Mark Scheme (FINAL)

Summer 2007

GCE

GCE Chemistry (6244/01)

Edexcel Limited. Registered in England and Wales No. 4496750

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

Examiners should look for qualities to reward rather than faults to penalise. This does NOT mean giving
credit for incorrect or inadequate answers, but it does mean allowing candidates to be rewarded for
answers showing correct application of principles and knowledge.

Examiners should therefore read carefully and consider every response: even if it is not what is expected
it may be worthy of credit.

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

Using the mark scheme

The mark scheme gives you:
• an idea of the types of response expected
• how individual marks are to be awarded
• the total mark for each question
• examples of responses that should NOT receive credit.

Candidates must make their meaning clear to the examiner to gain the mark. Make sure that the answer
makes sense. Do not give credit for correct words/phrases which are put together in a meaningless
manner. Answers must be in the correct context.

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.
 EXPECTED ANSWER ACCEPT REJECT MARK
1. (a) (i) Mg2+(g) (+) O2-(g) if state symbols missing (1)
If 2e− included in box

(ii) ∆H 1 (Enthalpy of) formation (of MgO) (1) (3)

∆H 2 (Enthalpy of) atomisation (of Mg) (1)

∆H 3 1st plus 2nd electron affinity (of O) Recognisable abbreviation

st nd such as “EA” for electron
OR 1 and 2 electron affinity (of O) (1)
affinity.
(iii) ∆H f = −602 = (+150) + (+2186) + (+249) + (+657) + LE Doubling electron affinity and/or (2)
OR atomisation values scores (0)
(LE =) -(+657)-(+249)-(+2186)-(+150)+(-602)(1)
any incorrect sign in algebraic
(LE =) -3844 (kJ mol ) (1)-1 expression (0)

Correct answer only with no working (1 max)

 EXPECTED ANSWER ACCEPT REJECT MARK
(b) (i) The electrons around the iodide ion are drawn (Mg ) polarises (I− ion)
2+
Any reference to atoms or (1)
towards the magnesium ion “distortion” if clearly linked molecules
to the iodide ion e.g. “Mg polarises…..”
“iodine/I/I2 is polarised”
“Mg ion”
“I ion” OR “iodine ion” Wrong polarisation e.g.
“magnesium ion is polarised”
“I− polarises Mg2+”

(ii) Radius/size (of ions) (1) Distance between ions “atomic radius” (2)
OR Sum of (ionic) radii
OR Type of crystal structure
OR Madelung constant

charge (on ions) (1) “Charge density”

(iii) Less (exothermic) (1) Smaller Higher/greater (2)

OR more endothermic
OR Less negative
OR Lower

covalent character (strengthens lattice) (1) Theoretical value based on Any implication of magnesium
purely/100 % ionic model iodide being totally covalent
Mark each aspect independently
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) (i) Enthalpy change when 1 mol of gaseous ions (1) Energy or heat Any implication of an (2)
endothermic process
e.g. energy required

“….1 mol of gaseous atoms”

is dissolved such that further dilution causes no “Added to water”/”reacts Just “hydrated”
further heat change (1) with water” instead of Just “completely hydrated”
“dissolved”
IGNORE “standard conditions”
Is dissolved to form an
Mark each aspect independently infinitely dilute solution
OR
Is dissolved in a
large/excess/infinite
amount of water
 EXPECTED ANSWER ACCEPT REJECT MARK
(ii) EITHER (4)
∆H SOLN = (−∆H LE + ∆H HYD ) (1)
Expression quoted or correctly used in at least one of
the calculations below

∆H SOLN MgSO4 = −(−2874) + (−1920) Answer only with no

working (1)
= +954(kJ mol −1 ) (1)

∆H SOLN BaSO4 = −(−2374) + (−1360) Answer only with no

= +1014(kJ mol −1 ) (1) working (1)

Enthalpy of solution of MgSO4 less endothermic/more Just “solubility/∆Hsoln depends

exothermic/more negative than for BaSO4, so MgSO4 on a balance between lattice and
more soluble than BaSO4 (or reverse argument) (1) hydration energies”

OR
(both) lattice energies and hydration enthalpies
decrease from MgSO4 to BaSO4 (or down group) (1)

(but) lattice energies change less (1) “The hydration energies (-)500 and (-)560 stated without
decrease faster…..” further explanation

∆H SOLN = (−∆H LE + ∆H HYD ) (1) stated in words or

symbols

so ∆Hsoln less exothermic/more endothermic/more Just “solubility/∆Hsolution depends

positive for BaSO4 so less soluble on a balance between lattice and
OR so ∆Hsoln more exothermic/more negative/less hydration energies”
endothermic for MgSO4 so MgSO4 more soluble (1)

(Total 17 marks)
 EXPECTED ANSWER ACCEPT REJECT MARK
2. (a) Any compressed formulae e.g. (2)

C2H5Br
OR CH3CH2Br

(1)
Any compressed formulae e.g.
CH3CONH2
OR

(1)
 EXPECTED ANSWER ACCEPT REJECT MARK
(b) Accept names or formulae, but ignore correct or (6)
incorrect conditions

