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1.

(a) The emf of a half-cell measured relative to the standard hydrogen electrode (1)
all solutions at 1 mol dm3 concentration and gases at 1 atm pressure / 101 kPa
and at a stated temperature / 298K (1) Standalone mark
ALLOW pressure of 100 kPa 2

(b) 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

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


OR
2Fe(s) + O2(g) + 2H2O(l) 2Fe(OH)2 (s)
Species (1)
balancing (1)
Do not allow species mark if electrons still in equation, but allow
balancing mark if 4e on both sides 2


(ii) E react = (+) 0.84 (V) (1)
Greater than zero therefore feasible (1) 2

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

E Zn2+ / Zn more negative than for Fe
OR

E Zn / Zn2+ more positive than for Fe
OR
Ecell for Zn being oxidised by O2 is more positive than for Fe
being oxidised by O2
OR

similar E arguments related to preferential oxidation with Sn (1) 3
disallow higher or bigger for more negative or more positive
[10]

2. (a) 3OCl 2Cl + ClO3 (1)

chlorine (in OCl) 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

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

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(ii) no. moles S 2 O 32 used = 12.5 0. 1 / 1000 = 1. 25 103 (1)

no. moles I2 = 1.25 103 / 2 = 6.25 104 (1)


no. moles ClO = no. moles 12 (1)
no. moles ClO in original 10 cm3 = 10 6.25 104
= 6.25 103 (1)
no. moles ClO in 1 dm3 = 100 6.25 103 (1) = 0.625 5

(iii) mass Cl2 = 0.625 71


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

(c) Cl2 is the stronger oxidising agent because Cl2 oxidises S from
(+)2 to (+)6 (1)
but l2 oxidises S from (+)2 to (+)2.50 (1) 2

QWC (d) O2 oxidises KI / iodide to l2. or balanced equation (1)


ll2 reacts with starch / paper to give blue / black (1) 2
[14]

3. (a) C10H8
ALLOW (C5H4)2
NOT (C6H4)2 1

(b) (i) 600


NOT + 600
NOT 600 1

(ii) Naphthalene is more/very stable than double bonds suggest (1)


Must be a comparison for the 1st mark
Therefore the electrons/bonds may be/are delocalised
(over the ring system)
OR it is a delocalised system (1)
No TE from (i)
Delocalised mark can be given if delocalisation mentioned in (iii) 2

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(iii) No
because it is likely to react like benzene / delocalised structure /
no double bonds
OR bromine not a strong enough electrophile without a catalyst
OR yes but only if bromine [NOT bromine solution] and a catalyst 1

(c) (i) Reagent


2-chloropropane (1)
ALLOW 1-chloropropane OR other halogenopropanes
NOT chloropropane
NOT bromo-2-propane
ALLOW formula with or without non-systematic name
ALLOW ClCH(CH3)2 OR (CH3)2CHCl OR C(CH3)2HCl OR ClC(CH3)2H
Catalyst
aluminium chloride / AlCl3/Al2Cl6
OR aluminium bromide / AlBr3
OR iron(III) chloride/FeCl3 (1)
NOT AlCl4()
NOT iron on its own
If both correct but wrong way round 1 (out of 2) 2

(ii) electrophilic (1)


substitution (1)
Can be given in any order
Mark independently 2
[9]

4. (a) (i) EITHER


E = (+) 0.15 (V) OR E (MnO4/ Mn2+) more positive or
greater than E
(Cl2 / Cl); accept reverse argument (1)
(so) MnO4 reacts with Cl OR Cl ions form Cl2
OR KMnO4 reacts with HCl (1)
OR
2MnO4 + 16H+ + 10Cl 2Mn2+ + 8H2O + 5Cl2 (1)
E = (+) 0.15(V) (1) 2

(ii) stated colour change of colourless to (pale) pink NOT purple OR


stays (pale) pink
OR pink to colourless
OR first excess of (coloured) manganate((VII))
IGNORE self-indicating
IGNORE references to Mn2+ 1

St Michael's Catholic Grammar School 3


(b) (i) (Multiply iron half-equation by five to) cancel out electrons
OR balance electrons 1

0.0200 20.10
(ii) Moles MnO4 =
1000
= 0.000402 mol MnO4 (1)

Moles Fe2+ per 25.0 cm3 = 5 0.000402


= 0.00201 mol Fe2+ (1)
200
Moles Fe2+ per 200 cm3 = 0.00201 mol Fe2+
25
= 0.01608 mol Fe2+ (1)
Mass of FeSO4 . 7H2O = 0.01608 278
= 4.47g or via concentrations (1)
4.47
Percentage purity = 100%
6.00
= 74.5% (1) ALLOW 74.7% / 75%
Correct answer + working (5)
ALLOW 2 or more sig figs
6.00
If start by dividing , and final answer is incorrect, candidate can
278
access first three marks only.
If third step omitted, answer 9.3% OR 9.33% OR 9.4% 5

(c) (i) E = + 1.46 ( 0.13) = ( + ) 1.59 (V)


Correct answer alone (1) 1

PbSO 4 precipitated (1)



[H + ( aq) ] not 1 mol dm 3 (1)
(ii) 2+ 3
any of these
[Pb ( aq) ] not 1 mol dm (1)
the conditions (in the car battery) are not standard (1)

temperature non-standard alone or not 1 atm pressure


alone does not score 1
[11]

5. (a) (i) Add silver nitrate (solution) (1) ACCEPT correct formula
(pale) yellow precipitate/solid(1)
OR
Add chlorine (solution)/bromine (solution) and hydrocarbon solvent (1)
Solvent goes purple/pink/violet (1)
2nd mark is dependent on 1st 2

(ii) Iodine /I and sulphur / S identified (1) -NOT I2 /I/iodide


Iodine

St Michael's Catholic Grammar School 4


initial (+)5 final 1 (1)
Sulphur
initial (+)4 final (+)6 (1)
ACCEPT as roman numerals
ACCEPT +/ on either side/sub or superscript
ACCEPT as words 3

(iii) 1 6 = 6, 3 +2 = +6 ALLOW TE from (ii)


OR total change in oxidation number of +6 for S, 6 for I
ACCEPT justification in terms of electrons 1

(b) (i) pipette


ALLOW burette
NOT measuring cylinder 1

(ii) Starch (solution) (1)


blue/dark blue/blue-black/black to colourless (1)
ALLOW max 1 if candidate states no indicator needed/self-indicating
with colour change brown/yellow to colourless
If no indicator given but correct colour change 1 (out of 2) 2

24.0
(iii) 2.4(0) 10 4 OR 0.00024 (mol)
1000
The mark is for the answer 1

2.40 10 4
(iv) = 1.2(0) 104 (mol) OR 0.00012 (mol)
2
ALLOW TE from (iii)
The mark is for the answer 1

(v) 1.2 104 100 = 0.012(0) (mol dm3)


ALLOW TE from (iv)
The mark is for the answer 1
[12]

St Michael's Catholic Grammar School 5


6. (i) (Buchner) flask / boiling tube connected to pump, glass tube
through stopper into solution
eg
pump
pump

or

ACCEPT
Air
pump

But must be a test tube and tube to bottom as shown 1

(ii) 8H+ 4H2O


ACCEPT multiples 1

(iii) Number of moles of manganate(VII) ion


20 0.020
= = 0.0004 (0) (1)
1000
Number of moles of electrons
= 5 0.00040 = 0.002(0) (1)
Number of moles of vanadium ions
10 0.10
= = 0.001 (1)
1000
(as vanadium(V) is formed by loss of 2 moles of electrons)
Oxidation number of vanadium in aerated solution is +3 (1) 4

(iv) It is a powerful oxidising agent, E = +1.51 V


OR
It is self-indicating 1
[7]

St Michael's Catholic Grammar School 6


7. (a) (i) uses E values to find Ereaction = (+) 1.57 (V) (1)
Reject 1.57
Zn + 2NO3 + 4H+ Zn2+ + 2NO2 + 2H2O (1) 2
Accept equation with equilibrium sign
Rejection equation with Zn on the right

(ii) Ereaction for the production of hydrogen is (+) 0.76 (V) (1)
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 than E H+/ H2 (1)

is a stronger oxidising agent than H+ (1) 2

(iii) hexaaquacopper(II) (1)


OH 2 2+
H2 O Cu OH 2
H2 O OH 2
OH 2

OR
OH 2
H2 O OH 2
H2 O OH 2
OH 2 (1)
Both marks stand alone
[IGNORE charge] 2
[IGNORE how H2O ligand is bonded to central cation]
Accept hexaquacopper(II)
Reject formula

(iv) ligand exchange/replacement/substitution (1)


[Cu(H2O)6]2+ + 4Cl CuCl42 + 6H2O (1)
OR
[Cu(H2O)6]2+ + 4HCl CuCl42 + 4H+ + 6H2O (1) 2
ALLOW
Accept H2CuCl4 + 2H+ for CuCl42 + 4H+

St Michael's Catholic Grammar School 7


(b) (i) E for the reaction is 0.39 (V) (so not feasible) [value is required]. 1
Accept Cu2+ being the oxidised form of the redox couple with
the more negative E, will not oxidise I

(ii) CuI is a solid (so conditions are not standard) (1)


Equilibrium is pulled over/moves to favour the r.h.s. (1) 2
Reject just conditions not standard

(iii) [Cu(NH3)4]+

OR [Cu(NH3)4(H2O)2]+ 1

Accept [Cu(NH3)2]+

Reject [Cu(NH3)6]+
Reject any 2+ complex

(iv) (atmospheric) oxygen (1)


oxidises Cu+ to Cu2+ (1) 2
Reject air for oxygen

(c) (i) starch (1)


blue-black/blue/black to colourless (1) 2
Reject clear for colourless

(ii) (If added too early) insoluble complex/black solid formed, 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. 1

St Michael's Catholic Grammar School 8


(iii) Amount thiosulphate = 0.01655 dm3 0.1 mol dm3 (1)
= amount Cu2+ in 25.0 cm3 = 1.655 103 mol (1)
amount of Cu2+ in 250 cm3 = 1.655 103 10 (1)
mass of Cu (in sample) = 1.655 102 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 5
[22]

8. (a) 3d104s1 and 3d10 1


Accept 4s13d10

(b) (i) QWC*


the (3)d subshell is full (1)
Accept orbitals (it must be plural) for sub-shell
Reject comments on partially filled sub-shell
so no d-d transitions are possible
OR no transitions in the right energy range are possible (1)
(and no light is absorbed)
Any mention of light emission loses 2nd mark 2

(ii) combine the halfreactions to get 2Cu+ Cu2+ + Cu (1)


IGNORE state symbols
and show that E for this is (+) 0.37 (V) (and as it is positive it is
feasible) (1)
conditional on correct reaction 2
Reject just > 0.3 (V)

(iii) activation energy (for the disproportionation) is high


OR
Cu+ is kinetically stable 1
Reject activation energy for one of the half-equations is too
high

St Michael's Catholic Grammar School 9


(c) (i) divides each by atomic mass (1)
divides by smallest to obtain Cu2SO6H2 (1) 2
Division by atomic number scores zero

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


If formula wrong but sulphate/ SO4 is present scores 1 (out of 2) 2
Accept Cu2SO4(OH)2
Accept Cu2(OH)2SO4
Accept (CuOH)2SO4
Reject HSO4 instead of SO4

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

Accept [Cu(NH3)4]2+

Reject [Cu(NH3)6]2+

(iv) ligand exchange / ligand substitution 1

(d) (i) QWC


(add aldehyde to 2,4DNP) to obtain precipitate/ppt/solid/crystals (1)
recrystallise derivative (1)
determine melting temperature of derivative (1)
compare with data tables (1) 4th mark conditional on melting
temperature of a derivative being measured 4
Reject any identification method based on IR, NMR or mass for
last 2 marks

(ii) the aldehyde is distilled off as it is formed 1


Reject any mention of reflux
Reject just the aldehyde is distilled off

(iii) propanoic acid OR CH3CH2COOH OR CH3CH2CO2H 1


Accept C2H5 for CH3CH2

St Michael's Catholic Grammar School 10


(iv) No (extra) oxygen present
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 1

(v) (At high pressure) all active sites are occupied/full


OR
(At higher pressures) rate controlled by availability of sites. 1
Accept reverse argument for low pressure
[20]

9. (a) (i) Cr: [Ar] 3d54s1


Cu: [Ar] 3d104s1
Both needed for the mark 1
Accept 4s13d5
Accept 4s13d10
Accept [Ar] written in full

(ii) all the others are 4s2 / have full 4s orbital (1)
Accept Cr and Cu/they do not have a full 4s orbital
Reject just only have one electron in 4s
OR
Have incomplete 4s orbital
The d subshell is more stable when either half or fully filled
OR
A specific example of chromium having half-filled or
copper having filled d sub-shell/set of d orbitals which
is more stable (1) 2
Accept sub-energy levels d shell
Reject half-filled or filled d orbital(s)

(b) (i) Octahedral drawn must be 3-D


IGNORE any or no charge 1
Accept H2O (bond to H) except on water molecules on left of
Cr

St Michael's Catholic Grammar School 11


(ii) Dative bond formed from electron pair/lone pair on oxygen
(of the water molecule) to the ion
This could be shown on a diagram 1
Accept a clear description of the dative bond
Reject dative alone or from water
Reject just dative bond formed from oxygen

(iii) [Cr(H2O)6]3+ + OH [Cr(H2O)5OH]2+ + H2O


OR
[Cr(H2O)6]3+ + 2OH [Cr(H2O)4(OH)2]+ + 2H2O
OR
[Cr(H2O)6]3+ + 3OH Cr(OH)3 + 6H2O
OR
[Cr(H2O)6]3+ + 3OH [Cr(H2O)3(OH)3] + 3H2O
First mark is for the correct Cr product
Second mark is conditional on the first and is for the rest
of the equation correct and balanced 2

(iv) Forms a green precipitate (1)


IGNORE initial colour of solution
(which reacts or dissolves or changes to)
a green solution (with excess reagent) (1)
Accept any shade of green
2nd mark is conditional on an initial ppt 2

(v) acid / acidic 1


Accept amphoteric/able to be deprotonated
Reject coloured ions/ligand exchange/ deprotonation /partially
filled d orbitals

