Summer 1997 CH2 Mark Scheme

H
1. Cinnamaldehyde, one of the steriosomers of which the structure

is used in

H CHO fragrances for its jasmine-like odour. It contains two functional groups, other than the benzene ring, which may be assumed to have their normal reactions and to behave independently of each other.
(a) Name the two functional groups present in the molecule.
Alkene (1) aldehyde/alkanal (1) (2)

(b)

The presence of unsaturation in this molecule can be shown by the reaction with bromine dissolved in hexane. (i) What is the observable result of this test?
decolourisation/solution goes colourless (1) not discolourisation or goes clear (1)

(ii)

CH=CH + Br2 CHBrCHBr (1)

Give the equation for the reaction occurring.

if equation uses molecular formulae then (0) (1)

(iii)

Give the mechanism for this reaction. You may use CH==CH to represent the molecule of cinnamaldehyde if you wish. BrBr Br :Br
C=C
+

correct arrows: on BrBr () on C=C () from Br (1) intermediate (1) the arrow on Br must not start from ve sign but lone pair is not required allow triangular ion intermediate (3)

(iv)

What type of mechanism is this?

electrophilic addition (1) (1)

(c)

How would you test for the presence of a >C==O group in this molecule?
2,4-DNP / Bradys reagent (1) orange-yellow (ie a colour from red yellow) ppt / solid / crystals (1) OR correct adehyde reagent ie ammoniacal silver nitrate / Fehlings / Benedicts plus observation (1) justification that adelhyde contains carbonyl group (1) (2)

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Summer 1997 CH2 Mark Scheme

(d)

Give the structure of another stereoisomer of cinnamaldehyde and explain how it arises. Structure:
structure of cis isomer clearly drawn (1) restricted/no rotation about >C=< (1) some reference to relevance of bond to restricted rotation (1) (3)

(e)

(i)

Give the structure of a molecule produced by reduction of cinnamaldehyde.

C6H5CH2CH2CH2OH or CH=CHCH2OH or CH2CH2COH (1)

(ii)

Suggest a reagent you would use to achieve this reduction.

H2 / Pt or LiAIH4/NaBH4 or Na / ethanol or metallic couple/ethanol (1) the reagent stated is consequential on the product given in answer eg if reduce CHO to CH2OH only then H2/Pt is incorrect (1) (Total 15 marks)

2.

(a)

State Hesss Law

enthalpy/heat/heat energy change (1) independent of route (1) allow a clear diagram (2)

(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)

(ii)

In the smelting of zinc ores, the following reaction occurs: ZnS(s) + 1O2(g) ZnO(s)

= 441 kJ mol1

Use this, together with the data below, to calculate a value for the enthalpy of formation of ZnS. Data: ZnS(s) + 1O2(g) ZnO(s) S(s) + O2(g) SO2 (g)

H H

= 441 kJ mol1 = 297 kJ mol1

correct answer by any method with full sensible working (5) if correct answer but no working then (1) only incorrect answer means max 4 as follows: (2) for cycle of H statement (penalise (1) for each error) (2) for substitution of correct values and signs in the appropriate equation (penalise (1) for each error) Example

Zn
348

+
297

S +

ZnS
441

ZnO

SO2

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Summer 1997 CH2 Mark Scheme

OR ZnS + 1O2 ZnO + SO2 Hreact 441 Hf[ZnS] = Hf[ZnO] + Hf[SO2] Hf[SnS] = 348 297 Hf[ZnS] = 204 ignore units (5)

(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) increasing the temperature at constant pressure;
left (1) OWTTE direction of endothermic reaction/ K decreases because H ve (1) (2)

(ii)

increasing he total pressure at constant temperature.

right (1) OWTTE number of gas molecules decreases (1) reduces pressure because gas molecules relate to pressure or volume (1) marks can be awarded for Kp explanation (3) (Total 13 marks)

3.

State Hesss Law

enthalpy/heat/heat energy change (1) independent of route (1) allow a clear diagram (Total 2 marks)

4.