Step A: NH3 (1)

Ignore state or dilution or solvent for ammonia

Step B: K2Cr2O7 (1) and H2SO4 (1) “Hydrochloric acid”/”HCl” instead Incorrect oxidation number
of “H2SO4” for dichromate(VI)
N.B. only award the acid/H2SO4 mark if a correct (or a
near-miss) oxidising agent given Cr2O72- and H+ (2) CrO42- alone (0)
OR
CrO42- and H+ (2)
OR
Acidified dichromate ions (2)
OR
Acidified K2Cr2O7 (2)
OR
acidified dichromate((VI)) (1)
OR
KMnO4 (1) and H2SO4 (1) Hydrochloric acid/HCl with
KMnO4 (0)
OR Incorrect oxidation number
alkaline KMnO4 (1) for manganate(VII)
then acidify (accept any acid) (1)

Step C: PCl5 OR SOCl2 OR PCl3 (1)

Step D: P2O5 OR P4O10 (1)

Step E: LiAlH4 (1) C2H5OH and Na NaBH4 (0)

OR H2 and Ni /Pt/Pd (catalyst)
OR Lithal
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) (i) (substituted) amide Polyamide (1)
OR (N-substituted) amide amine
OR secondary amide
OR 2◦ amide

H O O
(ii) (2)
N (CH2)6 N C (CH2)4 C

H
H O

− CONH
peptide link N C (1)

Rest of molecule and continuation bonds (1)

2nd mark is CQ on a polyamide being drawn

(d) Loss of smell: HCl as a reactant and (2)

+ +
CH 3CH 2 NH 2 + H + → CH 3CH 2 NH 3 (1) CH 3CH 2 NH 3 Cl − as product
(charges are not required).

Return of smell:
+
CH3CH2 NH3 + OH− →CH3CH2 NH2 + H2O CH3CH2NH3+ + NaOH →
CH3CH2NH2 + H2O + Na+ (1)
OR
CH3CH2NH3Cl + NaOH → CH3CH2NH2 + H2O + NaCl (1)
(Total 13 marks)
 EXPECTED ANSWER ACCEPT REJECT MARK
3. (a) (4)

Do not worry about general shape of the curve, the scoring

points are:

• Starting pH ~ 1 and finishing pH between 9 and 11 (1)

• Vertical at 25 cm3 (1)

• Vertical range: at least three pH units in the range 3 to 8

pH range 3 to 5
e.g. pH range 3 to 6 OR 3 to 7 OR 3 to 8 OR 4 to 7
OR 4 to 8 OR 5 to 8 (1)
(do not need to start/finish on whole numbers)

• Middle of vertical pH range between 4 and 6 (1)

 EXPECTED ANSWER ACCEPT REJECT MARK
(b) Bromocresol green (1)
Indicator(s) CQ on graph [check table on question paper] More than one indicator for
extended vertical regions

(c) pH change around equivalence point too small Too small a vertical (region) (2)
OR pH changes over too big a volume (1) OR no vertical (region)
OR no point of inflexion
OR no sudden change in pH
OR no straight section

for a sharp colour change of indicator (1) No sharp/clear/precise end point No suitable indicator
OR very small range over which OR No “easy” colour
indicator changes colour change

[If say ammonia is a strong base or ethanoic acid is a

strong acid, or both, (0 out of 2)]

(Total 7 marks)
 EXPECTED ANSWER ACCEPT REJECT MARK
4. (a) O (1)
H H
H C

O C C H

H H
(b) ester (1)

(c) (i) Moles: C2H5OH: 3.75 (1) (2)

Moles: HCOOC2H5 : 2.50 and moles H2O : 2.50 (1) for both

(ii) Kc =
[ HCOOC2 H 5 ][ H 2O] Obviously round (1)
[ HCOOH ][C2 H 5OH ] brackets “( )”

(iii) 2.50 × 2.50 (2.50) 2 1st mark if 485 used

Kc = 0.485 0.485 Kc = = 3.33 only scores as V in expression (2)
0.50 × 3.75 0.50 × 3.75
0.485 (1) 0.485 (2) if it is stated that V cancels
Must have clearly divided moles of each component by either here or in (iv)
0.485 for 1st mark e.g.
[HCOOC2H5] = [H2O] = 5.16 (mol dm-3) If [ H 2 O] omitted in (ii), then
and [HCOOH] = 1.03 (mol dm-3) answer
and [C2H5OH] = 7.73 (mol dm-3) K c = 0.647 mol-1dm3
(2) but this will give
= 3.33 (1) stand alone mark
K c = 1.33 mol-1dm3 with V
IGNORE sig.figs. omitted from calculation (1)

(iv) No, (as) equal numbers of moles on both sides “equal powers/moles on both “concentrations
OR volumes cancel sides” cancel” (1)
OR mol dm-3 cancel OR “ powers cancel”
OR units cancel
OR crossing out units to show they cancel Mark CQ on K c expression in (ii)
 EXPECTED ANSWER ACCEPT REJECT MARK
(d) (i) (as reaction) endothermic (1) Exothermic in backward (4)
direction (or words to that
effect)