St Michael's Catholic Grammar School 12


(c) (i) Check working correct answer can be obtained by not dividing
by 2 for 2nd mark and not multiplying by 2 for 4th mark
amount thiosulphate in titre = 0.0372 dm3 0.100 mol dm3
= 3.72 103 mol (1)
3.72 10 3
amount I2 = (1) = 1.86 103 mol
2
2nd mark cq on amount thiosulphate
amount dichromate in 25 cm3
1.86 10 3
= (1) = 6.2 104 mol
3
3rd mark cq on amount I2

Total mass Cr = 6.2 104 mol 2 10 52 g mol1 (1)


= 0.645 g
4th mark cq on amount dichromate
% of Cr = 64.5 % (1)
IGNORE SF unless rounded to 1 SF cq on mass Cr, provided less than 1 g
Accept 64.48 %

OR
amount thiosulphate for whole sample
= 0.0372 dm3 0.100 mol dm3 10
= 3.72 102 mol (1)
amount I2 = 1.86 102 mol (1)

amount dichromate = 6.2 103 mol (1)


mass Cr = 6.2 103 mol 2 52 g mol1 (1)
= 0.645 g
% of Cr = 64.5% (1)
IGNORE SF unless rounded to 1sf Mark consequentially, as above
Note:
Correct answer with no working (3) 5

(ii) Colour at the end point would be green which


would prevent the loss of iodine colour being seen
OR
colour change at end point would be disguised by the colour of Cr3+ 1
Accept chromium instead of Cr3+
Reject end point disguised by colour of Cr2O72/orange
[16]

St Michael's Catholic Grammar School 13


10. (a) MnO4 needs acid to be reduced to Mn2+ 1

(b) 5 1

(c) (i) 1.79 104 1

(ii) 1.79 104 mols of Fe2+ in one tablet


1
mols of MnO4 = 1.79 104 (1)
5
0.01 mol in 1000 cm3
1 1000 1.79 10 4
1.79 104 in
5 0.01 5
= 3.58
= 3.6 cm3 (1) 2

(iii) No, titration value too low


Either: use more tablets
Or: use more dilute solution of KMnO4 1

(d) QWC
(It is acceptable because) well below the maximum safe limit (1)
Not significantly different from recommended daily dose
OR Variation in body mass means that different doses are acceptable
OR only if max 1 tablet per day is written on the bottle (1) 2
[8]

St Michael's Catholic Grammar School 14


1. (a) (i) The potential difference between a standard hydrogen electrode
and the (half-) cell (1)
all concentrations measured at 1 mol dm3 and any gases are at 1 atm pressure (1)
2
(ii) Fluorine or F2 (1) 1

(b) (i) all/listed (1) 1


(ii) iodine and bromine (1) 1
(iii) This answer is consequential on part (ii)
Mix solution of Cr(II) - blue with the oxidising agent given in (ii) (1)
goes green and stays green / but does not go orange (1) 2
[7]

2. (a) (i) [Ar]3d6 (1) 1


allow 1s2 etc

(b) (i) Zn / Iron (1) not the zinc ion or iron ion
more negative potential than -0.28V (1)
NB this mark must show evidence of use of the data
gives +E for reduction reaction (1)
consequential on second mark 3

(ii) rate too slow / activation energy too high / kinetically stable /
allow oxide layer if metal electrode specified (1)
non-standard conditions (1) 2

(c) (i) Co(H2O)62+ (1) 1


(ii) Example:
Co(H2O)62+ + 4Cl CoCl42 + 6 H2O
Any valid equation that shows a ligand exchange but begins with
Co(H2O)62+ (1)
ligand exchange correctly balanced (1) 2
[9]

3. (a) (i) Use E values for reduction of Fe3+ to Fe2+ by Zn (E cell = + 1.53V) (1)
and Fe2+ to Fe by Zn (Ecell = +0.32V)(1)
They have positive E so are feasible (1) NOT will happen
OR
ALLOW Zn2+/Zn is more negative than both Fe3+/Fe2+ and Fe2+/Fe (1)
so zinc is a stronger reducing agent (1)
so zinc reducing both is feasible (1) 3

1
(ii) Reduction of Fe2+ has high activation energy / kinetically stable 1

(b) (i) Mn O4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O


Species (1)
Balance (1)
Any state symbols ignored. 2

(ii) purple colour of MnO4 lost (1)


end point when yellow / colourless solution (1)
becomes (permanently) pink (1) 3

(c) Amount MnO4 in 1st titration = 0.0182 dm3 0.0200 mol dm3
= 3.64 104 mol (1)
Amount Fe2+ in original solution = 5 above value = 1.82 103 mol (1)
Amount Fe2+ in 2nd titration = amount of Fe2+ and Fe3+ original solution (1)
= 0.0253 dm3 0.0200 mol dm3 5 = 2.53 103 mol
Amount of Fe3+ in original solution = 0.00253 0.00182 = 7.10 104 mol (1)
Amount zinc needed to reduce Fe3+ = 0.000710 = 0.000355 mol
Mass of zinc = 0.000355 mol 65.4 g mol1 = 0.0232 g (1) 2,3 or 4 SF
Consequential on their moles iron
The marks are for the following processes:
Either volume of MnO4 to moles of MnO4 (1)

Convert to moles of Fe2+ by multiplying either moles of MnO4 by 5 (1)

Realising that 2nd titration measures total number of moles of iron (1))
Subtracting to get original moles Fe3+ (1)
Going to moles Zn then mass Zn (1)

OR
Volume MnO4 for Fe3+, which has been reduced by zinc (1) 3rd point

= 25.3 cm3 18.2 cm3 = 0.0253 dm3 0.0182 dm3 = 0.0071 dm3 (1) 4th
point
Amount of MnO4 = 0.0071 dm3 0.0200 mol dm3 = 1.42 104 mol (1) 1st
point
Amount Fe3+ reduced by zinc = 5 above value = 7.10 104 mol (1) 2nd
point
Amount zinc needed = 7.10 104 = 3.55 104 mol
mass of zinc needed = 3.55 104 mol 65.4 g mol1 = 0.00232 g (1) 5th
point 5

(d) (i) [Fe(H2O)6]2+ + H2O [Fe(H2O)5OH]+ + H3O+

2
H3O+ in equation (1)
other ion in equation (1)
(Fe 2+) polarises the OH bond in ligand (1) 3

(ii) [Fe(H2O)6]3+ more acidic than [Fe(H2O)6]2+ (1)


Fe3+ higher charge density than Fe2+ (1)
Fe3+ ion if more polarising (1) 3
[20]

4. (a) (i) The potential (difference) / e.m.f. (of a halfcell) relative to the
standard hydrogen electrode (1)
Concentrations (of all ions) 1 mol dm3 and
(any gases at) pressure 1 atm (1)
Ignore any references to temperature 2
(ii) One from:
Can only measure a potential difference
Or
So that comparisons can be made between any half cells 1

(b) (i) 5H2O2 + 2MnO4 + 6H+ 5O2 + 2Mn2+ + 8H2O (2)


(1) for species
(1) for balancing the correct species
E reaction = + 0.84 (V) (1)
or if just states 0.84, must mention that this is a positive value 3

(ii) Fizzing/bubbles (1)


(pink) colour lost / stays colourless (1)
(end point) solution remains pink / pale purple (1) 3
(iii) 2H2O2 2H2O + O2 (1)
O (in H2O2) oxidised from 1 to 0 (in O2) (1)
O (in H2O2) reduced from 1 to 2 (in H2O) (1) 3
[12]

3
5. (a) (i) Fe [Ar]
3d64s2
or 3d64s2
or 3d64s2
or 4s23d6 (1)
Fe2+ [Ar]
3d6
or 3d6
or 3d64s0 (1)
Letter d must be lower case
Any additional letters of numbers (0) 2

(ii) The mark is for the shape

ALLOW bond to H of H2O (except on left side if OH2 is given)


IGNORE charge unless incorrect 1

(iii) [Fe(H2O)6]2+ + 2OH [Fe(OH)2(H2O)4] + 2H2O


OR
[Fe(H2O)6]2+ + 2OH Fe(OH)2 + 6H2O
OR equations with 2NaOH as reactant and 2Na + as product
IGNORE state symbols 1

4
(iv) Green precipitate / solid foxy-red / red-brown / brown / orange
Both colours and precipitate / solid needed
NOT darkens 1

(v) N2 + 3H2 / 2NH3

OR equation with Cl2 1

(b) (i) Emf of cell / potential difference of cell containing Fe2+ and Fe (1)
and standard hydrogen electrode / half cell NOT SHE
OR hydrogen electrode and 1 mol dm3 H+ and 1 atm H2 (1)
1 mol dm3 Fe2+
IGNORE temperature 3

QWC*(ii) Emf of hydrogen electrode is zero stated or implied (e.g. if


calculate Ecell = +0.44(V)) (1)
Fe + 2H+ Fe2+ + H2 (1) equation stand alone
Potential for the reaction is positive so reaction is feasible (1)
OR
H+ and ()H2 has a more +ve electrode potential than Fe2+ and Fe (1)
H+ will oxidise Fe / H+ is an oxidising agent / Fe is a reducing
agent for H+ / other correct redox statement (1)
Fe + 2H+ Fe2+ + H2 (1) stand alone 3

(iii) High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions 1

(c) 2Fe3+ + 2I 2Fe2+ + I2 or words E0 = (+) 0.23V (1)


So I would reduce Fe3+ / Fe3+ would oxidise I / E0 positive so reaction
L R (1)
OR reverse argument (2)
OR
Fe3+ and Fe2+ has a more positive electrode potential than I2 and I (1)
I will reduce Fe3+ / Fe3+ will oxidise I (1) 2
[15]

5
6. (a) The emf of a half-cell measured relative to the standard hydrogen electrode (1)
all solutions at 1 mol dm3 concentration and gases at 1 atm pressure / 101 kPa
and at a stated temperature / 298K (1) Standalone mark
ALLOW pressure of 100 kPa 2

(b) 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

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


OR
2Fe(s) + O2(g) + 2H2O(l) 2Fe(OH)2 (s)
Species (1)
balancing (1)
Do not allow species mark if electrons still in equation, but allow
balancing mark if 4e on both sides 2


(ii) E react = (+) 0.84 (V) (1)
Greater than zero therefore feasible (1) 2

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

E Zn2+ / Zn more negative than for Fe
OR

E Zn / Zn2+ more positive than for Fe
OR
Ecell for Zn being oxidised by O2 is more positive than for Fe
being oxidised by O2
OR

similar E arguments related to preferential oxidation with Sn (1) 3
disallow higher or bigger for more negative or more positive
[10]

7. (a) (i) Forms ions which have partially filled d-orbitals


OR
Forms ions which have a partially filled d-subshell 1

(ii) Scandiurn / Sc and Zinc / Zn 1

6
(b) (i) Fe2+ [Ar] 3d6
Mn2+ [Ar] 3d5 (1) for both correct 1
(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

(c) Shape (1)


Bonding to correct atoms (1)
(4) (4)

CN CN
NC CN
NC CN
Fe Fe
OR
NC CN
NC CN
CN CN
2

(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(ll) / Mn2+ (1) NOT standalone mark 4

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

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


unchanged (at +5) 1
(iii) First green colour : VO2+ and VO2+ (1)

Second green colour : V3+ / [V(H2O)6 ]3+ (1)

Violet colour : V2+ / [V(H2O)6 ]2+, (1) 3


[16]

8. (a) 3OCl 2Cl + ClO3 (1)

chlorine (in OCl) 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

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

7
(ii) no. moles S 2 O 32 used = 12.5 0. 1 / 1000 = 1. 25 103 (1)

no. moles I2 = 1.25 103 / 2 = 6.25 104 (1)


no. moles ClO = no. moles 12 (1)
no. moles ClO in original 10 cm3 = 10 6.25 104
= 6.25 103 (1)
no. moles ClO in 1 dm3 = 100 6.25 103 (1) = 0.625 5

(iii) mass Cl2 = 0.625 71


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

(c) Cl2 is the stronger oxidising agent because Cl2 oxidises S from
(+)2 to (+)6 (1)
but l2 oxidises S from (+)2 to (+)2.50 (1) 2

QWC (d) O2 oxidises KI / iodide to l2. or balanced equation (1)


ll2 reacts with starch / paper to give blue / black (1) 2
[14]

9. (a) (i) EITHER


E = (+) 0.15 (V) OR E (MnO4/ Mn2+) more positive or
greater than E
(Cl2 / Cl); accept reverse argument (1)
(so) MnO4 reacts with Cl OR Cl ions form Cl2
OR KMnO4 reacts with HCl (1)
OR
2MnO4 + 16H+ + 10Cl 2Mn2+ + 8H2O + 5Cl2 (1)
E = (+) 0.15(V) (1) 2

(ii) stated colour change of colourless to (pale) pink NOT purple OR


stays (pale) pink
OR pink to colourless
OR first excess of (coloured) manganate((VII))
IGNORE self-indicating
IGNORE references to Mn2+ 1

8
(b) (i) (Multiply iron half-equation by five to) cancel out electrons
OR balance electrons 1

0.0200 20.10
(ii) Moles MnO4 =
1000
= 0.000402 mol MnO4 (1)

Moles Fe2+ per 25.0 cm3 = 5 0.000402


= 0.00201 mol Fe2+ (1)
200
Moles Fe2+ per 200 cm3 = 0.00201 mol Fe2+
25
= 0.01608 mol Fe2+ (1)
Mass of FeSO4 . 7H2O = 0.01608 278
= 4.47g or via concentrations (1)
4.47
Percentage purity = 100%
6.00
= 74.5% (1) ALLOW 74.7% / 75%
Correct answer + working (5)
ALLOW 2 or more sig figs
6.00
If start by dividing , and final answer is incorrect, candidate can
278
access first three marks only.
If third step omitted, answer 9.3% OR 9.33% OR 9.4% 5

(c) (i) E = + 1.46 ( 0.13) = ( + ) 1.59 (V)


Correct answer alone (1) 1

PbSO 4 precipitated (1)


+ 3
[H ( aq) ] not 1 mol dm (1)
(ii) 2+ 3
any of these
[Pb ( aq) ] not 1 mol dm (1)
the conditions (in the car battery) are not standard (1)

temperature non-standard alone or not 1 atm pressure


alone does not score 1
[11]

