) + 2 x ( 349) + LE
or LE= 82916455010642 x(+122) 2x(349)
ie 1 mark for multiplying Ha of Cl by 2
1 mark for multiplying EA of Cl(g) by 2
(b)
(i)
(ii)
(iii)
5
[18]
26.
(a)
(i)
Al2Cl6
Initial:
2
Equil:
0.5
Equil conc: 0.05
Kc =
AlCl3 2
Al 2 Cl 6
2 AlCl3
0
3 (1)
0.3 (1)
(1)
(ii)
Cl
Cl
Al
Cl
Cl
Al
Cl
Cl
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(b)
(i)
C 2H 5
+ C 2 H 5 Cl
+ HCl
1
(ii)
(1)
CH 2 CH 3
+
(1)
:ClAlCl3 )
C 2H 5
(1)
C2H5
+ HCl + (AlCl 3 ) + H +
4
(iii)
(c)
(i)
(ii)
3+
3
[20]
27.
(a)
(b)
Pressure exerted by the gas if it alone occupied the same volume at the
same temperature/mole fraction total pressure
p ( N 2 ) p (O 2 )
(i)
Kp =
(ii)
p( NO) 2
1
1
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(c)
(d)
Kp increases (1)
Equilibrium moves to r.h.s. (1)
which is the exothermic direction (1)
(i)
Kp = p (Ni(CO)4) / p(CO)
(ii)
2
[12]
28.
(a)
(b)
(c)
(i)
(ii)
(iii)
None (1)
If temperature too low, rate too slow/high temperature gives fast rate(1),
but if too high, yield too small/high yield needs low temperature (1)
therefore a compromise temperature (of 450 C) (1)
and catalyst for quick rate (at temperature 450 C)/catalyst not effective
if temperature below 400 C (1)
)
)
)
)
) Any one
)
)
)
)
[9]
29.
(a)
(i)
Kc =
(ii)
No effect (1)
Increases (1)
(iii)
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(b)
(i)
H H
H
C C C
H N+
H
H
H
OR
O
C
O
(ii)
(iii)
+
NH3
H 3C C
NH3
COO
+ H+
H3C C
NH3
H 3C C
COOH
COO
(H 3CCH(NH 3 )COOH) +
H 3 CCH(NH 3)COOH +
NH2
+ OH
H 3C
C COO + H 2 O
H
NH2
H 3C C COOH
H
(c)
(i)
(ii)
(iii)
1
[13]
30.
(a)
www.edexcel-cie.com
(b)
(i)
QWC(ii)
400-500 C / 673-773 K
[any temperature or range of temperatures within these ranges]
(iii)
(c)
(i)
(ii)
(1)
Max 3
(1)
(1)
(e)
(f)
2
1
1
[16]
31.
(a)
(i)
KP = p (CO2)
(ii)
1.48 (atm)
IGNORE p [
(b)
(i)
Kp =
p(Cl 2 ) p(NO) 2
(ii)
(p(NOCl)) 2
2NOCl
1
must have atm1
1.48
2NO
1
Cl2
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Start
1
0
0
0.22
+0.22
+0.11
eq moles
0.78
0.22
0.11
total moles of gas
1.11
mole fractions
above values 1.11 (1)
0.7027
0.1982
0.09910
partial pressure / atm above values 5.00 (1)
3.51
0.991
0.495
2
0.495 atm (0.991 atm)
Kp =
(1)
(3.51 atm) 2
= 0.0395/ 0.0394 atm (1)
range of answers 0.0408 / 0.041 0.039 / 0.0392 NOT 0.04
ACCEPT 2 S. F
Correct answer plus some recognisable working (5)
(1)
Equilibrium moles
Dividing by total moles
Multiplying by total pressure
Substituting equilibrium values into expression for KP
(iii)
(iv)
2
[12]
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32.
(a)
KC =
(1)
+ 2CH3COOH
Ester
+2H2O
0.320
0.640 (1)
3.56 7.112
0.889 5.112
7.11
180
23.2
= 7.76 / 7.8 / 7.74 etc. (1)
There are no units for K (1)
KC =
(b)
(c)
(ii)
(d)
1054
100 (1)
1240
2
Any acid with two COOH groups or its acid dichloride or its dimethyl
ester (1)
Accept HOOCCOOH
No, because the acid would hydrolyse / is a catalyst for the hydrolysis
of the ester.
OR
Yes, not hydrolysed at low temperature / only hydrolysed at high
temperature
The ester cannot form (intermolecular) hydrogen bonds but the acid can (1)
The ester does not have a +hydrogen atom
OR
the acid has +hydrogen / polar OH / O and H have a large difference in
electronegativities (1)
thus less energy / heat is required to separate molecules of the ester (1)
but as ethanoic acid has fewer electrons than propanoic acid, (1)
it has weaker intermolecular instantaneous induced dipole / induced
dipole forces / van der Waals / dispersion / London forces (1)
Allow vdW
5
[18]
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33.
(a)
(i)
(1)
cycle with state symbols or as energy level diagram. (1)
labels (in symbols, words or numbers) (1)
Hsoln = Hlat + Hhyd Ca2+ + 2 Hhyd OH OR values
Hlat = 1650 + 2 (460) (16.2) (1)
= 2553.8
(ii)
(b)
(i)
(ii)
(c)
) (1)
) OR formulae (1)
) (1)
4
[18]
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