Kc decreases (1) If state exothermic in forward

direction, 1 mark only (out of
4) for CQ “increase in Kc”

numerator in quotient (has to) decrease

OR denominator in quotient (has to) increase
OR fraction (has to) decrease (1)

yield of HCOOC2H5 decreases (1)

(ii) no effect as catalysts do not affect (the value of) K (1)

OR
no effect as catalysts do not affect the position of
equilibrium
OR
no effect as catalysts do not affect the yield
OR
No effect as catalysts increase the rate of the forward and
backward reactions equally/to the same extent
OR
no effect as catalysts only increase the rate Just “catalysts
OR increase rate”
no effect as catalysts only alter the rate

“no effect” can be stated or implied

IGNORE any references to activation energy

(Total 13 marks)
 EXPECTED ANSWER ACCEPT REJECT MARK
5. IGNORE state symbols throughout this question.

(a) (i) Na2O + H2O → 2NaOH .. → 2 Na + OH −

OR (1)
.. → 2 Na + + 2OH −

Multiples e.g.
2Na2O + 2H2O → 4NaOH

(ii) ionic Giant ionic (1)

OR electrovalent
(b) (i) P4 O10 + 6 H 2 O → 4 H 3 PO 4 Multiples
OR
P2 O5 + 3H 2 O → 2 H 3 PO4 (1)

(ii) covalent ‘molecular covalent’ ‘convalent’ (1)

‘simple covalent’ OR ‘giant covalent’
OR dative covalent

(c) basic (oxides) to acidic (oxides) (1) both words needed The elements change from (2)
IGNORE references to Al2O3 basic to acidic
IGNORE references to amphoteric character of Al2O3

metallic character (of the elements) decreases (1) metal to non-metal

IGNORE “across group” if used instead of “across period”

 EXPECTED ANSWER ACCEPT REJECT MARK
(d) (i) CO 2 + H 2 O ⇌ H + HCO3
+ − CO2 + H2O ⇌ 2H++ CO32- JUST (1)
OR CO 2 + H 2 O ⇌ H 2 CO3
OR
CO2 + 2H2O ⇌ H3O+ + HCO3-
CO 2 + H 2 O ⇌ H 2 CO3 ⇌ H+ +
HCO3-
OR
CO 2 + H 2 O ⇌ H 2 CO3 ⇌ 2H++
CO32-

“→” instead of “⇌”

(ii) PbO + 2 H + → Pb 2+ + H 2 O PbO with other acids (2)

OR
PbO + 2 HNO3 → Pb( NO3 ) 2 + H 2 O (1) Any equations with
PbO2
−
PbO + 2OH − + H 2 O → Pb(OH ) 4 2 −
formation of Pb(OH ) 6 4
OR
OR Na 4 Pb(OH ) 6
PbO + 2 NaOH + H 2 O → Na 2 Pb(OH ) 4
OR
PbO + 2NaOH → Na2PbO2 + H2O (1)
 EXPECTED ANSWER ACCEPT REJECT MARK
(e) Increases as Just “increases” on its (2)
own (0)
OR “increases”
followed by incorrect
justification (0)

EITHER
oxides acidic at the top of the group (1) Oxides more basic down group 1 (out of 2)
amphoteric at bottom of group (1) OR oxides less acidic down group 1 (out of 2)
[amphoteric must be stated for the 2nd mark]

OR
atoms become larger (1) atoms have more shielding/shells/energy levels Just “more electrons”
OR “(outer) electrons further from nucleus”
[no need to refer to atoms in this case] OR “the elements
become larger”

(so) more easily lose electrons

OR have lower ionisation energies
OR more easily form positive ions (in compounds) (1)
[allow 2nd mark even if no specific reference has been
made to atoms]

[N.B. Marking cannot allow points taken from both the

EITHER and OR arguments together]

(Total 11 marks)
 EXPECTED ANSWER ACCEPT REJECT MARK
6. (a) (i) CH 3 CH 2 CH 2 OH
(1) C 2 H 5 CH 2 OH C 3 H 7 OH (2)
OR full structural formula
e.g.
H H H
H C C C OH
H H H
OR
H H H
H C C C O H
H H H

Reduction
Redox
OR nucleophilic addition (1)
“Nucleophilic reduction”
IGNORE heterolytic
 EXPECTED ANSWER ACCEPT REJECT MARK
(ii) O O (2)
O
CH3CH2C C2H5C CH3CH2C
OH O-
OH
(1) OR
OR CH3CH2COOH
OR CH3CH2CO2H O
OR C2H5COOH C 2H 5C
OR C2H5CO2H O-
C2H5 instead of CH3CH2
OR full structural formula
e.g.
H H O
H C C C
H H OH

OR

H H O
H C C C
H H O H
oxidation
OR redox (1)
“oxidisation”
 EXPECTED ANSWER ACCEPT REJECT MARK
(iii) CH 3 CH 2 CH (OH )C ≡ N (1) C2 H 5CH (OH )CN (2)
OR
CH 3CH 2CH (OH )CN
OR full structural formula
e.g.
H H OH
H C C C CN
H H H
OR
H
H H O
H C C C C N
H H H
nucleophilic addition (1) both words needed
IGNORE “heterolytic”

