GCE

Edexcel GCE
Chemistry (9080)

January 2006

Mark Scheme
Chemistry (9080)
Edexcel GCE
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January 2006
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 Contents

Unit 6245/01 page 1

Unit 6246/01A (Practical Test) Page 9

Unit 6246/02 Page 15

i
Mark schemes are prepared by the Principal Examiners and revised, together with the
relevant questions, by a panel of senior examiners and subject teachers. The
schemes are further amended at the Standardisation meetings attended by all
examiners. The Standardisation meeting ensures as far as possible that the mark
scheme covers the candidates’ responses to questions and that every examiner
understands and applies it in the same way. This scheme does not include any
details of the discussions that took place in the meeting, nor does it include all the
possible alternative answers or equivalent statements that were considered to be
worthy of credit.

It is emphasised that these mark schemes are working documents that apply to these
papers in this examination series. Every effort is made to ensure a consistent
approach to marking from one examination series to another, but each marking point
has to be judged in the context of the candidates’ responses and in relation to the
other questions in the paper. It should not be assumed that future mark schemes
will adopt exactly the same marking points as this one.

Edexcel cannot under any circumstances discuss or comment on the marking of

individual scripts. Any enquiries about the marks awarded to individual
candidates can be dealt with only through the official Enquiry About Results
procedure.

Using Mark Schemes

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. Phrases/words in bold indicate that the meaning of the phrase or the actual
word is essential to the answer.
4. 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.
5. 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.

ii
Unit 6245/01
1. (a)
The emf of a half-cell measured relative to the standard hydrogen electrode (1)

all solutions at 1 mol dm-3 concentration and gases at 1 atm pressure/101kPa

and at a stated temperature / 298K (1) Standalone mark
ALLOW pressure of 100 kPa (2 marks)

(b) (i) Introducing another metal wire would set up its own p.d. / can only
measure a potential difference / need source and sink for electrons /
voltmeter requires two connections (1 mark)

(ii)

Hydrogen/H2(g)
1 atm / 101kPa

(1)

Pt / platinum
Hydrogen ions /
H+(aq) / (1)
hydrochloric acid
1 mol dm-3
(3 marks)
(1)

H2 or H+ with no conditions max (2)

(c) (i) + -
2Fe(s) + O2(g) + 2H2O(l) Æ 2Fe2 (aq) + 4OH (aq) or multiples

OR

2Fe(s) + O2(g) + 2H2O(l) Æ 2Fe(OH)2(s)

Species (1)

balancing (1)
Do not allow species mark if electrons still in equation, but allow
(2 marks)
balancing mark if 4e on both sides
(ii) ∆Eθreact = (+) 0.84 (V) (1) (2 marks)
Greater than zero therefore feasible (1)

1
QWC* (iii)
Zn oxidises preferentially to Fe/Zinc acts as sacrificial (anode) (1)
If Sn used (and damaged), Fe oxidises preferentially (1)
Disallow “oxidises more readily”
Eθ Zn2+/Zn more negative than for Fe
OR
Eθ Zn/Zn2+ more positive than for Fe
OR
Eθcell for Zn being oxidised by O2 is more positive than for Fe being oxidised by
O2
OR
similar Eθ arguments related to preferential oxidation with Sn (1) (3 marks)
disallow “higher” or “bigger” for more negative or more positive

Total 13 marks

2 (a) Delocalisation / π-system (1)

due to overlap of six p-orbitals

OR
Due to overlap of p-orbitals around the ring (1)

Confers stability/ benzene at a lower energy level / more energy needed to break
bonds compared with having three separate π / double bonds / cyclohexatriene,
Kekule structure (1) Standalone mark (3 marks)

(b) 1st step: sulphuric and nitric acid (1)

concentrated (1)
Intermediate: Nitrobenzene / C6H5NO2 (1)
2nd Step: Tin / iron and conc HCl (followed by addition of alkali) (1)
disallow Sn or Fe as catalyst (4 marks)

2
(c) (i) AlBr3/FeBr3 / AlCl3 / Al2Cl6 / FeCl3 / Fe2Cl6 (1 mark)

(ii) AlBr3 + CH3CH2Br CH3CH2+ + AlBr4− (1)

ALLOW C2H5+ in this equation only

(3)
Arrows
Do not allow to C2H5+ (4 marks)
ALLOW to point/go to + charge

ALLOW C2H5 in intermediate

(iii) Electrophilic substitution (1 mark)