9
10. (a) (i) uses E values to find Ereaction = (+) 1.57 (V) (1)
Reject 1.57
Zn + 2NO3 + 4H+ Zn2+ + 2NO2 + 2H2O (1) 2
Accept equation with equilibrium sign
Rejection equation with Zn on the right

(ii) Ereaction for the production of hydrogen is (+) 0.76 (V) (1)
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 than E H+/ H2 (1)

is a stronger oxidising agent than H+ (1) 2

(iii) hexaaquacopper(II) (1)


OH 2 2+
H2 O Cu OH 2
H2 O OH 2
OH 2

OR
OH 2
H2 O OH 2
H2 O OH 2
OH 2 (1)
Both marks stand alone
[IGNORE charge] 2
[IGNORE how H2O ligand is bonded to central cation]
Accept hexaquacopper(II)
Reject formula

(iv) ligand exchange/replacement/substitution (1)


[Cu(H2O)6]2+ + 4Cl CuCl42 + 6H2O (1)
OR
[Cu(H2O)6]2+ + 4HCl CuCl42 + 4H+ + 6H2O (1) 2
ALLOW
Accept H2CuCl4 + 2H+ for CuCl42 + 4H+

10
(b) (i) E for the reaction is 0.39 (V) (so not feasible) [value is required]. 1
Accept Cu2+ being the oxidised form of the redox couple with
the more negative E, will not oxidise I

(ii) CuI is a solid (so conditions are not standard) (1)


Equilibrium is pulled over/moves to favour the r.h.s. (1) 2
Reject just conditions not standard

(iii) [Cu(NH3)4]+

OR [Cu(NH3)4(H2O)2]+ 1

Accept [Cu(NH3)2]+

Reject [Cu(NH3)6]+
Reject any 2+ complex

(iv) (atmospheric) oxygen (1)


oxidises Cu+ to Cu2+ (1) 2
Reject air for oxygen

(c) (i) starch (1)


blue-black/blue/black to colourless (1) 2
Reject clear for colourless

(ii) (If added too early) insoluble complex/black solid formed, 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. 1

11
(iii) Amount thiosulphate = 0.01655 dm3 0.1 mol dm3 (1)
= amount Cu2+ in 25.0 cm3 = 1.655 103 mol (1)
amount of Cu2+ in 250 cm3 = 1.655 103 10 (1)
mass of Cu (in sample) = 1.655 102 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 5
[22]

11. (a) e.m.f. of a half cell relative/compared to a (standard) hydrogen electrode


OR
voltage produced from a half cell joined to a hydrogen electrode (1)
Accept potential (difference) /voltage for emf
Accept emf of a cell with standard hydrogen as the left
electrode
Accept a description of the half cell e.g. a metal dipping into a
solution of its ions
Reject SHE
(solutions at) 1 mol dm3 concentration, (gases at) 1 atm/100 kPa/
105Pa/ 1 Bar pressure and stated temperature (1)
all 3 conditions needed STAND ALONE 2
Accept 101 kPa
Accept 298 K or 25 C
If any other temperature is quoted it must be as an example of a
stated temperature
Reject constant pressure STP
Reject room temperature
Reject just 273 K

(b) Can only measure a potential difference/emf


(if a reference electrode is present)
OR
voltmeter needs 2 connections
OR
Cannot measure the potential difference between a metal and a
solution of its ions 1
Reject just electron source and sink
Reject to make comparisons between half cells

12
(c) (i) 1st mark
(simultaneous) oxidation and reduction of a (single) species/
substance/ reactant/compound/chemical
Reject oxidation and reduction occur at the same time
Or the oxidation state/number is both increased and
decreased of a (single) species/ substance/ reactant/
compound/chemical
Reject oxidation states are
Or a (single) species/ substance/ reactant/compound/
chemical both loses and gains electrons (1)
2nd mark
For a given type of atom within an ion/ molecule
Or Illustrated by a suitable example in which the
individual atom is identified (1) 2

(ii) 2H2O2 2H2O + O2 (1)

Reject 2H+ on both sides of equation


Ecell = (+) 1.09 (V) (1)
Reject greater than any other stated number
Ecell is positive/greater than 0 so the reaction is feasible (1)
3rd mark must be cq on sign of Ecell 3

(iii) activation energy of the reaction may be high


OR
reaction too slow to be observed 1
Reject just Not enough energy to overcome the activation
energy
Reject conditions are non-standard
Reject just kinetically stable
[9]

12. (a) (i) The activation energy for the reaction is high
or to ensure that more molecules have E Ea. 1
Accept E > Ea
Reject to overcome Ea alone
Reject reactants kinetically stable;
reactants thermodynamically stable

13
(ii) protonates the alcohol (1)
Reject as a catalyst alone
providing H2O as the leaving group which is more easily displaced
by the bromide ion/is a better leaving group than hydroxide (1)
OR
reacts with NaBr (1)
to give HBr (which is the attacking reagent) (1) 2

(iii) H-bonding between water and the alcohol not strong


enough to overcome hydrophobic interactions /effect of
alkyl group (1)
acid and alcohol form ionic species/C4H9OH2+ which
is more soluble (1) 2
Accept butyl group

(iv) Removes acid 1


Accept neutralises HCl /HBr
Accept neutralises acid

(v) Removes water 1


Accept absorbs water
Accept dries the product

(vi) Electric heating mantle or sand bath or oil bath (1)


Accept water bath
Reject heat under reflux
Reject no naked flame
Reject fume cupboard
because the alcohol/reaction mixture/bromobutane is
flammable or because the heating is uniform and less
likely to crack the flask (1)
This mark is conditional on the first being scored. 2
Reject volatile for flammable

14
(b) QWC
EITHER
Intermediate (ion) in SN1 is planar (1)
Accept intermediate carbocation is a planar molecule
intermediate molecule alone loses this mark
equal attack (by hydroxide ions) from either side (1)
produces a racemic mixture (1)
Reject attack by bromide ions
Note: Statement that the SN2 mechanism is consistent with
the information cannot score any marks.
OR
SN2 involves attack from one side (1)
so configuration of the product would be inverted (1)
leading to retention of optical activity so must be SN1 (1)
Accept forms one optical isomer only
Statement that the reaction is SN1 alone scores zero. 3

(c) (i) Orange green 1

(ii) Cr2O72 + 6e + 14H+ 2Cr3+ + 7H2O (1)

(3CH3CH(OH)CH2CH3 3CH3COCH2CH3 + 6H+ + 6e)


Cr2O72 + 3CH3CH(OH)CH2CH3 + 8H+ 2Cr3+ + 7H2O +
3CH3COCH2CH3 (1)
No consequential marking on incorrect equations. 2
Accept C4H9OH and C4H8O

Accept equation having non-cancelled H+ ions


Reject equation having non-cancelled electrons

(iii) The broad peak/absorption/trough around 3400 cm1 due to OH (1)


Accept 3230 3550
Reject broad transmission
has disappeared in the product to be replaced by C=O at 1700 cm1 (1)
Accept 1680 1750
If no reference to both groups responsible for the peaks then max (1)
OR
If no reference to both wavenumbers responsible for the
peaks then max (1) 2

15
(d) (i) Addition of barium ions pulls equilibrium to r.h.s. (1)
increases [H+] and so lower pH/the pH falls (1) stand-alone mark 2
Reject ..so gets more acidic

(ii) lower pH/pH falls 1


Reject mixture is more acidic for lower pH
[20]

13. A
[1]

14. A
[1]

15. C
[1]

16. D
[1]

17. (a) B 1

(b) C 1
[2]

18. (a) (i) Fe[Ar] 3d64s2 in either order, allowing superscripts to be subscripts
Fe[Ar] 3d6 or 3d64s0 in either order, allowing
superscripts to be subscripts
Letter d must be lower case 1
Reject any other letters

16
(ii)
OH 2
H2O OH 2
2+
Fe
H2O OH 2
OH 2

OH 2 OH 2

OR H2O Fe 2+ OH 2

H2O
OH 2

OR
H2O
H2O OH 2

Fe 2+

H2O OH 2
H2O

Instead of dotted line


ALLOW bond to H of H2O (accept on left side if OH2 is given)
IGNORE charge unless incorrect 1

(iii) [Fe(H2O)6]2+ + 2OH [Fe(OH)2(H2O)4] + 2H2O


OR
[Fe(H2O)6]2+ + 2OH Fe(OH)2 + 6H2O 1

(iv) Green precipitate/solid Foxy-red/red-brown/


brown/orange
Both colours and precipitate/solid needed 1
Reject just Darkens

(b) (i) QWC


Emf of cell/ potential difference of cell containing Fe (1)
dipping into a 1 mol dm3 Fe2+ solution (1)
And standard hydrogen electrode/half cell
OR hydrogen electrode and 1 mol dm3 H+ and 1 atm
H2
OR description of standard hydrogen electrode (1)
IGNORE temperature 3
RejectSHE

17
(ii) QWC
Emf of hydrogen electrode is zero stated or implied
e.g. if calculate Ecell = +0.44 V (1)
Potential for the reaction is positive so reaction is feasible
OR Fe half cell has more negative electrode potential
OR H+ and ()H2 has a more positive electrode potential (1) 2

(iii) High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions 1
[10]

18
1. (a) 1s2 2s2 2p6 3s2 3p6 3d6 4s2/4s2 3d6 OR 3d8 (4s0) (1)
Incomplete d shell (in the ion) (1) 2

(b) (i) Ni(CO)4 1


(ii) 0 1

(c) (i) Ni(H2O)62+ (aq) + NH3(aq) Ni(H2O)5(NH3)2+ (aq) + H2O(I) 1


QWC* (ii) S is likely to be small / close to zero (1) No TE
Same number of moles/molecules/particles in the same states
on both sides of the equation (1) 2

(d) (i) Ag+(aq) + Cl(aq) Ag(+)Cl()(s) 1


(ii) 1 mole of AgCl has a mass of 143.5/(108+35.5) (1)
OR 143.3 from Data Book (or 143.4)
Number of moles of AgCl = 6.133/143.5 = 0.0427(4) 0.04280 (1)
Number of moles of complex = 0.04274/2 = 0.02137
Therefore mass of 1 mole = 5.000/0.02137 = 234/234.4 (1)
3SF sufficient but not 2SF 3

(iii) 59 + 18 x + 17 (6 x) +71 = 234


232 + x = 234
x=2 1
([Ni(H2O)2(NH3)4]Cl2) Formula NOT needed for mark
(iv) The two water molecules could be at 180 or 90 to one another

Octahedral structure (1)


ALLOW the word octahedral to explain diagram's shape 2
[14]

2. (a) (i) 1s22s22p63s23p64s13d5


OR
1s22s22p63s23p63d54s1 1
QWC*(ii) V and Mn have two 4s electrons / filled 4s (orbital) Cr has one (1)
due to stability of half-filled shell/4s and 3d levels have similar
energies (1) 2

1
QWC*(b) Cr3+(aq), Cr2+(aq)(IPt) 0.41(V) (1)
[O2(g) + 2H2O(l)], 4OH(aq)(IPt) +0.4(0) (V) (1)
ALLOW a state symbol omission in each.
ALLOW half equations
Can be given in a cell diagram
by application of the anti-clockwise rule oxygen will oxidise Cr2+
OR
E0 cell = (+) 0.81(V) and this is greater than (+) 0.6 (V)
OR
Cr2+ has more negative electrode potential so will reduce oxygen /
oxygen more positive etc. (1) 3

QWC*(c) (i) Water acts as a ligand by a non-bonding pair (of electrons on


the oxygen atom) (1)
Making a dative (covalent)/co-ordinate bond (to the chromium ion) (1) 2
(ii) Bidentate/chelate/bridging 1

QWC*(iii) Two peaks in the NMR spectrum (1)


Due to two different environments of hydrogen atoms /
H in H2O and H in CH3 (1)
Mark independently 2

QWC*(iv) Any two:


C-H just below 3000 / 2962-2853 / 1485-1365
O-H 3200-3800
C=O 1700-1750
C-O 1230 - 1250
ALLOW values or ranges within these ranges
If more than two given, 1 for each incorrect 2

(d) (i) 3C2H6O to 3C2H4O provided 1 Na2Cr2O7 (1)


4H2SO4 and 7H2O (1)
ACCEPT multiples 2
(ii) Orange to green
ALLOW qualified green e.g. blue-green
NOT green to orange 1
(iii) (Sodium dichromate(VI)) is a carcinogen / toxic / irritant
In any combination
Lose mark for anything else with these. 1
[17]
Mark Scheme

2
3. (a) (i) Add silver nitrate (solution) (1) ACCEPT correct formula
(pale) yellow precipitate/solid(1)
OR
Add chlorine (solution)/bromine (solution) and hydrocarbon solvent (1)
Solvent goes purple/pink/violet (1)
2nd mark is dependent on 1st 2

(ii) Iodine /I and sulphur / S identified (1) -NOT I2 /I/iodide


Iodine
initial (+)5 final 1 (1)
Sulphur
initial (+)4 final (+)6 (1)
ACCEPT as roman numerals
ACCEPT +/ on either side/sub or superscript
ACCEPT as words 3

(iii) 1 6 = 6, 3 +2 = +6 ALLOW TE from (ii)


OR total change in oxidation number of +6 for S, 6 for I
ACCEPT justification in terms of electrons 1

(b) (i) pipette


ALLOW burette
NOT measuring cylinder 1

(ii) Starch (solution) (1)


blue/dark blue/blue-black/black to colourless (1)
ALLOW max 1 if candidate states no indicator needed/self-indicating
with colour change brown/yellow to colourless
If no indicator given but correct colour change 1 (out of 2) 2

24.0
(iii) 2.4(0) 10 4 OR 0.00024 (mol)
1000
The mark is for the answer 1

2.40 10 4
(iv) = 1.2(0) 104 (mol) OR 0.00012 (mol)
2
ALLOW TE from (iii)
The mark is for the answer 1

3
(v) 1.2 104 100 = 0.012(0) (mol dm3)
ALLOW TE from (iv)
The mark is for the answer 1
[12]