(b) (i) Mg + C 2 H 5 Br → C 2 H 5 MgBr C2H5BrMg (1)

IGNORE charges C2H5MgI

(ii) Dry ethoxyethane (1)

OR dry ether
IGNORE references to I2 OR heat
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) (i) With propanone: (4)
Structure: (CH3)2C(OH)CH2CH3 (1) C2H5 in lieu of CH2CH3 C 5 H 11OH
OR
the full structural formula
e.g.
H3C OH H
C C C H
H3C H H
OR

H H H
H C O H
C C C H
H C
H H
H H

CQ structure provided it is a
tertiary alcohol

Name:
2-methylbutan-2-ol CQ name provided that it is a
OR 2-hydroxy-2-methylbutane (1) tertiary alcohol

IGNORE punctuation
 EXPECTED ANSWER ACCEPT REJECT MARK
With butanal: the full structural formula
Structure: e.g.
CH 3 CH 2 CH 2 CH (OH )CH 2 CH 3 (1) H H H H H H C 6 H 13 OH
H C C C C C C H
H H H OH H H
OR
H H H H H H
H C C C C C C H
H H H O H H
H
CQ structure provided it is
a secondary alcohol

Name:
hexan-3-ol (1) hexane-3-ol
CQ name provided that it is
a secondary alcohol

(ii) Butanal/the molecule/it is (2)

C O planar
H
OR Butanal/the molecule/it is
(group in butanal) is planar (1)
linear

References to carbocations
attacked (with equal probability) from two directions (1)
OR carbonium ions
OR Planar intermediates
Mark each aspect independently unless reference
OR SN1 mechanisms scores (0
made to carbocations etc
out of 2)
(Total 14 marks)
Mark Scheme (FINAL)
Summer 2007

GCE

GCE Chemistry (6245/01)

Edexcel Limited. Registered in England and Wales No. 4496750

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

Examiners should look for qualities to reward rather than faults to penalise. This does NOT mean
giving credit for incorrect or inadequate answers, but it does mean allowing candidates to be
rewarded for answers showing correct application of principles and knowledge.

Examiners should therefore read carefully and consider every response: even if it is not what is
expected it may be worthy of credit.

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

Using the mark scheme

The mark scheme gives you:
• an idea of the types of response expected
• how individual marks are to be awarded
• the total mark for each question
• examples of responses that should NOT receive credit.

Candidates must make their meaning clear to the examiner to gain the mark. Make sure that the
answer makes sense. Do not give credit for correct words/phrases which are put together in a
meaningless manner. Answers must be in the correct context.

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.

2
 EXPECTED ANSWER ACCEPT REJECT MARK
1 (a) (i) effervescence (1) bubbles, fizzing Gas/CO2 evolved (2)
COOH present/acid/ acidic/contains H+ (1) Just ‘acid-base
reaction’
[if wrong gas is identified second mark is lost]

(ii) Decolourises (1) “clear” used instead (3)

OR brown/orange/yellow to colourless of “colourless”

compound contains C=C / unsaturated (1) Alkene Just ‘double bond’

white precipitate so is a phenol (1) Activated benzene ring/OH

on benzene ring

(b) (i) Four (1) Correct description of the Rotates plane of (2)
(Two) cis/trans (or geometric), and (two) idea of cis-trans or optical plane-polarised light
chiral/optical isomers/ enantiomers (1) isomerism without the name
OR
Two cis-trans/geometric isomers (1)
Two optical isomers/enantiomers (1)
OR
cis-trans/geometric isomers and
optical isomers/enantiomers (1 only)
(ii) Molecule has a chiral centre/chiral carbon/carbon Asymmetric carbon (2)
with four different groups (1) atom/chiral molecule

having non-superimposable mirror images (1)

3
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) NaOH (solution) (1) W identified as secondary
Q halogenoalkane (1) so no (5)
W NaOH needed (1) for first
C* two marks

acidify with /add excess HNO3 (1) Neutralise with nitric acid just “add HNO3”
[If HCl is added here, only the NaOH mark can score]

add silver nitrate (solution) (1)

white precipitate (1)

soluble in dilute/aqueous ammonia (1) “dilute and concentrated “Concentrated

ammonia” ammonia” alone
If no NaOH max (4)

If HNO3 added only before NaOH, or no acid is added at all,

then can score 3rd, 4th and 5th marks

If order of addition is NaOH, AgNO3, HNO3 can score (5)

If no NaOH and no HNO3, can score last 3 marks

If any reagent other than silver nitrate, including

ammoniacal silver nitrate, is used only the 1st and 2nd
marks can score
Total 14 marks

4
 EXPECTED ANSWER ACCEPT REJECT MARK
2 (a) (i) Both orders correct (1)
Q (3)
W Expt 1 + 2: as [B] doubles rate x4 so second order
C* (wrt B)

OR
As [B] doubles with [A] constant rate x4 so second
order (wrt B) (1)

Expt 1 + 3: as [A] doubles rate x2 so first order (wrt

A)