3
QWC* (d)
136

Boiling VAP
point / °C

LIQ 80

100% 60% 0%

% of ethylbenzene in mixture

EXPLANATION:
At least two horizontal and two vertical tie-lines drawn from 60%
ethylbenzene (1)

Vapour condensed and then reboiled (1)

Vapour (from 60% ethylbenzene liquid) gets richer in the more volatile
component (benzene) / residue gets richer in ethylbenzene (1)

Pure benzene distilled off / ethylbenzene left as residue (1)

4th mark not a stand alone mark (4 marks)

If no correct tie lines drawn, max (2)

Total 17 marks

4
3 (a) (i) Forms ions which have partially filled d-orbitals
OR
Forms ions which have a partially filled d-subshell (1 mark)

(ii) Scandium / Sc and Zinc / Zn (1 mark)

+ 6
(b) (i) Fe2 [Ar] 3d
+ 5
Mn2 [Ar] 3d (1) for both correct
(1 mark)

(ii) Fe3+ is 3d5 / half filled d-subshell which is more stable than 3d6 (1)
+
Mn2 is (already) 3d5 (which is more stable than 3d4) (1) (2 marks)

(c) Shape (1)

Bonding to correct atoms (1)

CN
(4-) NC CN (4-)
CN OR
NC CN Fe
Fe
NC CN NC CN
CN CN (2 marks)
−
(d) Two As atoms oxidised from +3 to +5 per mole of As2O3 (loss of 4e ) (1)

−
∴ if 5 moles oxidised, total 20e lost / change in oxidation no. = 20 (1)

− -
∴ 4 moles MnO4 reduced, total 20e gained / change in oxidation no. 20
−
∴ each Mn(VII) gains 5e /change in oxidation no. 5 (1)

∴ Mn(II) / Mn2+ (1) NOT standalone mark (4 marks)

- + +
(e) (i) VO3 + 2H / 2H3O+ Æ VO2 + H2O / 3H2O (1 mark)

(ii) No because oxidation no. of V is +5 in VO2+ / Oxidation no. of V unchanged

(at +5) (1 mark)
+ 2+
(iii) First green colour : VO2 and VO (1)
3+
Second green colour : V / [V(H2O)6]3+ (1)
2+ 2+
Violet colour : V / [V(H2O)6] (1) (3 marks)

Total 16 marks

5
4 (a) (i) Correct points (1)
Smooth curve (1)

t½

t½

(2 marks)

(ii)
First half life 15 min ( ± 1 min ) (1)
(2 marks)
Second half life 15 min ( ± 1 min ) (1)

If not shown on graph max (1)

(iii) 1st order (1)
t½ is constant (1) (2 marks)

(b) (i) Zero (1 mark)

(ii)
Rate = k [2-bromo-2-methylbutane] ALLOW a formula (1 mark)
Mark consequentially on (a)(iii) and (b) (i)
(iii)

Mark consequentially on (ii), i.e. If SN2 mechanism given in (b)(ii, then

one mark for each arrow (2) and transition state including sign (1) (3 marks)

(c) C2H5
The intermediate /carbocation / is planar (1)
C+
H CH3

(Equal) attack from either side (1) (3 marks)

(therefore) racemic mixture (produced) (1) Standalone mark
Total 14 marks

6
5 (a) (i) Elimination / dehydration (1 mark)

(ii) Concentrated sulphuric acid / concentrated phosphoric acid / aluminium

oxide (1 mark)
ACCEPT correct formula
(1 mark)
(iii) Hydrolysis

(iv) Esterification (1 mark)

(v) CH3OH / methanol (1 mark)

(b) (i) EITHER

OR

Lone pairs not essential

Arrows may start from minus of O−
ALLOW CN− OR −CN
(4 marks)
+
(ii) High [H ]
-
insufficient CN (available for nucleophilic attack) (1)

+
Low [H ]
+
insufficient H / HCN for the second stage (1)
+ + (2 marks)
High [[H ] surpresses ionisation / shifts equilibrium to left and low [H ]
shifts equilibrium to right max (1)

7
(c) (i) (Free) radical / peroxide (1 mark)

(ii)
H CH3
C C
H COOCH3
Correct repeating unit (1)
Continuation bonds dependent on a 2 carbon skeleton unit (1) (2 marks)