4. (i) (Buchner) flask / boiling tube connected to pump, glass tube


through stopper into solution
eg
pump
pump

or

ACCEPT
Air
pump

But must be a test tube and tube to bottom as shown 1

(ii) 8H+ 4H2O


ACCEPT multiples 1

(iii) Number of moles of manganate(VII) ion


20 0.020
= = 0.0004 (0) (1)
1000
Number of moles of electrons
= 5 0.00040 = 0.002(0) (1)
Number of moles of vanadium ions
10 0.10
= = 0.001 (1)
1000
(as vanadium(V) is formed by loss of 2 moles of electrons)
Oxidation number of vanadium in aerated solution is +3 (1) 4

4
(iv) It is a powerful oxidising agent, E = +1.51 V
OR
It is self-indicating 1
[7]

5. (a) (i) uses E values to find Ereaction = (+) 1.57 (V) (1)
Reject 1.57
Zn + 2NO3 + 4H+ Zn2+ + 2NO2 + 2H2O (1) 2
Accept equation with equilibrium sign
Rejection equation with Zn on the right

(ii) Ereaction for the production of hydrogen is (+) 0.76 (V) (1)
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 than E H+/ H2 (1)

is a stronger oxidising agent than H+ (1) 2

(iii) hexaaquacopper(II) (1)


OH 2 2+
H2 O Cu OH 2
H2 O OH 2
OH 2

OR
OH 2
H2 O OH 2
H2 O OH 2
OH 2 (1)
Both marks stand alone
[IGNORE charge] 2
[IGNORE how H2O ligand is bonded to central cation]
Accept hexaquacopper(II)
Reject formula

5
(iv) ligand exchange/replacement/substitution (1)
[Cu(H2O)6]2+ + 4Cl CuCl42 + 6H2O (1)
OR
[Cu(H2O)6]2+ + 4HCl CuCl42 + 4H+ + 6H2O (1) 2
ALLOW
Accept H2CuCl4 + 2H+ for CuCl42 + 4H+

(b) (i) E for the reaction is 0.39 (V) (so not feasible) [value is required]. 1
Accept Cu2+ being the oxidised form of the redox couple with
the more negative E, will not oxidise I

(ii) CuI is a solid (so conditions are not standard) (1)


Equilibrium is pulled over/moves to favour the r.h.s. (1) 2
Reject just conditions not standard

(iii) [Cu(NH3)4]+

OR [Cu(NH3)4(H2O)2]+ 1

Accept [Cu(NH3)2]+

Reject [Cu(NH3)6]+
Reject any 2+ complex

(iv) (atmospheric) oxygen (1)


oxidises Cu+ to Cu2+ (1) 2
Reject air for oxygen

(c) (i) starch (1)


blue-black/blue/black to colourless (1) 2
Reject clear for colourless

(ii) (If added too early) insoluble complex/black solid formed, 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. 1

6
(iii) Amount thiosulphate = 0.01655 dm3 0.1 mol dm3 (1)
= amount Cu2+ in 25.0 cm3 = 1.655 103 mol (1)
amount of Cu2+ in 250 cm3 = 1.655 103 10 (1)
mass of Cu (in sample) = 1.655 102 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 5
[22]

6. (a) 3d104s1 and 3d10 1


Accept 4s13d10

(b) (i) QWC*


the (3)d subshell is full (1)
Accept orbitals (it must be plural) for sub-shell
Reject comments on partially filled sub-shell
so no d-d transitions are possible
OR no transitions in the right energy range are possible (1)
(and no light is absorbed)
Any mention of light emission loses 2nd mark 2

(ii) combine the halfreactions to get 2Cu+ Cu2+ + Cu (1)


IGNORE state symbols
and show that E for this is (+) 0.37 (V) (and as it is positive it is
feasible) (1)
conditional on correct reaction 2
Reject just > 0.3 (V)

(iii) activation energy (for the disproportionation) is high


OR
Cu+ is kinetically stable 1
Reject activation energy for one of the half-equations is too
high

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


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

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

7
If formula wrong but sulphate/ SO4 is present scores 1 (out of 2) 2
Accept Cu2SO4(OH)2
Accept Cu2(OH)2SO4
Accept (CuOH)2SO4
Reject HSO4 instead of SO4

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

Accept [Cu(NH3)4]2+

Reject [Cu(NH3)6]2+

(iv) ligand exchange / ligand substitution 1

(d) (i) QWC


(add aldehyde to 2,4DNP) to obtain precipitate/ppt/solid/crystals (1)
recrystallise derivative (1)
determine melting temperature of derivative (1)
compare with data tables (1) 4th mark conditional on melting
temperature of a derivative being measured 4
Reject any identification method based on IR, NMR or mass for
last 2 marks

(ii) the aldehyde is distilled off as it is formed 1


Reject any mention of reflux
Reject just the aldehyde is distilled off

(iii) propanoic acid OR CH3CH2COOH OR CH3CH2CO2H 1


Accept C2H5 for CH3CH2

(iv) No (extra) oxygen present


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 1

8
(v) (At high pressure) all active sites are occupied/full
OR
(At higher pressures) rate controlled by availability of sites. 1
Accept reverse argument for low pressure
[20]

7. (a) (i) Cr: [Ar] 3d54s1


Cu: [Ar] 3d104s1
Both needed for the mark 1
Accept 4s13d5
Accept 4s13d10
Accept [Ar] written in full

(ii) all the others are 4s2 / have full 4s orbital (1)
Accept Cr and Cu/they do not have a full 4s orbital
Reject just only have one electron in 4s
OR
Have incomplete 4s orbital
The d subshell is more stable when either half or fully filled
OR
A specific example of chromium having half-filled or
copper having filled d sub-shell/set of d orbitals which
is more stable (1) 2
Accept sub-energy levels d shell
Reject half-filled or filled d orbital(s)

(b) (i) Octahedral drawn must be 3-D


IGNORE any or no charge 1
Accept H2O (bond to H) except on water molecules on left of
Cr

(ii) Dative bond formed from electron pair/lone pair on oxygen


(of the water molecule) to the ion
This could be shown on a diagram 1
Accept a clear description of the dative bond
Reject dative alone or from water
Reject just dative bond formed from oxygen

9
(iii) [Cr(H2O)6]3+ + OH [Cr(H2O)5OH]2+ + H2O
OR
[Cr(H2O)6]3+ + 2OH [Cr(H2O)4(OH)2]+ + 2H2O
OR
[Cr(H2O)6]3+ + 3OH Cr(OH)3 + 6H2O
OR
[Cr(H2O)6]3+ + 3OH [Cr(H2O)3(OH)3] + 3H2O
First mark is for the correct Cr product
Second mark is conditional on the first and is for the rest
of the equation correct and balanced 2

(iv) Forms a green precipitate (1)


IGNORE initial colour of solution
(which reacts or dissolves or changes to)
a green solution (with excess reagent) (1)
Accept any shade of green
2nd mark is conditional on an initial ppt 2

(v) acid / acidic 1


Accept amphoteric/able to be deprotonated
Reject coloured ions/ligand exchange/ deprotonation /partially
filled d orbitals

(c) (i) Check working correct answer can be obtained by not dividing
by 2 for 2nd mark and not multiplying by 2 for 4th mark
amount thiosulphate in titre = 0.0372 dm3 0.100 mol dm3
= 3.72 103 mol (1)
3.72 10 3
amount I2 = (1) = 1.86 103 mol
2
2nd mark cq on amount thiosulphate
amount dichromate in 25 cm3
1.86 10 3
= (1) = 6.2 104 mol
3
3rd mark cq on amount I2

Total mass Cr = 6.2 104 mol 2 10 52 g mol1 (1)


= 0.645 g
4th mark cq on amount dichromate
% of Cr = 64.5 % (1)
IGNORE SF unless rounded to 1 SF cq on mass Cr, provided less than 1 g
Accept 64.48 %

10
OR
amount thiosulphate for whole sample
= 0.0372 dm3 0.100 mol dm3 10
= 3.72 102 mol (1)
amount I2 = 1.86 102 mol (1)

amount dichromate = 6.2 103 mol (1)


mass Cr = 6.2 103 mol 2 52 g mol1 (1)
= 0.645 g
% of Cr = 64.5% (1)
IGNORE SF unless rounded to 1sf Mark consequentially, as above
Note:
Correct answer with no working (3) 5

(ii) Colour at the end point would be green which


would prevent the loss of iodine colour being seen
OR
colour change at end point would be disguised by the colour of Cr3+ 1
Accept chromium instead of Cr3+
Reject end point disguised by colour of Cr2O72/orange
[16]

8. (a) B 1

(b) C 1
[2]

9. C
[1]

10. D
[1]

11. D
[1]

11
12. (a) (i) Fe[Ar] 3d64s2 in either order, allowing superscripts to be subscripts
Fe[Ar] 3d6 or 3d64s0 in either order, allowing
superscripts to be subscripts
Letter d must be lower case 1
Reject any other letters

(ii)
OH 2
H2O OH 2
2+
Fe
H2O OH 2
OH 2

OH 2 OH 2

OR H2O Fe 2+ OH 2

H2O
OH 2

OR
H2O
H2O OH 2

Fe 2+

H2O OH 2
H2O

Instead of dotted line


ALLOW bond to H of H2O (accept on left side if OH2 is given)
IGNORE charge unless incorrect 1

(iii) [Fe(H2O)6]2+ + 2OH [Fe(OH)2(H2O)4] + 2H2O


OR
[Fe(H2O)6]2+ + 2OH Fe(OH)2 + 6H2O 1

(iv) Green precipitate/solid Foxy-red/red-brown/


brown/orange
Both colours and precipitate/solid needed 1
Reject just Darkens

12
(b) (i) QWC
Emf of cell/ potential difference of cell containing Fe (1)
dipping into a 1 mol dm3 Fe2+ solution (1)
And standard hydrogen electrode/half cell
OR hydrogen electrode and 1 mol dm3 H+ and 1 atm
H2
OR description of standard hydrogen electrode (1)
IGNORE temperature 3
RejectSHE

(ii) QWC
Emf of hydrogen electrode is zero stated or implied
e.g. if calculate Ecell = +0.44 V (1)
Potential for the reaction is positive so reaction is feasible
OR Fe half cell has more negative electrode potential
OR H+ and ()H2 has a more positive electrode potential (1) 2

(iii) High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions 1
[10]

13
3d 4s
1. (a) 2
Mn [Ar]
2+
Mn [Ar]

(b) (i) [Mn(H2O)6]2+ 1

(ii) [Mn(H2O)6]2+ + 2NH3 Mn(OH)2 + 2NH4+ + 4H2O


or
[Mn(H2O)6]2+ + 2NH3 [Mn(H2O)4(OH)2] + 2NH4+
or
[Mn(H2O)6]2+ + 2OH Mn(OH)2 + 6H2O
or
[Mn(H2O)6]2+ + 2OH [Mn(OH)2(H2O)4] + 2 H2O
Any of above score 2 marks as follows:(1) mark for species (1) mark for balance
Deprotonation or Acid /base (1) 3

(iii) (Mn(II) is ) oxidised / undergoes oxidation (1)


to Mn(IV) / Mn(III) / to higher oxidation state/ will increase (1)
Variable oxidation states (1)
coloured compounds (1) 4
(c) (i) from +4 to +6/ up by 2 / +2 1
(ii) Amount of KMnO4 = 0.0228 0.0216 mol 1

= 4.925 104mol

(iii) Amount of SO32 in 25cm3 = 5/2 4.925 104mol 1

= 1.231 x 103 mol


(iv) Amount of SO32 in 250cm3 = 10 1.231 103 mol (1)
= 1.231 102 mol
Mass of pure Na2SO3 = 126 x 1.231 102 g (1)
= 1.551g 2
(v) Purity of sample = (1.551g/ 1.75g) x 100%
= 88.6% 1
[16]

1
2. (a) (i) The potential difference between a standard hydrogen electrode
and the (half-) cell (1)
all concentrations measured at 1 mol dm3 and any gases are at 1 atm pressure (1)
2
(ii) Fluorine or F2 (1) 1

(b) (i) all/listed (1) 1


(ii) iodine and bromine (1) 1
(iii) This answer is consequential on part (ii)
Mix solution of Cr(II) - blue with the oxidising agent given in (ii) (1)
goes green and stays green / but does not go orange (1) 2
[7]

3. (a) Sc [Ar]
Cr [Ar]
Cr 3+ [Ar]

Cr3+ consequential on structure for Cr 3

(b) Electronic configuration differs from previous element by an


electron in a d (sub) shell / electrons are filling the d-shell (1)
transition elements have one ion with partially-filled d-shell (1) 2
Not highest energy shell is the d-shell
outer electron in d shell

(c) (i) [Ar]

Ligand electrons
2
Correct electron structure for complex ion (1)
ligand electrons identified (1) 6 pairs identified stand alone mark
Consequential on structure of Cr3+

2
3+
(ii) OH2
H 2O OH 2
Cr
H 2O OH 2
OH2

There must be some attempt to show a 3-D structure


Octahedral could rescue a poor diagram

(iii) d-orbitals split (in energy by ligands) / or diagram to illustrate


electron transitions / jumps from lower to higher energy level (1)
absorbs light in visible region (1) 3

(d) (i) Green precipitate (1)


(deep) green solution in excess sodium hydroxide (1) 2

(ii) Deprotonation / acid base (1) 1


[14]

4. (a) (i) [Ar]3d6 (1) 1


allow 1s2 etc

(b) (i) Zn / Iron (1) not the zinc ion or iron ion
more negative potential than -0.28V (1)
NB this mark must show evidence of use of the data
gives +E for reduction reaction (1)
consequential on second mark 3

(ii) rate too slow / activation energy too high / kinetically stable /
allow oxide layer if metal electrode specified (1)
non-standard conditions (1) 2

(c) (i) Co(H2O)62+ (1) 1


(ii) Example:
Co(H2O)62+ + 4Cl CoCl42 + 6 H2O
Any valid equation that shows a ligand exchange but begins with
Co(H2O)62+ (1)
ligand exchange correctly balanced (1) 2
[9]

5. (a) An element that has at least one of its ions has an incomplete d shell (1) 1

3
(b) (i) Coloured ions / compounds/ complexes/ solutions (1)
variable oxidation states (1) 2

(ii) Cr(H2O)62+ / hexa aqua chromium (II) ion (1)