OR
As [A] doubles with [B] constant rate x2 so first
order (wrt A) (1)

Omission of experiment numbers or failure to refer

to constant concentration of the other reagent
penalise once only
(ii) rate = k [A] [B]2 Must be consequential on (i) (1)
Can use upper or lower case “k”

(iii) k= 0.000195 = 0.195 (1) mol – 2 dm 6 s -1 (1) Both marks consequential on

2
0.10 x 0.10 (ii), but rate equation must (2)
[IGNORE s.f. in answer] include k

[If wrong experiment chosen only unit mark

available]

5
 EXPECTED ANSWER ACCEPT REJECT MARK
(b) (i) Increasing T means molecules have/collide with greater
Q energy (1) (3)
W
C* so a greater proportion /more of the molecules collide
with/have E > Ea/the activation energy (1)

so a greater proportion of the collisions are successful

OR
more of the collisions are successful/more successful
collisions in a given time (1)

(ii) (at least) two steps (1) Accept number more than
two (2)
Simultaneous collision of three particles is unlikely
OR valid mechanism e.g.
A+B → AB fast
AB + B → AB2 slow
OR
A+B →AB slow
AB + B →AB2 fast (1)

6
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) Value of slope = - 1.2 × 104 Any number between - 1.15 (4)
× 104 and - 1.25 × 104
Negative sign (1) Value (1) inclusive

Multiply by -8.31 (1)

Divide by 1000 to give 104 (kJ mol-1 ) (1) allow 95.5 – 104
[units not essential but penalise wrong units] consequential on slope

Correct answer with some working (4)

Correct answer with no working (3)
Penalise -1 mark if final answer is negative

IGNORE sig figs

Total 15 marks

7
 EXPECTED ANSWER ACCEPT REJECT MARK
o
3 (a) (i) uses E values to find Ereaction = (+) 1.57 (V) (1) - 1.57 (2)

Zn + 2NO3 – + 4H+ Æ Zn2+ + 2NO2 + 2H2O (1) Equation with equilibrium Equation with Zn on
sign the right

(ii) Ereaction for the production of hydrogen is (+) 0.76 (V) (1) (2)

smaller than reaction in (i) so is less likely (1)

OR
NO3- being the oxidised form of a redox couple with a
more positive E o than E o H+/½ H2 (1)
is a stronger oxidising agent than H+ (1)
(iii) hexaaquacopper(II) (1) hexaquacopper(II) formula (2)
OH2 2+
H2O Cu OH2
H 2O OH2
OH2

OR

(1)
Both marks stand alone
[IGNORE charge]
[IGNORE how H2O ligand is bonded to central cation]

8
 EXPECTED ANSWER ACCEPT REJECT MARK
(iv) ligand exchange/replacement/substitution (1) (2)

[Cu(H2O)6]2+ + 4Cl – ⇌ CuCl42 – + 6H2O (1) ALLOW →

OR
Accept H2CuCl4 + 2H+ for
[Cu(H2O)6]2+
+ 4HCl ⇌ CuCl4 2– +
+ 4H + 6H2O (1) CuCl42 – + 4H+
2+
(b) (i) Eo for the reaction is – 0.39 (V) (so not feasible) [value is Cu being the oxidised (1)
required]. form of the redox couple
with the more negative
E o , will not oxidise I−

(ii) CuI is a solid (so conditions are not standard) (1) Just ‘conditions not (2)
standard’
Equilibrium is pulled over/moves to favour the r.h.s.
(1)

(iii) [Cu(NH3)4]+ [Cu(NH3)2]+ [Cu(NH3)6]+ (1)

Any 2+ complex
OR [Cu(NH3)4(H2O)2]+

(iv) (atmospheric) oxygen (1) Air for oxygen (2)

oxidises Cu+ to Cu2+ (1)

9
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) (i) starch (1) (2)
blue-black/blue/black to colourless (1) Clear for colourless

(ii) (If added too early) insoluble complex/black solid formed, (1)
making titre too low

OR (If added too early) insoluble complex/black solid

formed, removes iodine from solution

OR (If added too early) insoluble complex/black solid

formed, causes inaccurate titre.

OR (If added too early) insoluble complex/black solid

formed, not all the iodine is titrated.

(iii) Amount thiosulphate = 0.01655 dm3 × 0.1 mol dm – 3 (1) (5)

= amount Cu2+ in 25.0 cm3 = 1.655 × 10 – 3 mol (1)

amount of Cu2+ in 250 cm3 = 1.655 × 10 – 3 × 10 (1)

mass of Cu (in sample) = 1.655 × 10 – 2 × 63.5 (1) = 1.051 g

% Cu in brass = 1.051 × 100/1.5 = 70 % (1)

[IGNORE sf]

[mass of 1.051g with working scores (4);

correct answer with no working scores (3).]
Mark consequentially
Total 22 marks

10
 EXPECTED ANSWER ACCEPT REJECT MARK
4 (a) Reagent: chloromethane/CH3Cl (1) Bromomethane/ (2)
CH3Br/iodomethane/ CH3I

Catalyst: (anhydrous) aluminium chloride/AlCl3/Al2Cl6 (1) iron(III) chloride/ bromide iron

OR equivalent bromides

Mark independently

(b) (i) (free) radical substitution (1)

(ii) Cl2 Æ 2Cl• (1) (4)

PhCH3 + Cl• Æ PhCH2• + HCl (1) Dot must not be
PhCH2• + Cl2 Æ PhCH2Cl + Cl• (1) on Ph penalise
once
any one of:
•
2 PhCH2 Æ PhCH2CH2Ph P instead of Ph
PhCH2• + Cl• Æ PhCH2Cl penalise once
2 Cl• Æ Cl2 (1)
[IGNORE curly arrows]
If the initiation or propagation steps are wrong, only the
termination step can score consequentially on any two of
their radicals.