(iii)
The polymer chain lengths are different (due to different termination steps) (1 mark)
/ different size molecules/ different numbers of monomer (units)

Total 15 marks

TOTAL FOR PAPER: 75 MARKS

8
Unit 6246/01A

1. (a) Purple/violet (1) TM compound / ion (1)

OR
Cr(III)/Cr3+
Mn(VII)/MnO4- Any two
3+
Fe(III)/Fe

(b) (i) Green/grey-green ppt (1) Cr(III)/Cr(OH)3/Cr3+/Cr(H2O)3(OH)3/

Insoluble in excess (1) chromium(III) (1)

(ii) green ppt (1) Cr(III)/Cr3+/Cr(OH)3 (1)

soluble in excess…..green solution (1) [Cr(OH)6]3- /chromite(1)

(iii) white ppt (1) SO42-/sulphate/BaSO4/barium sulphate (1)

If coloured ppt in observation (0), but allow

inference
IGNORE HSO4−

(c) yellow filtrate (1) Oxidation/redox/reduction(1)

to Cr(VI)/CrO42-/chromate (1)
allow redox from green solution but not
chromate
(Total 14 marks)

9
2 (a) (i) B immiscible/ two layers/ insoluble (1) long chain/high Mr /
OR description of insoluble/mixture hydrocarbon, halogenoalkane, ester,
aromatic/non-polar (1)

C miscible/one layer/soluble (1) (short chain)

ain) H-b
H-bonding with water or
alcohol, carbonyl compounds, amine,
carboxylic acid ; polar(1)
NOT salts

(ii) B no observable change/stays orange (1) “Not oxidisable”/not reducing/not primary

or secondary alcohol/not aldehyde/tert
C (pale) blue/green (1) alcohol/ketone (1)

Oxidisable/ reducing agent/1o or 2o alcohol

(1) [OR] aldehyde (1)

(iii) B brown ppt (1) alkene (1)

NOT just “brown” or brown solution ALLOW inference from just “brown”

C brown ppt after 10 mins (1)

(b) (i) 3230-3550

OR single value between 3300 and 3500 (1)
OH (1)
IGNORE CH assignment

(ii) 1° / 2° / “1o or 2o “ alcohol (1)

(Total 15 marks)

10
3. (a) Comparison with Supervisor’s results
Two results recorded within 0.20 cm3 (1)

All volumes recorded to 0.05 cm3 (1)

Allow one slip but withhold this mark if any reading in wrong box
Allow initial reading of 0, 0.0 and 0.00 NOT 50

All subtractions completed correctly (1)

Mean titre: for correctly averaging chosen titres or for choosing identical values
and for recording to 0.05 cm3 or 2 or 3 d.p. (1)
if already penalised for bad recording do not penalise again.

ACCURACY

If the candidate has made an arithmetical error in the Table then the examiner
must calculate a new average.
• For an averaging error simply calculate a new value using the candidates’
chosen values
• If a wrongly subtracted titre has been used in the mean then chose any two
identical titres or take an average of the closest two.

Calculate the difference between the candidate’s mean titre and that of the
supervisor. Record the difference as “d=…” Award marks for accuracy as follows:

difference
d= ±0.20 ±0.30 ±0.40 ±0.50
mark 4 3 2 1

PENALTY
If the candidate has averaged titres that differ by more than 0.20 cm3 then the
examiner must subtract marks from the accuracy mark. The examiner must also
subtract marks if the mean has been corrected because of incorrect subtraction,
and new titres outside 0.20 cm3 have been used.

range [r] between titres 0.00-0.20 0.21-0.30 0.31-0.40 0.41-0.50 0.51-0.60

subtract from accuracy 0 1 2 3 4
mark

Examiner to show this as d-r= max [4]

show this even if r=0 (8 marks)

11
(b) (i) 0.13
Amount of sodium thiosulphate = x titre
1000

(=X mol) (1 mark)

x
Amount of MIO3 =
6
(= y mol) (1 mark)

y
Concentration KIO3 = x1000
25

(= Z mol dm-3)
Correct concentration scores (3) without intermediate steps (1 mark)

(ii) M = 4 (1)
Z

A(r) = M – 175 (1)

IGNORE SF (2 marks)
Mark consequential on titre
(Total 13 marks)