Not Cr2+ or Cr(II). 1

(c) (i) Cr Cl H2 O 2
19.5 / 52 40 / 35.5 40.5 / 18 (1)
0.375 1.127 2.25
0.375/0.375 1.127/0.375 2.25/0.375 (1)
1 3 6
NB 2 method marks

(ii) Violet Cr(H2O)63+.3Cl (1)


Green is [Cr(H2O)5Cl]2+2Cl.H2O (1) 2
NB for 2 marks must make clear which is which and must be a
salt which adds up to Cr(H2O)6Cl3
[8]

6. (a) (i) 1

(ii) 1

Allow single headed arrows or other suitable notation


[Mark (ii) consequentially on (i)]

(b) (i) Covalent (1)


Coordinate or dative (1) 2
(ii) Deprotonation or acid-base 1
(iii) [Cr(H2O)3(OH)3] or Cr(OH)3 1
(iv) Ligand exchange or ligand substitution 1
(v) [Cr(NH3)6]3+ or [Cr(OH)x (H2O)y(NH3)z]charge 1
x + y + z = 6, z at least one, correct charge will be between 0 and +3, x = max 3

4
(c) d orbitals/subshell/energy level split (in energy by
ligands)/diagram to illustrate (1)
Electron transitions/jumps from lower to higher energy level (1)
Absorbs light in visible region/reference to white light (1) 3
If imply or state that emission is occurring, only the first
marking point is available
[11]

7. (a) (i) 1s22s22p63s23p63d84s2 1


(ii) 1s22s22p63s23p6 3d8 1

(b)
OH2
H2 O OH 2
Ni
H2 O OH 2
OH2
(1)
Shape mark
Must be 3D ie wedges or dashes
labelled covalent between OH OR arrow to H2Oand labelled covalent
bond (1)
labelled dative covalent between O atom and ion (1) 3

(c) (i) [Ni(H2O)4(OH)2]


ALLOW Ni(OH)2 1

(ii) Deprotonation (1)


two successive deprotonations / neutral species producing insoluble
compound (1) 2

(iii) Ligand exchange (1)


giving (soluble) [Ni(H2O)0 or 2(NH3)6 or 4]2+ OR in words (1) 2
[10]

5
8. (a) (i) Use E values for reduction of Fe3+ to Fe2+ by Zn (E cell = + 1.53V) (1)
and Fe2+ to Fe by Zn (Ecell = +0.32V)(1)
They have positive E so are feasible (1) NOT will happen
OR
ALLOW Zn2+/Zn is more negative than both Fe3+/Fe2+ and Fe2+/Fe (1)
so zinc is a stronger reducing agent (1)
so zinc reducing both is feasible (1) 3

(ii) Reduction of Fe2+ has high activation energy / kinetically stable 1

(b) (i) Mn O4 + 5Fe2+ + 8H+ Mn2+ + 5Fe3+ + 4H2O


Species (1)
Balance (1)
Any state symbols ignored. 2

(ii) purple colour of MnO4 lost (1)


end point when yellow / colourless solution (1)
becomes (permanently) pink (1) 3

(c) Amount MnO4 in 1st titration = 0.0182 dm3 0.0200 mol dm3
= 3.64 104 mol (1)
Amount Fe2+ in original solution = 5 above value = 1.82 103 mol (1)
Amount Fe2+ in 2nd titration = amount of Fe2+ and Fe3+ original solution (1)
= 0.0253 dm3 0.0200 mol dm3 5 = 2.53 103 mol
Amount of Fe3+ in original solution = 0.00253 0.00182 = 7.10 104 mol (1)
Amount zinc needed to reduce Fe3+ = 0.000710 = 0.000355 mol
Mass of zinc = 0.000355 mol 65.4 g mol1 = 0.0232 g (1) 2,3 or 4 SF
Consequential on their moles iron
The marks are for the following processes:
Either volume of MnO4 to moles of MnO4 (1)

Convert to moles of Fe2+ by multiplying either moles of MnO4 by 5 (1)

Realising that 2nd titration measures total number of moles of iron (1))
Subtracting to get original moles Fe3+ (1)
Going to moles Zn then mass Zn (1)

6
OR
Volume MnO4 for Fe3+, which has been reduced by zinc (1) 3rd point

= 25.3 cm3 18.2 cm3 = 0.0253 dm3 0.0182 dm3 = 0.0071 dm3 (1) 4th
point
Amount of MnO4 = 0.0071 dm3 0.0200 mol dm3 = 1.42 104 mol (1) 1st
point
Amount Fe3+ reduced by zinc = 5 above value = 7.10 104 mol (1) 2nd
point
Amount zinc needed = 7.10 104 = 3.55 104 mol
mass of zinc needed = 3.55 104 mol 65.4 g mol1 = 0.00232 g (1) 5th
point 5

(d) (i) [Fe(H2O)6]2+ + H2O [Fe(H2O)5OH]+ + H3O+


H3O+ in equation (1)
other ion in equation (1)
(Fe 2+) polarises the OH bond in ligand (1) 3

(ii) [Fe(H2O)6]3+ more acidic than [Fe(H2O)6]2+ (1)


Fe3+ higher charge density than Fe2+ (1)
Fe3+ ion if more polarising (1) 3
[20]

9. (a) (i) 1s22s22p63s23p63d104s2 accept any order 1


(ii) 1s22s22p63s23p63d10 Conseq on (a) (i) 1
(b) d-block: last (added) electron is in a d(sub) shell / orbital (1)
Not transition: does not form ions with partially filled d-(sub) shell /
orbitals (1) 2
(c) 3D-drawing e.g. wedges / hatches or perspective diagram (1)
Labels covalent bond within water molecule (1). This must be drawn
out /use of a key is acceptable.
Shows dative covalent bond from water to central Zn2+ (1)
Labels a 90 angle (1)
Ignore absence of charge on ion 4

7
(d) (i) White precipitate /solid /suspension (1) NOT powder
Colourless solution (in excess ammonia) NOT clear (1) 2
(ii) [Zn(H2O)6] + 2NH3 [Zn(OH)2(H2O)4]+ 2NH4
2+ +

Or
[Zn(H2O)6]2+ + 2OH [Zn(OH)2(H2O)4]+ 2H2O
Or
[Zn(H2O)6]2+ + 2OH Zn(OH)2 + 6H2O
Or
[Zn(H2O)6]2+ + 2NH3 Zn(OH)2 + 2NH4+ + 4H2O (1)
[Zn(OH)2(H2O)4] + 4NH3 [Zn(NH3)4(H2O)2]2+ + 2OH + 2H2O
Or
Zn(OH)2 + 4NH3 [Zn(NH3)4]2+ + 2OH
(1) for cation formed
(1) for balancing equation with the correct species (2) 3

(e) (i) d-(sub) shell / orbitals are full / 3d10 arrangement of electrons (1)
No jumps of d-electrons /no d-d transitions (1)
Any mention of e falling back down or no splitting of d-orbitals and
second mark is not awarded 2
(ii) Cr is a transition metal / Cr can have d-d transitions /CrO42 is
yellow / Cr(+6) or Cr(VI) is yellow 1
[16]

10. (a) (i) Fe [Ar]


3d64s2
or 3d64s2
or 3d64s2
or 4s23d6 (1)
Fe2+ [Ar]
3d6
or 3d6
or 3d64s0 (1)
Letter d must be lower case
Any additional letters of numbers (0) 2

8
(ii) The mark is for the shape

ALLOW bond to H of H2O (except on left side if OH2 is given)


IGNORE charge unless incorrect 1

(iii) [Fe(H2O)6]2+ + 2OH [Fe(OH)2(H2O)4] + 2H2O


OR
[Fe(H2O)6]2+ + 2OH Fe(OH)2 + 6H2O
OR equations with 2NaOH as reactant and 2Na + as product
IGNORE state symbols 1

(iv) Green precipitate / solid foxy-red / red-brown / brown / orange


Both colours and precipitate / solid needed
NOT darkens 1

(v) N2 + 3H2 / 2NH3

OR equation with Cl2 1

9
(b) (i) Emf of cell / potential difference of cell containing Fe2+ and Fe (1)
and standard hydrogen electrode / half cell NOT SHE
OR hydrogen electrode and 1 mol dm3 H+ and 1 atm H2 (1)
1 mol dm3 Fe2+
IGNORE temperature 3

QWC*(ii) Emf of hydrogen electrode is zero stated or implied (e.g. if


calculate Ecell = +0.44(V)) (1)
Fe + 2H+ Fe2+ + H2 (1) equation stand alone
Potential for the reaction is positive so reaction is feasible (1)
OR
H+ and ()H2 has a more +ve electrode potential than Fe2+ and Fe (1)
H+ will oxidise Fe / H+ is an oxidising agent / Fe is a reducing
agent for H+ / other correct redox statement (1)
Fe + 2H+ Fe2+ + H2 (1) stand alone 3

(iii) High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions 1

(c) 2Fe3+ + 2I 2Fe2+ + I2 or words E0 = (+) 0.23V (1)


So I would reduce Fe3+ / Fe3+ would oxidise I / E0 positive so reaction
L R (1)
OR reverse argument (2)
OR
Fe3+ and Fe2+ has a more positive electrode potential than I2 and I (1)
I will reduce Fe3+ / Fe3+ will oxidise I (1) 2
[15]

11. (a) (i) Forms ions which have partially filled d-orbitals
OR
Forms ions which have a partially filled d-subshell 1

(ii) Scandiurn / Sc and Zinc / Zn 1

(b) (i) Fe2+ [Ar] 3d6


Mn2+ [Ar] 3d5 (1) for both correct 1
(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

10
(c) Shape (1)
Bonding to correct atoms (1)
(4) (4)

CN CN
NC CN
NC CN
Fe Fe
OR
NC CN
NC CN
CN CN
2

(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(ll) / Mn2+ (1) NOT standalone mark 4

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

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


unchanged (at +5) 1
(iii) First green colour : VO2+ and VO2+ (1)

Second green colour : V3+ / [V(H2O)6 ]3+ (1)

Violet colour : V2+ / [V(H2O)6 ]2+, (1) 3


[16]

12. (a) 3OCl 2Cl + ClO3 (1)

chlorine (in OCl) 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

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

11
(ii) no. moles S 2 O 32 used = 12.5 0. 1 / 1000 = 1. 25 103 (1)

no. moles I2 = 1.25 103 / 2 = 6.25 104 (1)


no. moles ClO = no. moles 12 (1)
no. moles ClO in original 10 cm3 = 10 6.25 104
= 6.25 103 (1)
no. moles ClO in 1 dm3 = 100 6.25 103 (1) = 0.625 5

(iii) mass Cl2 = 0.625 71


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

(c) Cl2 is the stronger oxidising agent because Cl2 oxidises S from
(+)2 to (+)6 (1)
but l2 oxidises S from (+)2 to (+)2.50 (1) 2

QWC (d) O2 oxidises KI / iodide to l2. or balanced equation (1)


ll2 reacts with starch / paper to give blue / black (1) 2
[14]

3d 4s
13. (a) [ Ar ] (1)
3d 4s
[ Ar ] (1)

Allow instead of and instead of 2

(b) Forms ion(s) which have a partially OR an incompletely filled


d-(sub)shell OR d-orbital(s) 1

(c) (i) Dative (covalent) OR co-ordinate (1)


Covalent (1) 2

12
(ii) [Ni(H2O)6]2+ + 2NH3 [Ni(OH)2(H2O4)] + 2NH +4
OR
[Ni(H2O)6]2+ + 2NH3 Ni(OH)2 + 4H2O + 2NH +4
OR
[Ni(H2O)6]2+ + 2OH [Ni(OH)2(H2O4)] + 2H2O
OR
[Ni(H2O)6]2+ + 2OH Ni(OH)2 + 6H2O
IGNORE state symbols
IGNORE missing square brackets in any formula 1

(iii) H+ removed (by NH3 OR OH) (1)


From (H2O) ligands (1)
NOT just from complex 2

(iv) Ligand exchange


OR ligand replacement
OR ligand substitution 1

(v) [Ni(OH)2(H2O)4] + 6NH3 [Ni(NH3)6]2+ + 2OH+ 4H2O


OR
Ni(OH)2 + 6NH3 [Ni(NH3)6]2+ + 2OH

Allow formation of [Ni(NH3)4]2+ OR [Ni(NH3)4(H2O)2]2+


cation formed (1)
balancing equation (1) 2

(d) d-orbitals split (in energy) by ligands (1)


QWC ALLOW d-sublevel
absorbs light (in visible region) (1)
NOT uv light
electron is promoted OR electron moves to a higher energy level (1)
Any mention of emission of light can only score 1st mark 3
[14]

13
1. (a) (i) *CH(CH3) (1) 1
(ii) (the three) OH groups (1)
allow adrenalin to form more hydrogen bonds with water
(than does benzedrine) (1) 2

(b) (i) 1

CH 2 CH(CH 3 )NH3 +(Cl )

Can use R in place of C6H5CH2CH(CH3) in both (i) and (ii)

(ii) 1
CH 2 CH(CH 3 )N C CH 3
(1)
H O

O
(iii)
CH 3 C CH 2 CH(CH 3 ) N C CH 3

O H
substitution(s) in ring at any position(s) (1)
production of amide (1) 2

(d) R NHCH 3 R H 2
C C C C
H H H NHCH 3

(e) (i) (CH(CH3)NH2)+ (1) 1

(ii) (CH2NHCH3)+ / (CH(OH)CH2)+ (1)


max 1 for (e) if no charges shown
must show some structure in answers ie. C2H5N(0) 1
[11]

2. (a) (i) The enthalpy / heat / heat energy change / released when 1 mol of benzene is
formed (1) from its elements (1) under standard conditions 2
(ii) The enthalpy / heat / heat energy change when 1 mol of benzene burns (1) in
excess oxygen / burns to form carbon dioxide plus water / is completely oxidized
under standard conditions (1)
The second mark is not awarded if standard conditions are not mentioned in part
(i) or (ii). 2

1
6C + 3H 2 C6 H6
(b)

H1 H2
6CO 2 + 3H 2 O
For correct cycle shown (1) or equivalent equations
H1 = 6 (394) + 3 (286) = 3222 kJ (1) for either showing calculation or
answer
Hf = 3222 (3273) = +51 kJ mol1 (1) 3

(c) Benzene has electrons delocalised (1) Therefore bond energy NOT that of CC or
C=C

localised (1)

Energy +215 Delocalised (1) consequential

+51
6C(s) + 3H 2 (g)

(d) (i) rate = k[benzene][bromine] 1


(ii) rate would be decreased (1)
Ea of rate determining step (or the idea of it) would be increased (1) 2
[14]

2
3. (a) CH3CO+ (1)
Candidate may not identify electophile but may score this mark if they use the
correct electrophile in the mechanism
CH3COCl + AlCl3 CH3CO+ + AlCl4 (1) 2

AlCl 4-
(1)
+ H
OCCH 3
COCH3
(1)
(1)

COCH3
+ HCl

In the mechanism the electrophile can be shown as


+
CH3CO Cl AlCl3

(b) Notes: The arrow for the first mark should start inside the ring and
go to the carbon of the CO group.
The arrow for the last mark should start on the bond and finish inside the ring.