11
 EXPECTED ANSWER ACCEPT REJECT MARK
(iii) flask and vertical condenser – need not be shown as separate (3)
items (1) [Ignore direction of water flow; penalise sealed
condenser] Allow the gas to be Bubbling gas into a
bubbled down a tube beaker OR other vessel
gas entry into liquid in flask (1) [allow tube to go through coaxial with the without a condenser 0
the side of the flask, but tube must not be blocked by flask condenser bore. (out of 3)
wall]

heating from a electric heater/heating mantle/sand

bath/water bath/oil bath (1) diagram or words
labelling of diagram not necessary Just ‘heat’, Bunsen
[IGNORE uv source]

12
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) (i) H CH2CN PhCH2CN (1)

C C N
H
C6H5CH2CN
(ii) hydrochloric acid / HCl (aq) OR dilute/aqueous sulphuric HCl alone (2)
acid/H2SO4 (aq) (1) Conc sulphuric acid

boil/heat (under reflux)/reflux (1) conditional on correct or Warm

nearly correct reagents i.e. “acid” or “H+ ”

OR
NaOH(aq) and boil (1)
Acidify (1)

(iii) ethanol and (conc) sulphuric acid (1) Formulae or names Alcohol for ethanol (2)
heat/warm/boil/reflux (1) conditional on presence of throughout Dilute sulphuric acid
ethanol

OR
PCl5 /PCl3/SOCl2 (1) Alcohol for ethanol
Add ethanol (1) conditional on first mark
PCl5 and ethanol (1) only
PCl5 in ethanol (0)

13
 EXPECTED ANSWER ACCEPT REJECT MARK
+
(d) (i) Ion at 105 is C6H5CO C6H5CO (2)
C 7 H5 O+

(1)

X is C6H5COOCH3/
C6H5CO2CH3/
C6H5COCH2OH

OR
O
CCH2OH

(1)

(ii) (2)
COOH CHO

OR

CH3 CH2OH
(1)

Side-chain(s) oxidised to COOH (1)

[N.B. one of the side-chains must be capable of being
oxidised to COOH to get 2nd mark]

14
 EXPECTED ANSWER ACCEPT REJECT MARK
(e) (i) PCl5 /Phosphorus pentachloride/phosphorus(V) chloride (1)
OR PCl3/ Phosphorus trichloride/phosphorus(III) chloride
OR SOCl2/Thionyl chloride/sulphur oxide dichloride

(ii) C
O
(2)
At least one ester link/ O fully shown (1) – stand alone

remainder of structure (1)

OR
O
O
O C C
OCH2CH2

[no need for n or brackets]

Check oxygen atoms carefully; must be four
If more than one repeating unit is shown the repeat unit
must be identified
(iii) (concentrated) acid/alkali (1) A named acid or Any substance that is (2)
alkali not an acid or an alkali
(ester link) would be hydrolysed
OR polymer would react to form the monomers/alcohol and Hydrolysis to acid
acid (1) conditional on 1st mark chloride
Total 24 marks

15
Mark Scheme (FINAL)
Summer 2007

GCE

GCE Chemistry (6246/02)

Edexcel Limited. Registered in England and Wales No. 4496750

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

Examiners should look for qualities to reward rather than faults to penalise. This does NOT mean giving
credit for incorrect or inadequate answers, but it does mean allowing candidates to be rewarded for
answers showing correct application of principles and knowledge.

Examiners should therefore read carefully and consider every response: even if it is not what is expected
it may be worthy of credit.

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

Using the mark scheme

The mark scheme gives you:
• an idea of the types of response expected
• how individual marks are to be awarded
• the total mark for each question
• examples of responses that should NOT receive credit.

Candidates must make their meaning clear to the examiner to gain the mark. Make sure that the answer
makes sense. Do not give credit for correct words/phrases which are put together in a meaningless
manner. Answers must be in the correct context.

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.
 EXPECTED ANSWER ACCEPT REJECT MARK
1 (a) The amount of a solid present is immaterial since Kc does not depend on (1)
this

OR solids do not appear in expression for equilibrium constants

IGNORE any references to solid in excess.

(b) Ag+ + I – Æ AgI (1)

IGNORE state symbols

(c) Correct answer with some working and correct units scores full marks. (8)
Otherwise steps in calculation must make it reasonably clear to examiner
what is being calculated (QWC).