12
4. Examiner to indicate which plan is applied at top of candidate’s answer

Plan A

Excess solid salt plus water (1) 9E

allow to reach equilibrium / to make saturated solutions (1) 9Q

Leave to settle / filter (1) 9S

Pipette (known volume of) solution (1) 9P

Add sulphuric acid and KI solution (1) 9I

Titrate vs. (standard) thiosulphate (1) 9T

Repeat until concordant titres (1) 9R

[Ca2+] = [iodate] (hence K) (1) 9C

2
If no 9E then start marking at 9 P

If no 9 I then do not award 9 T or 9 R so 9C is also withheld

Plan B

Excess solid plus water 9E (1)

Reach equilibrium 9Q (1)
Settle/filter 9S (1)
Pipette volume of solution 9P (1)
Add (excess) reagent to ppt calcium ions 9P1 (1)
Filter 9F (1)
Dry and weigh 9D (1)
Calculations 9C (1)

If no excess solid start marking at point 4

Plan C

Known mass of excess solid 9E (1) in known volume of water 9V (1)

Allow to equilibrate 9Q (1)
Filter 9F (1)
Dry and Weigh 9W (1)
Find mass dissolved 9S (1)
Find concentrations 9J (1)
Calculations to find K 9K (1)

(Total 8 marks)

13
14
Unit 6246/02

1. (a) 3OCl- → 2Cl- + ClO3- (1)

chlorine (in OCI-) is (simultaneously) oxidised from +1 to +5 (1)

and reduced from +1 to -1 (1)
If only oxidation numbers given max 1 (out of 2)
If oxidation numbers omitted max 1 (out of 2) (3 marks)

(b) (i) blue/black to colourless (1 mark)

(ii) no. moles S2O32- used = 12.5 x 0.1 / 1000 = 1.25 x 10-3 (1)

no. moles I2 = 1.25 x 10-3 / 2 = 6.25 x 10-4 (1)

no. moles ClO- = no. moles I2 (1)
no.moles ClO- in original 10 cm3 = 10 x 6.25 x 10-4
= 6.25 x 10-3 (1)
no.moles ClO- in 1 dm3 = 100 x 6.25 x 10-3 (1) = 0.625 (5 marks

(iii) mass Cl2 = 0.625 x 71

= 44.4 (g)
mark consequentially on (ii)
must be 3s.f. in final answer (1 mark)

(c) Cl2 is the stronger oxidising agent because Cl2 oxidises S from
(+)2 to (+)6 (1)
but I2 oxidises S from (+)2 to (+)2.50 (1) (2 marks)

QWC (d) Cl2 oxidises KI / iodide to I2. or balanced equation (1)

II2 reacts with starch/paper to give blue/black (1) (2 marks)

Total for Question: 14 marks

15
2 (a) (lattice of) cations/positive ions/Mg2+ (1)
attracted to delocalised / sea / cloud of electrons (1)
which are mobile/can move (1) (3 marks)

QWC (b) Mg2+ smaller (radius) than Ba2+ / magnesium ion is smaller and has the
same charge (as a barium ion) (1)
do not allow charge density unless explained
Greater polarisation/distortion of carbonate ion/anion (1) (2 marks)

(c) Either
Step 1 : Magnesium in dry ether/ethoxyethane (1)

add (solid) CO2 / dry ice (1) add methanal / HCHO (1)
Then add water / dilute acid / or Then H+/Cr2O72- or acidified
formula or H+ (1) (potassium) dichromate (1)

OR
Add KCN/potassium (or sodium) cyanide (1)
In aqueous ethanol (1) (3 marks)
Then heat / reflux with acid/H+ (1)

(d) (i) [H3O+] = 7.94 x 10-4 (mol dm-3) (1)

[HA]=
[H O ]
3
+ 2
OR
(7.94 × 10 −4 ) 2
(1)
Ka 1.35 × 10 −5

[HA] = 0.0467 (mol dm-3) (1) IGNORE S.F. (3 marks)

(ii) CH3CH2COOH+H2O ⇌ CH3CH2COO-+H3O+

/ CH3CH2COOH ⇌ CH3CH2COO-+H+ (1)

[CH3CH2COO-] small / acid is only dissociated to a small extent /

slightly (1)
NOT “acid not fully/partially dissociated”

Adding H+ causes large change in [A-] , but small change in [HA] (1) (3 marks)

16
(iii) [weak acid] = 0.0429 / or moles weak acid = 0.0015 / or vol of weak
acid = 15 cm3 (1)