AlCl 4-
(1)
+ H
OCCH 3
COCH3
(1)
(1)

COCH3
+ HCl

3
(c) There are several routes through this; all can score full marks
CN
CH3 O
C CH3 C OH
(1)
(1)
+ HCN
Dilute HCl (1) Heat 9under
reflux) (1)
Slightly acidic / slightly alkaline / or
buffered at name pH between 5 Dilute NaOH (1) followed
and 9 / mixture of KCN and acid. / by acid (1)
HCN plus KCN (1) CO 2 H

CH3 C OH

5
[10]

4. (a) 2S2O32 + l2 S4O6+2 + 2I or clearly stated (1)


amount of thio = 26.8 0.1 / 1000 = 2.68 103 mol (1)
ratio of copper to thio is 1:1 (1)
total amount of copper = 2.68 103 mol 10 = 2.68 102 mol (1)
mass of copper = 2.68 102 mol 63.5 g mol1 = 1.70g (1)
purity = 1.70 100 / 1.74 = 97.8 / 97.7 % (1) 6
allow 2 to 4 sig figs in final answer mark consequentially

(b) The increase in successive ionisation energies is similar (1)


compensated for by bond formation or hydration enthalpy or
energy or lattice enthalpy (1)
catalysis involves metal ion moving from one oxidation state
to another (1)
and back (1) 4

(c) (i) Sodium nitrite + aq / conc / dilute HCl / hydrochloric acid (1)
any temperature between 0 and 10 C or a range between 0 & 2
10 C (1)

(ii) If too cold reaction too slow (1)


if too warm product or nitrous acid decomposes / products
would be phenol and nitrogen (1) 2

4
+
N N(Cl) + OH
(iii)


N N OH + H + (Cl or HCl)

3 structures (2)
2 structures (1)
Balance (1)
It is not necessary to show the full structure for the diazo compound
e.g C6H5N2+ is acceptable.
Conditions phenol in alkali (1) yellow / orange / red ppt (1) 5

(d) Conc HNO 3 +


(1) Sn (1) + conc 6
conc H 2 SO4 HCl (1)
NO2 NH 2
30 to (1) heat (1)
55 C (1)
Condition mark depends on reasonable reagents
If give alternative route then 1 for each error
Name of nitrobenzene acceptable
[25]

5. (a) (i) Aluminium chloride or AICl3 or iron(III) chloride or FeCl3 (1)


catalyst (1) 2

CH 3 COCl AlCl 3 CH 3 CO + + AlCl 4 (1)

CH 3 CO + COCH 3
(1)
+ H (1)
(AlCl 4)
(1)

(ii)
COCH 3
+ HCl (+ AlCl 3 )

Marks:
formation of electrophile
attack on electrophile from ring
intermediate
removal of proton 4

(b) Esterification / condensation (1)

5
O
CH 3 C O

(1) 2

OH OH OH
(c) (i) OH

OH
OH
Three correct 2 marks. 2 correct 1 mark 2

(ii)
O O
O O C CH 2 C

Ester link (1)


polymer / with correct benzene ring links (1) 2

(d) Benzene diazonium chloride (solution) / ion shown or C6H5N+N (1)


Sodium nitrite and hydrochloric acid (1)
010C (1)
alkaline solution (of phenol) (1)
[16]

6. (a)
H
O C H
H
H C H
C C

C C
H C H

H
Fully displayed showing all C, H and circle or kekul structure. 1

6
(b) Understanding of electrophile positive/electron deficient entity
ACCEPT Species that accepts a lone pair of electrons (1)
Understanding of substitution exchange/replace for another entity / atom /
hydrogen (1) 2

(c)
OCH3
NO2

Must contain a hexagon (with ring or kekul inside)


Bonds must go from ring to O of OCH3, and
to N of NO2 1

(d) C7H7OBr )
C7H6OBr2 ) Any two
C7H5OBr3 )
HBr ) 2

(e) (i) Methoxybenzenesulph/fonic acid 1


(ii) Detergents/drugs/dyes 1

(f) (i) D hydrogen / H2 (1)


E (Raney) nickel / nickle / Ni /Platinum /Pt (1) 2
(ii) Addition (1)
Reduction (1) 2

(g) (i) Petroleum/crude oil/coal 1


(ii) Not carcinogenic / (cumulative) poison / toxic use of benzene in
schools is illegal 1
[14]

7. (a) (i) Conc. sulphuric acid(1)


Conc. nitric acid (1) 2
[Conc. must be stated, or implied, for both acids]

7
(ii) HNO3 + H2SO4 H2O + HSO4 + NO2+ (1)
Can be shown in two stages
Or
HNO3 + 2H2SO4 H3O+ + 2HSO4 + NO2+ (1)
NO 2+ NO 2

+ H (1) for intermediate


(1)
(1)

NO 2
(+ H + )

I.e. curved arrow from benzene ring of electrons towards N in NO2+


ion (1)
Intermediate correctly drawn, including positive charge (1)
Curved arrow from C-H bond back into benzene ring (1) 4

(iii) Electrophilic substitution 1

(b) 3
NO 2 NO 2 NO 2
NO 2

NO 2 NO 2 O2 N NO 2
NO 2
(1) (1) (1)
Vertical/right hand substituents must be shown with C to N bond
[Mark consequentially on structural formula given for
nitrobenzene in (a)(ii)]

(c) Tin / iron and concentrated hydrochloric acid/conc. HCl (1)


Heat (under reflux) (1) 2
Second mark consequential on correct / near miss reagents

8
(d) (i) H H 1

N C C H
O H
Allow:
NH C CH3
O

(ii) Dissolve in minimum volume (1)


Of boiling/hot solvent (or any specified solvent other than water)
(1)
Filter through a heated funnel (1)
Cool or leave to crystallise (1)
Filter under suction/filter using Buchner funnel (1)
Wash crystals with cold solvent (1) 6
NB If no solvent used, no marks available at all in part (d)(ii)
[19]

8. (a) (i) It is non-superimposable on mirror image/ it has a single asymmetric


carbon atom 1
(ii) rotates the plane (of polarisation) (1)
of (plane) polarised (monochromatic) light (1)
OR
Use a polarimeter (1)
rotates the plane (of polarisation) of the light (1) 2
(iii) product is an equimolar mixture/racemic mixture (1)
so rotations cancel (1) 2

(b) NH3 +Cl on the amino group (1)


COO Na+ on the carboxyl group (1) 2
(c) Zwifterions structure (1)
There is ionic attraction between adjacent zwitterions (1) 2

9
(d) (i) (polymer formed by) elimination/ removal of a small molecule/ water
(between two monomers) 1
(ii) any CIOC***COCl (1) and H2N*CH2*NH2 (1) 2
(iii) structure consequential on answer to (ii) showing amide link (1)
and extension of the chain (1) 2
(iv)
H H H H
N C C N C C N C C
H CH 3 O CH3 O H CH 3 O
CONH drawn out (1)
Show 3 units (1) 2
[16]

9. (a) (i) 240 (kJ mol1) 1


(ii) 360 (kJ mol1)
Penalise incorrect units once only 1
(iii) Overlap of p-orbitals / (system) (1)
(results in) delocalisation (1)
makes benzene (more) stable (by 152 kJ mol1) (1)
QWC* 3

10
(b) (i) AlBr3/ AIC13 / FeBr3 / Fe
Formula must be correct; no names 1
(ii) Ignore curly arrows in this first step; mark species only
(consistent with catalyst)
+
Br 2 + AlBr 3 Br + AlBr4 (1)

Br
Br
+ +
Br + +H

(1) (1) structure


(1) arrow
Alternative way of showing part played by catalyst

Br BrAlBr3

Allow Kekul intermediate 4


+ Br
H

(iii) Electrophilic substitution 1


[11]

10. (a) 6

solution X Y
Sodium fizzing/ effervescence/ no reaction /
carbonate bubbles (1) no bubbles (1)
Bradys reagent no change/ yellow /orange / orange-red or
(2,4-dinitro (stays) yellow/orange (1) yellow-orange precipitate /
phenyl hydrazine) (crystalline) solid (1)
Potassium no change Goes from orange to green/
dichromate + /(stays) orange (1) brownish green/dull green (1)
sulphuric acid

11
(b) (i) 1

Do not allow if bond is obviously to wrong atom from benzene


ring

(ii) 1

(iii) Undisplayed ester + unchanged CHO (1)


Correctly displayed for both groups (1) 2

(iv) sulphuric acid / hydrochloric acid 1


(v) Cl (and O) electronegative/electron withdrawing (1)
So C+ is more/ very susceptible to nucleophilic attack/ more +/
more electrophilic (1) 2

(c) (i) Electrophiles / electrophilic 1


(ii) Br+/ Br+/ Br+ Br 1
(iii) Any substitution product with Br on benzene ring, and other 1
groups unchanged
(iv) lone pairs / electrons on phenolic group make ring more 1
negative than in benzene / lone pairs on OH donated to ring
[17]

12
11. (a) (i) Fuming sulphuric acid / conc.sulphuric acid & sulphur trioxide (1)
Warm/(heat under) reflux/ hot/ high temperature (1)
[fuming/conc. could appear as a condition]
OR
concentrated sulphuric acid
(heat under) reflux for several hours (1) 2
(ii) SO3/ SO3H+ 1

(b) (i) OR C6H5Br 1

(ii) Substitution (1) Electrophile (1) 2


(iii) As oxygen lone pair is delocalised into ring / interacts with e in ring (1)
Benzene ring more attractive to electrophiles/greater electron
density/more nucleophilic (1) 2

(c) (i) Ethylbenzene/Phenylethane 1


(ii) Aluminium chloride reacts with chloroethane (1)
Inducing a positive charge on the ethyl group (1)
OR correct equation showing charges
AlCl3 + CH3CH2Cl AlCl4 + CH3CH2 (2) 2

(d) (i) UV/sun light 1


(ii) 1,2,3,4,5,6-(hexa)chloro cyclohexane 1
[13]

13
12. (a) (i) C6H5ONa+ / C6H5ONa / C6H5O 1
Do not allow covalent O-Na
(ii)

1
No other Isomer allowed
OR

IGNORE bond to H of OH

(iii)

1
No ring substitution allowed

(b) (i) NaNO2 / sodium nitrate / nitrate(III) (1)


conc aq / dil HCl / hydrochloric acid (1)
NOT HCI
Any temperature between 0 - 10 C
OR range between 0 - 10 C (1)
NOT less than 10 C
IGNORE everything before phenylamine eg starting from benzene
Conditions are dependent on correct or nearly correct reagents 3

14
(ii)

Correct diazonium ion (1) if - +N=N the + must be on correct N


Correct equation (1)
IGNORE position of OH group
Can include Cl if equation is balanced
ALLOW + C6H5OH . + H+ 2

(iii) Alkaline / alkali / sodium hydroxide / NaOH / KOH / potassium hydroxide /


sodium carbonate / sodium hydrogencarbonate
IGNORE temperature 1
[9]

13. (a) (i) Chloromethane / bromomethane (1)


ALLOW methyl chloride
(anhydrous) aluminium chloride (1)
NOT iron (III) chloride / bromide
ALLOW formulae 2

(ii) Substitution (1)


Electrophilic (1)
In any order
1 for each extra incorrect type eg addition as well as substitution 2

(iii) CH3Cl + AlCl3 AlCl4 and CH3+ / CH3+ AlCl4 (1)


ALLOW TE with FeCl3
and the positive ion/electrophile is then attracted to the (delocalised)
electrons in the benzene ring/negative benzene ring (1) 2

15
(b) (i)

2 (or 3 or 4)-chloro(-1-)methylbenzene (1) must be consistent


with formula
ALLOW 1-chloro-4-methyl benzene / 1methyl-4-chlorobenzene etc 2

(ii) Chlorine (in an inert solvent) (1)


NOT aq/H2O
iron OR iron(III) chloride (1)
Mark independently
ALLOW formulae 2

(c) (i) Substitution (1)


Nucleophilic (1)
IGNORE hydrolysis
NOT SN1
NOT hydrogenation 2

(ii) second order


because the halogenoalkane is a primary one / two particles/both
reactants are involved in RDS (1)
Formulae showing carbon atom has a + with OH attacking it

If SN1 ALLOW max 1 for showing halogenoalkane ionising in


slowest step 2

(d) (Full) oxidation /redox

16
NOT reduction
NOT partial oxidation 1

(e) Any 2
set them on fire/heat (1)
both burn with a sooty flame (1)
add sodium (1)
both give off bubbles of gas /hydrogen/fizz/effervesce/sodium will
disappear/white solid forms (1)
add PCl5 (1)
misty fumes of HCl (1)
nitric and sulphuric acid (1) NOT nitration
produces yellow/brown/red products (1) NOT brown gas disappears
If they describe esterification to produce oily drops of the same ester
max 2
NOT reagents which produce no reaction eg. Bradys reagent
NOT decolorise bromine water
NOT decolorise bromine and iron / iron bromide 4
[19]

14. (a) (i) C3H5 (1)


7.2 / 24 = 0.3mol CO2 / 0.3 mol C (1)
4.5 2
4.5/18 = 0.25mol H2O / = 0.5 mol / g H (1)
18
ALLOW deductions based on one calculation
3.6
e.g. 0.5g H 3.6g C = 0.3 mol C.
12
Follow through their reasoning if it logically arrives at the
correct ratio (2)
4.1 4.1 4.1
e.g. mol A 6 mol C 6 24 dm3 CO2 etc 3
82 82 82