(initial amount) I - = 0.100 mol dm – 3 x 0.050 dm3 = 5 x 10 – 3 mol (1)

Amount Ag+ = 0.100 mol dm – 3 x 0.031 dm3 = 3.1 x 10 – 3 mol (1)

∴equilibrium amount I -= 3.1 x 10 – 3 mol (1)

I - reacted = (5 – 3.1) x 10 – 3 mol = 1.9 x 10 – 3 mol (1)

If this subtraction is not carried out then the next mark (for calculating
amount of sulphate) can not be awarded.

thus amount of sulphate = ½ x 1.9 x 10 – 3 (= 9.5 x 10 –4 mol) (1)

3.1 x 10 -3 mol
conc iodide = 3
(= 0.062 mol dm – 3)
0.05 dm
0.95 x 10 -3 mol
AND conc sulphate = 3
(= 0.019 mol dm – 3) (1)
0.05 dm
The mark is for the process of dividing by 0.05 dm3

Kc = 0.019/0.0622 = 4.94 (1) Answer must be to 2 or more S.F.

Value consequential on dividing their moles by a volume.

mol – 1 dm 3
(1) Stand alone
Total 10 marks

1
 EXPECTED ANSWER ACCEPT REJECT MARK
2 (a) (i) Pairs: acid NH4+ /ammonium ion and base NH3 /ammonia (1)
+
acid H3O / hydronium ion and base H2O / water Hydroxonium ion

(ii) [NH 3 ] [ H 3O + ] [NH3 ] [ H ]

+ Answers including [H2O] (1)
Ka = +
ignore lower case k Ka = +
[ NH 4 ] [ NH 4 ]

(iii) [ H3O+] = 10 – 5 mol dm – 3 (1) (4)

Assumption ionization of NH4+ (negligibly) small (1) [NH4+] = [NH4Cl]

or NH4Cl totally ionized

Assumption [NH3] = [ H3O+] (1)

thus [NH4Cl] = (1 x 10 – 5 )2 / 5.62 x 10 – 10

= 0.178 mol dm – 3 (1)
Answer to 2 or more S.F.

(iv) methyl red (1)

(2)
Q indicator constant or pKIn must be near the endpoint pH pKIn in the steep part of
W OR indicator constant or pKIn must be near 5 (1) the graph
C* 2nd mark conditional on correct indicator or it is a weak base-strong
acid titration

(b) CN– + H2O HCN + OH– Accept “→” instead of (1)

IGNORE state symbols “⇌”

2
 EXPECTED ANSWER ACCEPT REJECT MARK
(c) (i) nucleophilic addition (1)

(ii) (3)
O(:)
C O C CN
Fish hook arrows
(:)CN (penalise once)
(1) for intermediate
(1) for both arrows

(1)
O(:) H CN OH
C CN C CN + (:)CN

OR for second step

O(:) H OH
C CN C CN

(1)
•Ignore the groups attached to the carbonyl carbon throughout
•The intermediate is not consequential on their first step
•The minus of the cyanide ion can be on either the C or the N
•The arrow can start from the minus of –CN in step 1 (but not from the
minus of CN-) and can start from the minus of O- in step 2
•The arrow from the bond must not go past the O atom
•Lone pairs not essential
•Single step addition of HCN or initial attack by H+/HCN scores zero
•Autoionisation of C=O can only score the last two marks ie max 2

3
 EXPECTED ANSWER ACCEPT REJECT MARK

(iii) if too acidic too small a concentration of cyanide ions (1) Not enough / too (2)
Q little CN-
W
C* if too alkaline too little HCN to donate the proton in the last step
OR H+ ion concentration too low (1)

(d) (i) rate = k[CH3CH2CH2Cl] [CN – ] ‘R’ or ‘r’ for rate [KCN] (1)
Must be an equation C3H7Cl] /
Must be [ ] NOT ( ) [1-chloropropane]/
Ignore upper case K [chloropropane]

[cyanide ion]/
[cyanide]

(ii) Mechanism based on (3)

SN1 scores 0

Fish hook arrows

(penalise once)

Arrow from N of CN

Curly arrow (1)

Curly arrow (1) Transition state (1)

• Must have partial bonds in transition state
• CN and Cl must be on opposite sides of central C in the transition state
• Accept negative charge on N of cyanide ion

(e) Useful for extending the carbon chain/skeleton for ascending a Just ‘Increasing the (1)
homologous series number of carbon
atoms in the molecule’
Total 20 marks

4
 EXPECTED ANSWER ACCEPT REJECT MARK
3 (a) Heat/enthalpy/energy change per mole for formation of a compound/substance (1) “Normal” OR “stable” Energy required (2)
Q IGNORE any mention of standard conditions or temperature instead of “standard” OR
W Energy given out
C*
(in a stated physical state) from its elements in their standard states (1)

(b) (i) ∆ H = (+90.2 x 4) + (– 242 x 6) – (– 46.1 x 4) (2)

= – 907 (kJ mol – 1) (2) IGNORE sf

Correct answer with no working scores (2)

One mark for correct use of all three coefficients
One mark for correct use of signs throughout

