Mark Scheme (Final)

January 2009

GCE

GCE Chemistry (6245/01)

Edexcel Limited. Registered in England and Wales No. 4496750

Registered Office: One90 High Holborn, London WC1V 7BH
 General Marking Guidance

• All candidates must receive the same treatment. Examiners must mark the first
candidate in exactly the same way as they mark the last.

• Mark schemes should be applied positively. Candidates must be rewarded for what
they have shown they can do rather than penalised for omissions.

• Examiners should mark according to the mark scheme not according to their
perception of where the grade boundaries may lie.

• There is no ceiling on achievement. All marks on the mark scheme should be used
appropriately.

• All the marks on the mark scheme are designed to be awarded. Examiners should
always award full marks if deserved, i.e. if the answer matches the mark scheme.
Examiners should also be prepared to award zero marks if the candidate’s
response is not worthy of credit according to the mark scheme.

• Where some judgement is required, mark schemes will provide the principles by
which marks will be awarded and exemplification may be limited.

• When examiners are in doubt regarding the application of the mark scheme to a
candidate’s response, the team leader must be consulted.

• Crossed out work should be marked UNLESS the candidate has replaced it with an
alternative response.

Using the mark scheme

1 / means that the responses are alternatives and either answer should receive full credit.
2 ( ) means that a phrase/word is not essential for the award of the mark, but helps the examiner to
get the sense of the expected answer.
3 [ ] words inside square brackets are instructions or guidance for examiners.
4 Phrases/words in bold indicate that the meaning of the phrase or the actual word is essential to
the answer.
5 ecf/TE/cq (error carried forward) means that a wrong answer given in an earlier part of a question
is used correctly in answer to a later part of the same question.

Quality of Written Communication

Questions which involve the writing of continuous prose will expect candidates to:

• show clarity of expression

• construct and present coherent arguments
• demonstrate an effective use of grammar, punctuation and spelling.

Full marks will be awarded if the candidate has demonstrated the above abilities.

Questions where QWC is likely to be particularly important are indicated “QWC” in the mark scheme BUT
this does not preclude others.
Question Correct Answer Acceptable Answers Reject Mark
Number
1 (a) Half arrows or just 2
3d 4 vertical lines
s

Cu+ ⇅ ⇅ ⇅ ⇅ ⇅

Cu2+ ⇅ ⇅ ⇅ ⇅ ↑
1 mark for each row

Question Correct Answer Acceptable Answers Reject Mark

Number
1 (b)(i) ligands split d orbitals (1) This first mark If sequence in wrong 3
QWC is stand alone order eg jump then
absorb
absorb light in (part) of visible region/all Or
colours except blue(1) Stand Alone any implication that
this is an emission
causes electron to jump / be promoted spectra
to a new level (1) then
only first mark
(orbitals splitting)
available

Question Correct Answer Acceptable Answers Reject Mark

Number
1 (b)(ii) No ligands to split (d) orbitals (1) No complex ion Full so cannot 1
Implication that all d orbitals the same /water ligand present jump

Question Correct Answer Acceptable Answers Reject Mark

Number
1 (c)(i) X CuCl OR Cu2Cl2 OR copper(I) Allow HCl on both 2
chloride(1) allow cuprous chloride sides

CuCl2 + Cu 2CuCl
or
CuCl2 + Cu Cu2Cl2(1)

Question Correct Answer Acceptable Answers Reject Mark

Number
1 (c)(ii) Redox (1) Reduction 1

Question Correct Answer Acceptable Answers Reject Mark

Number
1 (c)(iii) Cu(NH3)2+ (1) 1

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Question Correct Answer Acceptable Reject Mark
Number Answers
1 (c)(iv) The copper(I) ion has a full d (sub) shell/d10 d orbitals 1
OR not
All d orbitals are full (1) splitting
(so d-d transitions impossible)
Or
No partly filled d