17
(ii)

Mark independently
ALLOW other three, four and five membered ring structures
ALLOW fully/partially displayed formulae
NOT open-chain structure with 2 C=C NOR C6H10Br2, open
chain with one C=C 2

(iii) Structural formula (1)

OR T.E. providing correct numbers of bonds


May be in equation
Ethanol/alcohol(ic) and heat / pressure / sealed tube (1)
C6H10Br2 + 4NH3 C6H14N2 + 2NH4Br (2)
ACCEPT HBr (for(1)) 4

(b)

ACCEPT any multiples / partial multiples


ALLOW allowed TE from (iii)
IGNORE ns 2
Condensation (polymerisation) (1)
[11]

18
15. (a) Delocalisation / -systern (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 / double bonds / cyclohexatriene,
Kekule structure (1) Standalone mark 3

(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

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

19
(ii) AlBr3 + CH3CH2Br CH3CH2+ + AlBr4 (1)
ALLOW C2H5+ in this equation only

2 3
+
CH 2 CH 3 H
(1) for arrow Intermediate (1)
CH 2 CH 3 CH 2 CH 3 + HBr + AlBr3
Br AlBr3
H

(1) for arrow from C H bond

OR

CH 2 CH 3
+
CH 2 CH 3 H
(1) for arrow Intermediate (1)
CH 2 CH 3 CH 2 CH 3
+
+ H
H

(1) for arrow


(3)
Arrows
Do not allow to C2H5+ 4
ALLOW to point / go to + charge
ALLOW C2H5 in intermediate
(iii) Electrophilic substitution 1
[13]

16. (a) C10H8


ALLOW (C5H4)2
NOT (C6H4)2 1

(b) (i) 600


NOT + 600
NOT 600 1

20
(ii) Naphthalene is more/very stable than double bonds suggest (1)
Must be a comparison for the 1st mark
Therefore the electrons/bonds may be/are delocalised
(over the ring system)
OR it is a delocalised system (1)
No TE from (i)
Delocalised mark can be given if delocalisation mentioned in (iii) 2

(iii) No
because it is likely to react like benzene / delocalised structure /
no double bonds
OR bromine not a strong enough electrophile without a catalyst
OR yes but only if bromine [NOT bromine solution] and a catalyst 1

(c) (i) Reagent


2-chloropropane (1)
ALLOW 1-chloropropane OR other halogenopropanes
NOT chloropropane
NOT bromo-2-propane
ALLOW formula with or without non-systematic name
ALLOW ClCH(CH3)2 OR (CH3)2CHCl OR C(CH3)2HCl OR ClC(CH3)2H
Catalyst
aluminium chloride / AlCl3/Al2Cl6
OR aluminium bromide / AlBr3
OR iron(III) chloride/FeCl3 (1)
NOT AlCl4()
NOT iron on its own
If both correct but wrong way round 1 (out of 2) 2

(ii) electrophilic (1)


substitution (1)
Can be given in any order
Mark independently 2
[9]

17. (a) (i) White precipitate OR white suspension OR white solid 1

21
(ii)
OH OH
Br Br
+3Br2 +3HBr

Br
2,4,6-tribromophenol (1)
rest of equation if for formation of a tribromophenol (1)
C6H5OH + 3Br2 C6H2Br3OH + 3HBr scores (1) 2

(iii)
O
O C
CH 3
C = O in ester must be shown 1

(iv) C (atom) is (very) + because Cl highly electronegative


OR Cl electron withdrawing (1)
IGNORE references to oxygen
(so C atom) susceptible to nucleophilic attack OR (so C atom)
strongly electrophilic (1)
IGNORE references to activation energy 2

(b) Sn and conc hydrochloric acid (accept conc HCl) OR Fe and conc
hydrochloric acid (accept conc HCl)
IGNORE any references to NaOH
IGNORE references to Fe or Sn as a catalyst 1

(c) (i) Sodium nitrite OR NaNO2 OR sodium nitrate(III) (1)


NOT JUST HNO2
Hydrochloric acid OR dilute sulphuric acid OR aqueous
sulphuric acid 2
ACCEPT HCl if qualified. Do not accept conc. sulphuric acid
Only award the hydrochloric acid mark if NaNO2 or KNO2 or HNO2
given as co-reagent

(ii) Below 0 C : reaction too slow (1)


Above 5 C : product decomposes OR diazonium ion decomposes (1) 2
NOT HNO2 decomposes

22
(iii)

N=N OH
OR O
instead of
OH group 1

(iv) Dissolve in minimum volume of boiling solvent OR dissolve in


minimum volume of hot solvent (1)
QWC NOT JUST small volume
[ALLOW any specified solvent including water]
Filter hot OR filter through heated funnel (1)
Cool or leave to crystallise (1)
Filter (under suction) (1)
Wash solid with cold solvent (and leave to dry)
OR wash solid with small volume of solvent (and leave to dry) (1) 5
[17]

18. (a) Nitric acid / HNO3 (1)


Dilute / 4M acid and boil/heat (1) 2

(b) Reduction
ALLOW redox 1

(c) (i) 4() aminophenol / 4()hydroxyphenylamine


OR 1()amino()4()hydroxybenzene etc
ALLOW para / p etc 1
(ii) Add copper(II) (sulphate solution) / Cu2+ (1)
Green / brown (precipitate) forms (1) 2

(d) (i)
OH ONa

(+ 2NaOH) (+ CH 3 CO 2 Na + H 2 O)

NHCOCH 3 NH 2
Organic formula fully correct (2)
Only one group reacting (1) 2

23
(ii) No because, phenol is not a strong enough acid to react with sodium
carbonate (1)
NOT because phenol is a weak acid 1

(e) (i) Van der Waals and (permanent) dipole (permanent) dipole, and
QWC hydrogen bonds (1)
Van der Waals between aromatic rings / everywhere / anywhere (1)
(Permanent) dipole force between carbonyl / C=O groups (1)
Hydrogen bonds eg between NH and O=C (1) 4
BUT must make it clear which atoms are involved

(ii) Van der Waals total forces in paracetamol are too strong
QWC OR
Hydrogen bonds in water are too strong
ALLOW carbon chain too long / large
ALLOW because of benzene ring 1

(f) (Broad) OH (stretching absorption from) (1)


3750 3200 (cm1) (1)
OR
(Broad) NH (stretching absorption from) (1)
3500 3140 (cm1) (1)
Bond must be specified for 1st mark but range mark is
not dependent on 1st mark 2

(g) (i) C8H9O2N+


Fully correct with charge 1

(ii) 43CH3CO+ / C2H3O+ / CHNO+


93C6H5O+ (1)
IGNORE charges unless both negative, then 1 max if fully correct
ACCEPT semi-structural formulae but NOT
+
OH
2

(h) No gastric / internal bleeding / suitable for younger children 1


[20]

24
19. (a) (i) Conc(entrated) / fuming sulphuric acid / sulphur trioxide / SO3 (1) 1
Accept oleum (1)
Reject sulphuric acid / H2SO4

(ii) Substitution (1)


Electrophilic (1) 2

(b) (i) To avoid losing too much vanillin (in the filtrate when
crystallisation occurs) OWTTE 1
Accept to maximise the yield
Reject answer only referring to saturation

(ii) Insoluble impurities removed by hot/ first filtration (1)


Soluble impurities remain in solution (1) 2

(iii) Measure mpt (1)


Compare with data OR sharp melting point (1) 2
Accept bpt. method can only score 2nd mark

(c) Vanillin is likely to be a product since ..


IR spectrum of product shows an absorption for aldehyde C=O
stretching /vibration (1)

at about 17401720 cm1 /any value within this range (1)
(This is absent in the 2-methoxyphenol IR spectrum) 2
[10]

20. (a) Reagent: chloromethane/CH3Cl (1)


Accept bromomethane/ CH3Br/iodomethane/ CH3I
Catalyst: (anhydrous) aluminium chloride/AlCl3/Al2Cl6 (1)
OR equivalent bromides
Accept iron(III) chloride/ bromide
Reject iron
Mark independently 2

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

25
(ii) Cl2 2Cl (1)
PhCH3 + Cl PhCH2 + HCl (1)
PhCH2 + Cl2 PhCH2Cl + Cl (1)
any one of:
2 PhCH2 PhCH2CH2Ph
PhCH2 + Cl PhCH2Cl
2 Cl 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. 4
Dot must not be on Ph penalise once
P instead of Ph penalise once

(iii) flask and vertical condenser need not be shown as separate items
(1) [Ignore direction of water flow; penalise sealed condenser]
gas entry into liquid in flask (1) [allow tube to go through the side
of the flask, but tube must not be blocked by flask wall]
Allow the gas to be bubbled down a tube coaxial with the
condenser bore.
Bubbling gas into a beaker OR other vessel without a
condenser 0 (out of 3)
heating from a electric heater/heating mantle/sand bath/water
bath/oil bath (1) diagram or words
labelling of diagram not necessary
[IGNORE uv source] 3
Reject just heat, Bunsen
[10]

21. (a) (i) methylbenzene/phenylmethane 1


(ii)
CH3
SO 3 H

1
Accept alternative substitution products with
SO3H group on other ring positions
SO3 H+
Accept multiple substitutions
Accept Displayed Formulae
Reject bonding to ring through H or O atom

26
(b) (i) (conc.) nitric acid (1)
Accept HNO3
Reject dilute, HNO3 (aq)
(conc.) sulphuric acid (1) Mark independently 2
Accept H2SO4
Reject H2SO4(aq)
Reject incorrect formula in conjunction with name

(ii) NO2+ 1

Reject NO2+

(c) (i) Substitution (1)


Electrophilic / electrophile (1) 2
Accept either way round
Reject incorrect type or mechanism in conjunction with correct
response

(ii) the ring is more susceptible to attack by electrophiles/


more nucleophilic/ ring has greater electron density (1)
as methyl group pushes electrons into ring/ toluene has a
dipole moment (1) 2

(d) Oxidation 1
Accept partial oxidation
Reject redox
Reject full oxidation

27
(e) sodium/ potassium dichromate((VI)) (1)
Accept Na2Cr2O7/ K2Cr2O7
sulphuric acid (1)
or
Potassium manganate ((VII)) (1)
Accept H2SO4
dil. or conc.
acidified dichromate = 1
or
KMnO4
Sulphuric acid (1) 2
Accept H2SO4
acidified manganate = 1
OR
Potassium manganate ((VII)) (1)
Sodium hydroxide (1)
Reject incorrect oxidation numbers
Reject incorrect Formula in conjunction with correct name
[12]

22. (a) (i)



O O

H C H

+
H N H

H
Positive charge must be on the N atom
The minus charge must be on the O in the CO if no
delocalisation shown 1
Accept delocalised carboxylate group with a negative charge
shown
Reject compressed structural formula

28
(ii) (H+ from) COOH (group) protonates the NH2(group) 1

Accept transfer of H+ from COOH to NH2


Or
self-protonation
Reject just protonation
Reject just acid-base reaction

(iii) Read the whole answer!


High energy needed to overcome (strong) ionic attractions (1)
Accept ionic bonds or ionic lattice instead of ionic
attractions
Reject just intermolecular forces
Or H bonding
Or van der Waals forces etc
award zero overall
between zwitterions (1)
Accept between adjacent species
Ignore reference to molecules if clearly used in the context
of attraction between ions 2

+
(b) (i) NH3CH2COOH / +H3NCH2COOH / +H3NCH2COOH
OR written right to left
OR
O OH

H C H

+
NH3 1
Accept CO2H
OR
NH3+Cl
Or NH3Cl
Reject molecular formula

29
(ii) NH2CH2COO / NH2CH2CO2 /

O O

H C H

NH2 1
Accept COONa
or
COONa+
Reject molecular formula

(iii) CH3CONHCH2COOH/
O OH

H C H

H N

C O

H C H

H 1
Accept CH3CONHCH2CO2H
OR no reaction (1)
Reject molecular formula

(iv) NH2CH2COOCH3 /
H

O O C H

C
H

H C H

H N H 1
Accept NH2CH2CO2CH3

30
(c) (i) (Glutamic acid molecule) has four different groups attached
to a C (atom)
Or
(Glutamic acid molecule) has four different groups attached
to a chiral centre
Accept contains an asymmetric carbon (atom)
Or
molecule has no plane of symmetry
Reject just has a chiral centre
Or
Just the molecule is asymmetrical
OR
has mirror images which are not superimposable 1

(ii) (the isomers) rotate the plane (or polarisation) of (plane-) polarised
light (1)
Accept .rotate plane polarised light
in opposite directions (1)
Reject just in different directions
Ignore any reference to polarimeter 2

(d) H2N(CH2)6NH2 (1)


ClOC(CH2)4COCl /
O O

ClC(CH 2)4C Cl (1)

[Monomers can be given in either order] 2


Accept NH2(CH2)6NH2
HOOC(CH2)4COOH / HO2C(CH2)4CO2H /
O O

HO C(CH 2)4 C OH
COOH(CH2)4COOH
Or COCl(CH2)4COCl
[13]

31
23. (a) (i)
SO3 H

Bond from benzene ring must be to the sulphur atom


Hydrogen atom must be linked to oxygen 1
Accept C6H5SO3H
Accept C6H5SO2OH
Reject C6H5HSO3

(ii) Fuming sulphuric acid / oleum / sulphur trioxide / SO3 / sulphur


trioxide or SO3 in sulphuric acid 1
Accept concentrated sulphuric acid / H2S2O7
Reject H2SO4 / H2SO4(aq) / sulphuric acid / dilute sulphuric
acid

(iii) (aromatic) Electrophilic substitution 1


Accept Electrophillic / Electrophylic / Eletrophilic substitution
Reject Electrophic substitution

(iv) SO3/ SO3H+


Ignore name if given with formula 1
Accept HSO3+

Reject sulphur trioxide / SO3+ / SO3

(b) (i)
SO3 H

H3 C CH 3
Allow TE from (a)(i) 1
Accept
SO3 H

CH 3 CH 3
Formula for 2,6-dimethyl benzene sulphonic acid

32
(ii) Reagent X: CH3Cl (1)
Catalyst Y: AlCl3 (1)
Allow TE from (b)(i) e.g. CH3CH2Cl if an ethylbenzene 2
Accept CH3Br / CH3I (1)
Accept Al2Cl6/AlBr3/AlI3 (1)
One correct name and one correct formula (2)
Names for both answers (1 max)