(ii) – 1268 (kJ mol – 1) (1)

IGNORE sf

(c) (i) Because it is the more exothermic (1)

(ii) changes the activation energy for a reaction by changing the mechanism/route (2)
Q (1)
W
C* lowers it for Reaction I more than for Reaction II
OR catalyst specific for Reaction I (1)

[Comparison is essential]

5
 EXPECTED ANSWER ACCEPT REJECT MARK
(d) (i) To protonate the nitric acid If candidate says to (2)
OR to generate NO2+ generate the
OR increases the concentration of NO2+ compared with nitric acid alone (1) electrophile, the
IGNORE comments concerning H2SO4 being a catalyst mark can be
awarded if NO2+ is
2H2SO4 + HNO3 Æ H3O+ + NO2+ + 2HSO4 – shown in the
or H2SO4 + HNO3 Æ H2O + NO2+ + HSO4 – (1) equation
or both of:
H2SO4 + HNO3 Æ H2NO3+ + HSO4 – then H2NO3+ Æ H2O + NO2+ OR
H2NO3+ + H2SO4 Æ H3O+ + NO2+ + HSO4 –

(ii) sulphuric acid protonates nitric acid Just “H2SO4 is dibasic (1)
and HNO3 is
OR nitric acid accepts a proton / H+ from the sulphuric acid (1) monobasic” or similar
arguments
Answer may refer to the equation forming H2NO3+
(iii) allow equivalent (3)
using the circled
symbol for benzene;

allow loss of H+ in
the last step

Curly arrow from double bond/ circle towards N of electrophile (1)

Correct intermediate. (if a broken ring is used for the delocalised electrons
it must extend over the other 5 carbons) (1)
Curly arrow from C-H bond back into ring (1)
(iv) Any dinitrobenzene isomer OR any trinitrobenzene (1)

6
 EXPECTED ANSWER ACCEPT REJECT MARK
(v) delocalised ( π ) electrons over the benzene ring (1) Delocalised pi system Just ‘Delocalised (3)
ring’
Q Just ‘Delocalised
W bonds’
C*
substitution regains/retains the stabilisation energy (1) Stability for stabilisation
energy
which would be lost if addition occurred (1)

(e) Alkaline (potassium) manganate(VII) (1) “permanganate” instead of Just “Alkaline (2)
“manganate(VII)” manganate”
OR Formulae KMnO4 + dilute acid
scores neither mark

any named acid (1) Formula e.g. HCl etc. Concentrated

consequential on correct answer or near miss for first mark. sulphuric acid

Total 20 marks

7
 EXPECTED ANSWER ACCEPT REJECT MARK
4 (a) 3d104s1 and 3d10 4s13d10 (1)

(b) (i) the (3)d sub-shell is full (1) Orbitals (it must be Comments on partially (2)
Q plural) for sub-shell filled sub-shell
W so no d-d transitions are possible
C OR no transitions in the right energy range are possible (1)
* (and no light is absorbed)
Any mention of light emission loses 2nd mark

(ii) combine the half-reactions to get 2Cu+ Æ Cu2+ + Cu (1)

IGNORE state symbols (2)

and show that Eo for this is (+) 0.37 (V) (and as it is positive it is Just ‘> 0.3 (V)’
feasible) (1)
conditional on correct reaction

(iii) activation energy (for the disproportionation) is high Activation energy for (1)
OR one of the half-
Cu+ is kinetically stable equations is too high

(c) (i) divides each by atomic mass (1) Division by atomic

number scores zero (2)
divides by smallest to obtain Cu2SO6H2 (1)

(ii) CuSO4.Cu(OH)2 (2) Cu2SO4(OH)2

Cu2(OH)2SO4 (2)
If formula wrong but sulphate/ SO4 is present scores 1 (out of 2) (CuOH)2SO4 HSO4 instead of SO4

(iii) [Cu(NH3)4(H2O)2]2+ [Cu(NH3)4]2+ [Cu(NH3)6]2+ (1)

(iv) ligand exchange / ligand substitution (1)

8
 EXPECTED ANSWER ACCEPT REJECT MARK
(d) (i) (add aldehyde to 2,4-DNP) to obtain precipitate/ppt/solid/crystals (1) (4)
Q
W recrystallise derivative (1)
C*
determine melting temperature of derivative (1) Any identification method
based on IR, NMR or mass
compare with data tables (1) 4th mark conditional on melting for last 2 marks
temperature of a derivative being measured

(ii) the aldehyde is distilled off as it is formed Any mention of reflux (1)

Just ’the aldehyde is

distilled off’

(iii) propanoic acid OR CH3CH2COOH OR CH3CH2CO2H C2H5 for CH3CH2 (1)

(iv) No (extra) oxygen present (1)

OR catalyst specific to formation of aldehyde / only lowers Ea of first
oxidation
OR presence of hydrogen gives reducing conditions
OR copper is not an oxidising agent
OR aldehydes rapidly leave catalyst surface

(v) (At high pressure) all active sites are occupied/full Reverse argument for (1)
low pressure

OR
(At higher pressures) rate controlled by availability of sites.
Total 20 marks