(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)

(ii)

In the smelting of zinc ores, the following reaction occurs: ZnS(s) + 1O2(g) ZnO(s)

= 441 kJ mol1

Use this, together with the data below, to calculate a value for the enthalpy of formation of ZnS. Data: ZnS(s) + 1O2(g) ZnO(s) S(s) + O2(g) SO2 (g)

H H

= 441 kJ mol1 = 297 kJ mol1

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Summer 1997 CH2 Mark Scheme

correct answer by any method with full sensible working (5) if correct answer but no working then (1) only incorrect answer means max 4 as follows: (2) for cycle of H statement (penalise (1) for each error) (2) for substitution of correct values and signs in the appropriate equation (penalise (1) for each error) Example

Zn
348

+
297

S +

ZnS
441

ZnO
OR

SO2

ZnS + 1O2 ZnO + SO2 Hreact 441 Hf[ZnS] = Hf[ZnO] + Hf[SO2] Hf[SnS] = 348 297 Hf[ZnS] = 204 ignore units (5) (Total 6 marks)

5.

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) increasing the temperature at constant pressure;
left (1) OWTTE direction of endothermic reaction/ K decreases because H ve (1) (2)

(ii)

increasing he total pressure at constant temperature.

right (1) OWTTE number of gas molecules decreases (1) reduces pressure because gas molecules relate to pressure or volume (1) marks can be awarded for Kp explanation (3) (Total 5 marks)

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Summer 1997 CH2 Mark Scheme

010009000003a300000004000a0000000000050000000b02090589fe050000000c024e00a7000400000 003010800050000000b0200000000050000000c020100010004000000030108000500000 00b0200000000050000000c0201000100050000000c02331d803e050000000b020000000 00500000006010100000007000000fc020100000000000000040000002d01000008000000 fa0200002c0200001f1a1700040000002d0101000a00000025030300ef2ee000dc3dda0ba4 00da0b08000000fa0200000000000000000000040000002d01020007000000fc020000fffff f000000040000002d01030004000000f0010100040000002d01000008000000fa0200002c 0200001f1a1700040000002d0101000a00000025030300910f531ca4005911dc3d5911040 000002d010200040000002d01030004000000f0010100030000000000 2SO3 (g)DH 6. (a) CH3CO2H + H2O CH3CO2H +HCI
(i) (ii) I II

When ethano

CH3CO2 + H3O+ CH3CO2H2 + Cl

When hydrogen chloride dissolves in ethanoic acid, the equilibrium established is: II

Comment on the role of the ethanoic acid in:

(acid) proton/H+ donor (1) if just acid (). (1) (base) proton/H+ acceptor/remover (1) if just base () (1)

(b)

What is the relationship between the species CH3CO2H2+ and CH3CO2H?

conjugate (acid/base) pair (1) (1)

(c)

The value of Ka for ethanoic acid at 298 K is 1.74 mol and for methanoic acid, HCO2H, it is 1.60 104 mol dm3 at the same temperature. (i) Write an expression for Ka for XH3CO2H.
+

105

dm3

[ H ][ CH 3CO2 ] Ka (1) if [H2O] included (0) accept [H3O+] [CH 3CO2 H ]

(1)

(ii)

Hence calculate the pH of a 0.100 mol dm3 solution of CH3CO2H at 298 K.

1.74 105 =

[ H + ]2 or [H+] = 1.32 103 (1) 01 .

(2)

pH = 2.88 / 2.9 / 2.90(1)

(d)

The pH of a 0.050 mol dm3 solution of HCO2H is 2.55. Using this, together with the data in (c) and your answer to (c)(i): (i) state which of the two acids is the stronger;
methanoic (1) (1)

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Summer 1997 CH2 Mark Scheme

(ii)

comment on the relative pH values of the two acids.

pH less for methanoic () despite it being more dilute () strength depends on Ka / degree of dissociation (1) pH depends on concentration as well as strength / pH is measure of concentration of hydrogen ions sensible comment on relative electron release effect of the methyl group (1) (3)

(e)

(i)

Sketch with reasonable accuracy on the axes below, how the pH changes during the titration of 20.0 cm3 of a 0.100 mol dm3 solution of methanoic acid with 0.050 mol dm3 sodium hydroxide solution.
correct start pH 2 3 (1) line must be rising for this mark to be awarded correct place for vertical line at 40 cm3 (1) correct range for vertical portion (or slightly off vertical) ie start at 6/7 end at 10/11 (1) (3)

(ii)

Select using the data below a suitable indicator for this titration. Give a brief reason for your choice based on the curve drawn in (e)(i). Indicator Bromocresol green Bromothymol blue Phenol red pH Range 3.5 5.4 6.0 7.6 6.8 8.4

Phenol red or bromothymol blue (1) pH range for colour change in correct pH range for vertical portion of graph (1) note: the choice of indicator is consequential on the straight vertical portion of the graph drawn (2) (Total 15 marks)

7.