Question Correct Answer Acceptable Answers Reject Mark

Number
1 (c)(v) Cu(NH3)42+ Cu(NH3)62+ 1
Or And
[Cu(NH3)4(H2O)2]2+ (1) Cu(NH3)2+
[ ] not essential

Question Correct Answer Acceptable Reject Mark

Number Answers
2 (a) Nucleophilic substitution (1) Hydrolysis 1

Question Correct Answer Acceptable Reject Mark

Number Answers
2 (b)(i) Expt 1 and 2/concentration of 1-brombutane 3
constant
Concentration of hydroxide trebled, rate x3
First order with respect to OH- (1)

Expt 2 and 3/concentration of hydroxide

constant.
Concentration of
1-bromobutane x4, rate x4. First order with
respect to
1-bromobutane.(1)
If both orders given with no explanation 1
(out of 2)

Rate = k[1-bromobutane] [hydroxide] (1)

mark rate equation consequently.

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Question Correct Answer Acceptable Reject Mark
Number Answers
2 (b)(ii) . 3
-
R
HO : R
(1) δ+ δ- -
H C – Br
HO ----C ---- Br
(1)
H H
H (1)

HO C H
+ :Br-
H
Both arrows must be in first step
Allow SN1 if rate equation in 2(b)(i) is zero order in OH- and first
order wrt. RBr
Allow arrow from negative charge
ignore δ+ and δ-
Lone pairs need not be shown

Question Correct Answer Acceptable Reject Mark

Number Answers
2 (c)(i) The SN1 mechanism 4
involves the production of a planar intermediate (1)

which can be attacked from both sides(of the plane)(1)

producing a racemic mixture/ equal amounts of both isomers/

both enantimorphs (1)
last mark stand alone

The SN2 mechanism

Either
involves attack from opposite side to Br
Or
would produce a single (inverted) optical isomer
or single enantiomorph
Or
Attack from one side only
Or
Intermediate not planar
(1)

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Question Correct Answer Acceptable Reject Mark
Number Answers
2 (c)(ii) The RDS is the slowest step (in a multi-step mechanism) References 2
(1) to those
species in
Breaking of bond between carbon and bromine/formation the rate
of carbocation / carbonium ion equation
Or sketch to show this
Or equation (1)

Question Correct Answer Acceptable Reject Mark

Number Answers
3 (a)(i) 3
H H (1) H H
| | | |
H – C = C – CH3 H – C - C+– CH3
|
H
(:)Br- (1)
H - Br
(1)
H H
| |
H – C – C – CH3
| |
H Br

If charge on wrong carbon leading to 1-bromoproduct only the 1st

mark may be awarded.

Question Correct Answer Acceptable Reject Mark

Number Answers
3 (a)(ii) Secondary intermediate/carbocation is the Secondary 1
more stable (1) bromopropane is
Or more stable
reverse argument
Or
drawings

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Question Correct Answer Acceptable Answers Reject Mark
Number
3 (b) EITHER only consider changes 3
Bonds broken
3 x C = C = 3 x 612 = (+)1836
3 x H – H = 3 x 436 = (+)1308
(+)3144
(1)

Bonds formed
3 x C – C = 3x 347 = (-)1041
6 x C – H = 6 x 413 = (-)2478
(-)3519 (1)
Enthalpy change = 3144 +(-3519)
=-375 kJ mol-1(1)

OR break and make all bonds

Bonds broken
3 x C – C = 3 x 347 = (+)1041

3 x C = C = 3 x 612 = (+)1836

6 x C – H = 6 x 413 = (+)2478

3 x H – H = 3 x 436 = (+)1308

(+)6663 (1)
Bonds formed
6 x C – C = 6x 347 = (-)2082 +375 is worth 2 marks
since only one error.
12 x C – H = 12 x 413 = (-)4956
mark the third mark
(-)7038 (1) consequentially
Enthalpy change = 6663 +(-7038)
=-375 (kJ mol-1
)(1)