(iii) Hydrogen chloride / HCl 1


Accept answer consequential on (b)(ii), e.g. HBr
Reject hydrochloric acid

(c) (i) 4-chloro-3, 5-dimethylphenol


3,5-dimethyl-4-chlorophenol 1
Accept no/wrong punctuation
Allow name based on hydroxybenzene
Allow cloro or methyl

(ii) Hydrogen bonding interactions between dettol and water are weaker
than those between water molecules
OR
Hydrogen bonding interactions between dettol and water are weaker
thatn the van der Waals forces in dettol
Look for good use of scientific language. Answer must include a
specific type of intermolecular force 1
Accept hydrogen bonding between dettol and water is weak
Reject dettol molecule is too big
Accept dettol can only form one H-bond with water/only has
one OH group to H-bond with water
Reject arguments based on lone pairs of electrons on OH group
being delocalised into the ring
[10]

24. (a) (i) (anhydrous) aluminium chloride


[Name or formulae] 1
Accept Al2Cl6
Accept AlBr3 FeBr3
Accept FeCl3
Reject Fe

33
(ii)
CH 3 CHCH 3 + AlCl 3 CH3 CHCH3 + AlCl 3 Br (1)
Br
H CH 3
CH 3 CHCH 3 + CH
+

(1) (1) CH 3

( Br AlCl 3 ) CH 3
H CH 3
CH
+ CH + (H +/ HBr + AlCl3 )
CH 3
(1) CH 3

OR
CH 3
H CH 3
H C Br AlCl 3
+ CH + Br AlCl 3
CH 3
(1) (1) (1) CH 3

( Br AlCl 3 ) CH 3
H CH 3
CH
+ CH + (H +/ HBr + AlCl3 )
CH 3
(1) CH 3

34
OR
CH3 CHCH 3
+ AlCl 3 CH 3 CHCH 3 + Br AlCl 3
Br +

+ H
CH 3 CHCH 3 CH(CH 3 )2
+

+HBr + AlCl 3
+ H Br AlCl 3
CH(CH 3 ) 2
CH(CH 3 ) 2

Equation for formation of electrophile (1)


IGNORE if incorrect arrows added at this point
First arrow must be from C=C or from or within ring
to C with + and can point to + (1)
Correct intermediate as shown in mechanism above (1)
Second arrow from CH bond into ring (1) 4
Accept either a delocalised or Kekule ring
If CH3CHBrCH3 CH3CH+CH3 + Br loses 1st mark but can
score 2nd, 3rd and 4th marks

(b) (i) CH3CH2CH2+ 1

Accept C2H5CH2+

Reject C3H7+

(ii) secondary carbocation is more stable than primary (1)


primary carbocation (CH3CH2CH2+) rearranges to produce
a secondary carbocation
OR
primary carbocation (CH3CH2CH2+) turns into a secondary
carbocation
OR
a description of the rearrangement e.g. a hydrogen atom
moves from the middle to the end (1) 2
Reject any reference to stability of intermediate /product

35
(c) (i) First mark
sodium nitrite /sodium nitrate(III)/NaNO2 (1)
Second mark
hydrochloric acid / HCl(aq) (1)
IGNORE concentration of acid
2nd mark is conditional on NaNO2 or HNO2 2
Reject HNO2
Reject HCl/hydrogen chloride

(ii) below 0 C reaction is too slow (1)


above 10 C the product/benzenediazonium ions
decomposes /hydrolysed (1) 2
Accept HNO2 decomposes

(iii)
N N

OH
N=N link, can be shown linear (1)
IGNORE other atoms
Remainder correct (1) 2
IGNORE position of OH group.
Accept ONa or O instead of OH
Reject N=NO

36
(d) (i) QWC
First two
add 2,4-dinitrophenylhydrazine/Bradys reagent (1)
orange/yellow ppt (1)
Allow this second mark if the name of the reagent is
slightly incorrect e.g. 2,4-diphenylhydrazine
Accept 2,4-dnp(h)
Accept any combination of yellow and orange
Must be ppt
Reject just Red ppt
Reject solid for ppt
OR
IR absorption due to C=O stretch (1)
at 1700 cm1 (1)
Third mark
Does not give a silver mirror with ammoniacal silver nitrate
(or Tollens reagent)
Accept no change with Tollens
OR
no red ppt/stays blue with Fehlings or Benedicts solution
Reject Iodoform
OR
H+/Cr2O72 does not change from orange to green/stays orange
OR
H+/MnO4 does not change from purple to colourless/stays purple (1) 3

(ii) the C=O group is polar and the nucleophile attacks the + carbon (1)
whereas C=C is non-polar/electron-rich, the double bond/-bond
is attacked by electrophiles (1)
OR
C=O is polar and C=C is nonpolar (1)
Nucleophile attacks the + carbon in C=O and
electrophiles attack the /double bond in C=C, which
is electron rich/non-polar (1) 2

37
(iii)

H3 C H3 C O:
C O C
H3 C H3 C CN

:CN


H3 C O: H CN H3 C OH
C C + :CN
H3 C CN H3 C CN
both curly arrows in 1st diagram, attack by cyanide, arrow
must start from C or ve charge on C not N and ve charge
must be present somewhere on ion; lone pair not essential.
Arrow must start from bond between C and O
and point towards the O (1)
Accept curly arrow from O to H+
Intermediate lone pair not essential but negative charge is
essential (1)
Arrow from O (lone pair not needed) or negative charge to HCN
or H+, this can be shown on the diagram of the intermediate (1)
If HCN is used the arrow from HCN bond is required
Any other ketone or aldehyde, max (2) 3
[22]

25. (a) (i) The activation energy for the reaction is high
or to ensure that more molecules have E Ea. 1
Accept E > Ea
Reject to overcome Ea alone
Reject reactants kinetically stable;
reactants thermodynamically stable

(ii) protonates the alcohol (1)


Reject as a catalyst alone
providing H2O as the leaving group which is more easily displaced
by the bromide ion/is a better leaving group than hydroxide (1)
OR
reacts with NaBr (1)
to give HBr (which is the attacking reagent) (1) 2

38
(iii) H-bonding between water and the alcohol not strong
enough to overcome hydrophobic interactions /effect of
alkyl group (1)
acid and alcohol form ionic species/C4H9OH2+ which
is more soluble (1) 2
Accept butyl group

(iv) Removes acid 1


Accept neutralises HCl /HBr
Accept neutralises acid

(v) Removes water 1


Accept absorbs water
Accept dries the product

(vi) Electric heating mantle or sand bath or oil bath (1)


Accept water bath
Reject heat under reflux
Reject no naked flame
Reject fume cupboard
because the alcohol/reaction mixture/bromobutane is
flammable or because the heating is uniform and less
likely to crack the flask (1)
This mark is conditional on the first being scored. 2
Reject volatile for flammable

39
(b) QWC
EITHER
Intermediate (ion) in SN1 is planar (1)
Accept intermediate carbocation is a planar molecule
intermediate molecule alone loses this mark
equal attack (by hydroxide ions) from either side (1)
produces a racemic mixture (1)
Reject attack by bromide ions
Note: Statement that the SN2 mechanism is consistent with
the information cannot score any marks.
OR
SN2 involves attack from one side (1)
so configuration of the product would be inverted (1)
leading to retention of optical activity so must be SN1 (1)
Accept forms one optical isomer only
Statement that the reaction is SN1 alone scores zero. 3

(c) (i) Orange green 1

(ii) Cr2O72 + 6e + 14H+ 2Cr3+ + 7H2O (1)

(3CH3CH(OH)CH2CH3 3CH3COCH2CH3 + 6H+ + 6e)


Cr2O72 + 3CH3CH(OH)CH2CH3 + 8H+ 2Cr3+ + 7H2O +
3CH3COCH2CH3 (1)
No consequential marking on incorrect equations. 2
Accept C4H9OH and C4H8O

Accept equation having non-cancelled H+ ions


Reject equation having non-cancelled electrons

(iii) The broad peak/absorption/trough around 3400 cm1 due to OH (1)


Accept 3230 3550
Reject broad transmission
has disappeared in the product to be replaced by C=O at 1700 cm1 (1)
Accept 1680 1750
If no reference to both groups responsible for the peaks then max (1)
OR
If no reference to both wavenumbers responsible for the
peaks then max (1) 2

40
(d) (i) Addition of barium ions pulls equilibrium to r.h.s. (1)
increases [H+] and so lower pH/the pH falls (1) stand-alone mark 2
Reject ..so gets more acidic

(ii) lower pH/pH falls 1


Reject mixture is more acidic for lower pH
[20]

26. (a) (i) Step 1


Reagent
Fuming sulphuric acid / sulphur trioxide/sulphur(VI) oxide/oleum (1)
Accept SO3/H2S2O7
Reject (Concentrated) sulphuric acid/H2SO4
Conditions
Reflux / heat (1)
Only allow heat for this mark if the reagent is reasonable
(e.g. conc sulphuric acid)
Accept if just stated temperature must be above 75 C
Step 2
Reagent
Sodium hydroxide (1) 3
Accept sodium carbonate/sodium
Accept hydrogencarbonate/sodium
Reject sodium chloride

(ii) Step 1
(electrophilic) substitution (1)
Accept sulphonation
Reject Nucleophilic substitution
Step 2
neutralisation or acid-base (1) 2

(b) (i) Friedel-Craft(s)


Accept phonetic spelling 1
Accept alkylation

41
(ii) Reagent
C12H25Cl
OR
C12H25Br (1)
Accept (1-)chlorododecane
C12H25I
Catalyst
AlCl3 (1) 2
Accept Al2Cl6
Accept Aluminium chloride
Reject AlCl4
Reject AlCl4
[8]

27. (a) Electrophilic substitution (1)


IGNORE extras eg Friedel Craft, alkylation UNLESS contradictory
1-chloro-(2)-methylpropane (1)
IGNORE punctuation
Accept (2)-methyl-1-chloropropane
Accept CH3CH(CH3)CH2Cl/CH(CH3)2CH2Cl
Accept Bromo/iodo for chloro
Reject 1-methyl-2-chloropropane
Reject missing 1 from position of Cl in name
Catalyst
AlCl3/aluminium chloride (1) 3
Accept Al2Cl6, AlBr3, FeBr3

(b) LiAlH4 is a source of H / hydride ion (1)

Hydrogen might reduce/attack benzene ring/ H wont attack


region of negative charge/ H can attack (+) C in keto group (1) 2
Reject comments on conditions or safety eg temperature,
pressure
Reject LiAlH4/H is a more powerful reducing agent

Reject H is a nucleophile/a stronger nucleophile


Reject any mention of attack on carboxylate ion (for 2nd mark)

42
(c) Note: although many candidates have calculated the empirical formula,
this is not required.
Molecular formula of ibuprofen = C13H18O2 (1)
Allow if given at end
Allow marks for masses and number of moles if answers are
rounded to 2 SF in OR but method is correct.
EITHER
Mr = 206 (1)
1
1g= mol = 4.854 103 mol
216
mass CO2 produced from 13 C
= 13 44 4.854 103 = 2.78 g (1)
mass H2O from 18 H
= 9 18 4.854 103 = 0.787 g (1)
OR
(2.78 12)
Mass C = = 0.758g
44
(0.786)
Mass H = = 0.0873g (1)
9
(0.758)
Moles C = = 0.0632
12
Moles H = 0.0873 (1)
Ratio C:H = 0.0632: 0.0873 = 13:18 (1) 4

(d) (i) (Aspirin and ibuprofen) both contain same (types of)
bond(s)(so absorb at same frequency/wavenumber) 1
Accept list of at least 4 bonds which are present in both
Reject groups for bonds

(ii) Data is required for mark


Y = paracetamol
Peak at 35003300 (NH)
IGNORE mention of amine
OR 35003140 (NH or amide)
OR 37503200 ((phenolic) OH)
OR Only Y has peaks above 3000 cm1 (so must contain
different type of bond to X and Z) 1
Reject CH in arene = 3030 as present in both
Reject 17001630 (amide)

43
(iii) 57 in Ibuprofen
C4H9+ /CH3CH(CH3)CH2+/CH(CH3)2CH2+
OR
C2O2H+/CCO2H+ (1)
Accept structural or displayed formulae
Do not allow lines at
15 (CH3+)
76 (C6H4+)
43 (C3H7+ or CH3CO+)
45 (COOH+)
as present in both
Aspirin
59 (1) OCOCH3+ /C2H3O2+ (1)
OR
121 (1) C6H4CO2H+ (1)
OR
180 (1) C9H8O4+ (parent ion) (1)
OR
137 (1) C6H4(CO2H)O+ (1)
Penalise no/wrong charges once only 3
[14]

28. A
[1]

29. B
[1]

30. D
[1]

31. B
[1]

44
32. A
[1]

33. B
[1]

34. C
[1]

35. D
[1]

36. (a) B 1

(b) B 1

(c) A 1

(d) D 1
[4]

37. (a) (i)


Br
+ Br 2
Br
188

45
(ii)
+
Br Br (1)

Br Br (1)

Br Br

Br
(1)

Br 3

(b) (i)
Br

+ Br 2 + HBr
1

(ii) Br2 + FeBr3 Br+ + FeBr4 / +


BrFeBr4 (1)
Step 1
Arrow from ring towards Br+ (1)
Intermediate (1)
Step 2
Arrow from bond, ring to H, to inside ring (and from FeBr4
to H+) and formation of products (1) 4

(iii) FeBr4 + H+ FeBr3 + HBr 1

(c) (i) QWC


Both attacked by an electrophile (1)
Due to stability of delocalised ring (1)
benzene attacked by (stronger electrophilic) Br+
rather than Br+ in Br2 (1) 3

46
(ii) QWC
Cyclohexene
Addition of Br does not involve bond breaking
/results in more exothermic reaction than loss of H+ (1)
Benzene
No Br available in benzene reaction (1) Stability of
ring regained by loss of H+ (1) 3

(d) Three / 3 1
[17]

47