(a)

The graph below represents the Maxwell-Boltzman distribution of molecular energies at a temperature T1 K.
Number of molecules with a given energy

Activation Energy

Energy

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Summer 1997 CH2 Mark Scheme

(i)

Sketch on the same axes, the curve which shows the distribution of molecular energies at a higher temperature T2 K. T2 is approximately 20 K greater than T1.
sketch showing peak moved to the right (1) lower peak than original (1) conditional on 1st mark (2)

(ii)

Use these graphs to explain how the rate of a gas phase reaction changes with increasing temperature.
higher T: the average energy of molecules increases (1) (hence) more molecules have energy grater than the activation energy/ sufficient energy to react / reference to area under curve (1) and collide more frequently / more effective collisions (1) OWTTE hence rate increase (1) (4)

(b)

For a gaseous reaction, state and explain what effect the addition of a catalyst would have on: (i) the energy distribution of the gas molecules;
no effect (1) energies of mols / depend only on temperature (1) (2)

(ii)

the activation energy for the reaction;

reduced (1) new route of lower activation energy provided (OWTTE) (1) (2)

(iii)

the rate of reaction.

increased (1) more molecules have sufficient(minimum) energy to react (1) (2)

(c)

Thioethanamide reacts with sodium hydroxide as follows: CH3CSNH2 2OH CH3CO2 + HS + NH3 The reaction is first order with respect to both thioethanamide and hydroxide ions. (i) Write the rate equation for this reaction.
rate = k[CH3CSNH2] [OH] (1) (1)

(ii)

What is the overall order of the reaction?

2 (1) (1)

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Summer 1997 CH2 Mark Scheme

(iii)

Given that the reaction occurs in two stages and the rate determining step is:
CH3CSNH2 + OH CH3CONH2 + HS

Write an equation for the second step in the reaction.

CH3CONH2 + OH CH3CO2 + NH3 (1) (1) (Total 15 marks)

8.

The graph below represents the MaxwellBoltzman distribution of molecular energies at a temperature T1 K.

Number of molecules with a given energy

Activation Energy
(i)

Energy

Sketch on the same axes, the curve which shows the distribution of molecular energies at a higher temperature T2 K. T2 is approximately 20 K greater than T1.
sketch showing peak moved to the right (1) lower peak than original (1) conditional on 1st mark (2)

(ii)

Use these graphs to explain how the rate of a gas phase reaction changes with increasing temperature.
higher T: the average energy of molecules increases (1) (hence) more molecules have energy grater than the activation energy/ sufficient energy to react / reference to area under curve (1) and collide more frequently / more effective collisions (1) OWTTE hence rate increase (1) (4) (Total 6 marks)

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Summer 1997 CH2 Mark Scheme

9.

For a gaseous reaction, state and explain what effect the addition of a catalyst would have on: (i) the energy distribution of the gas molecules;
no effect (1) energies of mols / depend only on temperature (1) (2)

(ii)

the activation energy for the reaction;

reduced (1) new route of lower activation energy provided (OWTTE) (1) (2)

(iii)

the rate of reaction.

increased (1) more molecules have sufficient(minimum) energy to react (1) (2) (Total 6 marks)

10.

Thioethanamide reacts with sodium hydroxide as follows: CH3CSNH2 2OH CH3CO2 + HS + NH3 The reaction is first order with respect to both thioethanamide and hydroxide ions. (i) Write the rate equation for this reaction.
rate = k[CH3CSNH2] [OH] (1) (1)

(ii)

What is the overall order of the reaction?

2 (1) (1)

(iii)

Given that the reaction occurs in two stages and the rate determining step is:
CH3CSNH2 + OH CH3CONH2 + HS

Write an equation for the second step in the reaction.

CH3CONH2 + OH CH3CO2 + NH3 (1) (1) (Total 3 marks)

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