Question Correct Answer Acceptable Answers Reject Mark

Number
3 (c)(i) The unused p electron orbitals overlap Any suggestion 2
(sidewayst to produce a π system that that sigma bond
extends over the whole ring of carbon being formed
atoms) (1)

Diagram (1)

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Question Correct Answer Acceptable Answers Reject Mark
Number
3 (c)(ii) Addition would disrupt the delocalised π Allow reverse 2
system (1) argument

Substitution restores or retains the

delocalised π system and this has greater
(energetic) stability (1)

Question Correct Answer Acceptable Answers Reject Mark

Number
3 (d)(i) One in which the solute shows high solubility 1
in hot but low in cold (1)

Question Correct Answer Acceptable Answers Reject Mark

Number
3 (d)(ii) Firsthot filtration/ second step (1) 1

Question Correct Answer Acceptable Answers Reject Mark

Number
3 (d)(iii) 1
Soluble impurities will not crystallise out
after cooling

OR Soluble impurities remain in solution

after cooling
OR Cold solution is not saturated with the
impurities (1)

Question Correct Answer Acceptable Answers Reject Mark

Number
3 (d)(iv) To remove any impure solvent/solution on 1
crystals (1)
Must be idea of liquid not solid

Allow remove any soluble impurities still in

the solution

Question Correct Answer Acceptable Answers Reject Mark

Number
3 (d)(v) Minimum (volume) of hot solvent “Bullets 1, 2 or 5” 1
OR
wash with (ice-)cold solvent
OR
I st filtration so that crystals not removed.
(1)

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Question Correct Answer Acceptable Answers Reject Mark
Number
4 Diagram Stand alone 5
Lozenge drawn (1)
At least 2 horizontal and 2 vertical tie bars
starting at 50/50 mixture (1)

Explanation – stand alone

Vapour richer in the more volatile
component/ hexane (1)
(Evaporates,)condenses and reboils(1)
Pure hexane distilled off (1)

If say heat at 69 oC and boil off hexane NO

marks for explanation

Question Correct Answer Acceptable Answers Reject Mark

Number
5(a) 3
Carbon Hydrogen Oxygen
81.82 6.06 12.12
12 1 16 (1)
= 6.818 = 6.06 = 0.7575
6.818 6.06 0.7575
0.7575 0.7575 0.7575
=9 =8 =1 (1)

Empirical formula = C9H8O

EF mass = 132
∴ Molecular formula = C9H8O (1)
Marking
1 mark for division by Ar
1 mark for division by smallest
1 mark for showing EF = MF by use of 132
Note the third mark is for showing that their
EF adds up to 132
OR
% C = 9x12x100 = 81.82 (1)
132
% H = 8x1x100 = 6.06 (1)
132
% O = 16x100 = 12.12
132
OR by difference for which ever one is not
calculated(1)

Question Correct Answer Acceptable Answers Reject Mark

Number
5 (b)(i) Carbonyl group 1
OR Aldehyde or ketone (both needed)
OR C=O group (1)

Question Correct Answer Acceptable Answers Reject Mark

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Number
5 (b)(ii) Aldehyde/CHO 1
OR
“Not a ketone” if mark awarded in (i) (1)

Question Correct Answer Acceptable Answers Reject Mark

Number
5 (b)(iii) Must have (one) C=C (1) Alkene 1
Ignore unsaturated
group

Question Correct Answer Acceptable Answers Reject Mark

Number
5 (c)(i) Side chain 1
EXCLUDED BY
C=C–C=O QUESTION
| | |
H H H

Question Correct Answer Acceptable Answers Reject Mark

Number
5 (c)(ii) Br H If give side chain in 2
5(c)(ii) allow marks

* C| - |C – C| = O here consequentially

H H H

(1) for correct structure or with the bromine

on carbon 2
(1) mark for indentification of chiral centre

Question Correct Answer Acceptable Answers Reject Mark

Number
5 (c)(iii) Substitution in the benzene ring (1) Reacts by substitution Nucleophilic 2
Addition to side chain (1) and addition without substitiution
OR clarification 1 mark
Substitution in the benzene ring (1) only
Different positions around the ring/multiple
substitution (1)

Question Correct Answer Acceptable Answers Reject Mark

Number
6 (a) (dirty/grey) green ppt (1) Any green 2

(Then a dark) green solution (1)

This mark does not depend on the colour of
the ppt.