[salt] = 0.0286 / or moles salt = 0.001 / or vol of salt = 10 cm3 (1)

[H+] = Ka x (acid/salt) = 2.025 x 10-5 (1)

pH = -log [H+] = 4.69 (1) (allow 1 dp or more)

(consequential throughout)

(note: allow any correct alternative processing methods for last 2

marks)

(note: common errors:

pH = 4.5 / 4.47 etc, with working, scores 3 marks..1 error made.
pH = 4.9 / 4.87 etc, with working, scores 2 marks.. 2 errors made) (4 marks)

Total 18 marks

17
3 (a) (i) CH3COCH3 (use expts 1 + 2) as conc doubles, rate doubles
first order (1)

I2 (use expts 1+3) as conc changes/halves, rate is constant

zero order (1)
if no explanations max 1 for both orders

H+ explanation (1) first order (1)

e.g.
expts 1+4 or 3+4 as [CH3COCH3] doubles and [H+] doubles, rate x4
but 1st order w.r.t.[CH3COCH3] so must be 1st order w.r.t.[H+]
OR
Expts 2+4 as [I2] doubles and [H+] doubles, rate doubles but zero order
w.r.t. [I2] so must be 1st order w.r.t. [H+]
(4 marks)

(ii) 2 consequential on (a) (1 mark)

(b) rate = k[CH3COCH3][H+] consequential on (a)(1)

k (= e.g 1.5 x 10-5 / 0.4 x 0.4) = 9.4 x 10-5 (1)

consequential on their rate equation units dm3 mol-1 s-1 (1) (3 marks)

QWC (c) step 1 – slow / rate determining step / step 2 – faster (1)
iodine has zero order (or is not in rate eqn) so.. does not take part in
a slow step / r.d.s. or is in a fast step or is in mechanism after r.d.s. (1) (2 marks)

(d) Expt 2 starts at 0.004 and Expt 3 at 0.002 (1)

Expt 2 : line steeper (1)
Expt 3 : line parallel (1) (3 marks)

(e) (i) (aqueous) sodium (or potassium) hydroxide / carbonate or formulae (1 mark)

(ii) water or any dilute acid or formula (1)

H H H
H C C C H
H O H
H (1)
ALLOW OH (2 marks)

(f) 1 peak propanone, 3 peaks propanal (1)

hydrogen in one environment, hydrogen in three environments (1)
[These could be shown on structural formulae]

ALLOW e.g. 1 peak propanone because H in one environment, for 1 mark (2 marks)

(Total 18 marks)

18
4 (a) C=C add (aqueous) bromine (1)
red-brown / brown / orange / yellow.. to colourless (1)

OR add alkaline KMnO4 (1)

brown ppt. (1)

OH add PCl5 (1)

steamy/misty/white fumes (1)

OR other suitable test: reagent (1) observation (1)

e.g.
Conc H2SO4 and carboxylic acid (1)
(fruity) smell (when poured into water) (1)
OR
sodium (1)
Gas which ignites with squeaky pop (1) (4 marks)

(b) (i) H H H H H H H H
H C C C C C C C C H
H CH3 H H H OH H H
OR (CH3)2CH(CH2)3CH(OH)C2H5 (1 mark)

(b) (ii) mass linalool in lavender oil = 0.65x2 = 1.3 g (1)

no. moles linalool = 1.3/140 = 9.29x10-3 (1)
vol hydrogen = 9.29x10-3 x2x24000 = 450 / 446 cm3 /
0.446 dm3 (1) consequential on (i)
SF : answer ≥2 (3 marks)

(c) (i)
H OH OH H H H H H
H C C C C C C C C OH
H CH3 H H H OH OH H

OR (CH3)2C(OH)CHOH(CH2)2(CHOH)2CH2OH (2)
If OH only added to one C=C (1) (2 marks)

QWC (ii) Product forms more H bonds with water (1)

more / five not one OH groups (1) (2 marks)

(d)

for both arrows (1)

for a carbocation (1)
for arrow (1)
for correct product (1)

arrow can come from the – on Br, but do not need to show lone pair on Br (4 marks)

19
(e) optical isomerism (1)
correct 3D diagrams (1)
eg.

H H

H11C6
C C H
2 3 H3C2 C C H
6 11
OH HO

Must be drawn as mirror images

(2 marks)

Total 18 marks

TOTAL FOR PAPER: 50 MARKS

20
21
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