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Question Correct Answer Acceptable Answers Reject Mark
Number
6 (b)(i) 1st mark 2
Both directions of change of position of
equilibrium given (1)

2nd mark
Explanation involving H+ in each case(1)

Question Correct Answer Acceptable Answers Reject Mark

Number
6 (b)(ii) Oxidation number of Cr in Cr2O72- and CrO42- No change in 1
is +6. (1) ON of Cr
Actual oxidation number of Cr must be
stated

Question Correct Answer Acceptable Answers Reject Mark

Number
6 (c)(i) 2Cr3+ + Zn ⇌ 2Cr2++ Zn2+ (1) Multiples 1
Ignore state symbols

Question Correct Answer Acceptable Answers Reject Mark

Number
6 (c)(ii) Cr2++ Zn ⇌ Cr + Zn2+ (1) Multiples 1
Ignore state symbols

Question Correct Answer Acceptable Answers Reject Mark

Number
6(c)(iii) E o for Zn reducing Cr3+ going to Cr2+ is+ 0.35 Answers based on other 2
(V) use of the data eg. As
and cell diagrams and loss
E o for reducing Cr2+ to Cr = -0.14(V) (1) of electrons can score
Both required for 1 mark full marks

because E o for second reaction is negative / Must be some reasoning

not feasible(1) for second mark

Second mark consequential on figures in

first part.

Note
If both E values correct final product is Cr2+
If E1 and E2 are both calculated as +ve - final
product is Cr
If E1 and E2 both calculated as negative final
product is Cr3+

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Question Correct Answer Acceptable Answers Reject Mark
Number
6 (d) Two possible routes ignore sig figs Alternative routes are 5
possible for full marks
1st mark
Amount of dichromate in used in titration Notes
= 19.00 x 0.0136 (1) If use 56 (Fe) in place
1000 of 132 they get 21.7%.
= 2.584 x 10-4 mol

2nd mark
Mols of iron =
6 x 19.00 x 0.0136 (1)
1000
= 0.00155 mol (1.550 x 10-3)

3rd mark
Total amount in 250 cm3
= 10 x 6 x 19.00 x 0.0136 (1)
1000
= 0.0155 mol (1.55 x 10-2)

OR
Conc of Fe2+
= 0.00155 (1)
0.025
= 0.0620 mol dm-3

4th mark
Mass of iron(II) sulphate
=152 x10x6 x 19.00 x 0.0136
1000
(1)
= 2.357 g

OR
Mass of FeSO4 in 250 cm3
= 0.0620 x 152
4
= 2.357 g dm-3

5th mark
Percentage of iron sulphate
2.357 x 100
4.00
= 58.9% (1) allow 59

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Question Correct Answer Acceptable Answers Reject Mark
Number
6 (e) Ist mark 4
QWC Viable separation technique after reaction If reflux to convert
with heating with acidified potassium primary right through to
dichromate(VI) (1) acid and secondary to
e.g. If change in colour of dichromate from ketone.
orange to green distil out product(as it is
formed) Allow dnp for ketone

2nd mark And a positive test for

If no change in colour tertiary alcohol (1) acid i.e not proof by
elimination.
3rd mark
Either
Test distillate of other two with Tollens’
reagent
If silver mirror aldehyde present and alcohol
was primary (1)

If no silver mirror ketone present and

alcohol was secondary(1)

OR
Fehling’s in place of Tollens’

If answer just describes tests without

chemical argument 1 out of the last two
marks

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