Académique Documents
Professionnel Documents
Culture Documents
D
[1]
2.
C
[1]
3.
A
[1]
4.
A
[1]
5.
C
[1]
6.
A
[1]
7.
C
[1]
8.
B
[1]
9.
A
[1]
10.
D
[1]
11.
B
[1]
12.
D
[1]
13.
C
[1]
14.
A
[1]
15.
A
[1]
16.
B
[1]
17.
B
[1]
18.
C
[1]
19.
B
[1]
20.
D
[1]
21.
(a)
(i)
Copper:
+
0 to +2/2+/2 /II/2 (1)
Nitrogen:
+
+
+5/5+/5 /V/5 to +4/4+/4 /IV/4 (1)
(ii)
Cu Cu
OR
_
+ 2e
2+
_
2+
Cu 2e Cu (1)
2+
Cu[(H2O)6]
NO 3
_
+
+ 2H + e NO2 + H2O
OR
_
NO 3
+
2
+ 4H + 2e 2NO2 + 2H2O (1)
OR
NO 3
_
+
+ 4H + 2e N2O4 + 2H2O (1)
/ not 1 M (1)
(i)
(ii)
2+
2+
(aq) (1)
2+
2
then (1) only : Zn + 4OH Zn(OH)4
Allow
2
Zn(OH)2(s) + 2OH (aq) ZnO2 (aq)+ 2H2O(l)
OR
(aq)
OR
equivalent non-ionic equations, including those with Zn
2+
+ 2NaOH etc
OR
Correct balanced equations starting with hexaqua or tetraqua cations
ALLOW the hydroxides to be shown as e.g. Zn(OH)2(H2O)4 (s)
provided that the whole equation balances.
Penalise missing /incorrect state symbols on product once only.
Ignore other state symbols
(iii)
QWC
First 2 marks:
zinc hydroxide/oxide amphoteric because it reacts with alkali (to give
a solution of a zincate) (1)
and reacts with acid (to give a salt) (1)
zinc hydroxide is / acts as both an acid and an alkali scores (1) only
Third mark:
hexaquazinc or hydrated zinc ions exchanged water for ammonia or
other named ligand (1)
OR
Zn(H2O)6
2+
(c)
(i)
I2 + 2S2O3
2I + S4O6
Non-ionic equation.
(ii)
QWC
Amount thiosulphate
3
= 2.102 g
% copper = (2.102 x 100) 3.00 (1)
some reagent used to fill the jet (which does not react with the iodine
solution) and so the titre is too high (1)
and hence the percentage value would be too high (1) Allow only if
the titre is said to be high
If the titre is thought to be too low then allow percentage value too
low for 2nd mark (1)
2
[23]
22.
(a)
(i)
OR
+
(1)
Ignore state symbols even if wrong
arrow showing attack on the nitronium ion with arrow going to N atom,
or into the C N gap (1)
Arrow must start at or inside ring
Ignore position of + charge
structure of the intermediate showing reasonable delocalisation (over
at least 3 carbon atoms) (1)
arrow from the bond showing the loss of H+ from the intermediate.
Removal by hydrogen sulphate ion preferable but not essential (1)
Kekul structures score full marks
If the electrophile is incorrect then the intermediate structure
mark is lost
(ii)
QWC
First mark:
(lone pair of) electrons on the oxygen atom or on the OH group is
delocalised / incorporated into the ring (1)
OR
the OH group is electron donating (1)
Second mark:
so the ring in phenol is more negative / has increased electron density
/ ring is more nucleophilic / hence more susceptible to electrophilic
attack (1)
OR
the OH group activates the ring (1)
Second mark stand alone
mark
OR
hydrogen (1) and platinum / palladium catalyst (1)
(b)
QWC
First mark:
steam is passed into the mixture
OR
water is added and mixture boiled or distilled or heated (1)
Second mark:
and the 2-nitrophenol / product vapour distilled off with the water
(and condensed) (1)
Advantage:
The 2-nitrophenol / product distils at a lower temperature / prevents
decomposition(1)
Stand alone
23.
(a)
(i)
complex compounds
(ii)
(i)
(ii)
QWC
(simultaneous) oxidation and reduction (1)
Allow redox
of a species / substance / reactant / compound / chemical / element (1) 2
(iii)
0.66(V) (1)
Allow TE from (b)(i)
nd
mark is
2
[10]
24.
(a)
1
Circles that encompass two atoms
(b)
First mark:
Recognition that paracetamol is not chiral / has no enantiomers
/ does not have optical isomers (1)
Second and third marks:
Any two of:
there is no racemisation so the product will not be a mixture (1)
no need to separate (the enantiomers) (1)
do not have to discard an unwanted enantiomer / atom economy is higher (1)
OR
converse arguments starting from (-)-carvone.
1,4-dnp
10
(d)
(i)
11
(e)
(i)
or
for both double bonds having HBr added (1)
ignore added hydrogens
for correct orientation in exocyclic double bond (1) stand alone
HBr can be eliminated using a hydrogen from the carbon on either side
of the bromine (1)
which would then give a double bond in a different position from that
in carvone (1)
this second mark can be answered using a skeletal / structural
formula (below)
Reference to substitution
12
(f)
(i)
QWC
Using an SN1mechanism:
selection of a chiral starting material (1)
curly arrow from C-X bond to X (1)
and intermediate carbocation (1)
curly arrow from nucleophile (can come from negative charge) (1)
planar intermediate attacked from either side to give a racemic mixture
OR
intermediate equally attacked from either side to give a racemic
mixture (1)
Using an SN2 mechanism:
selection of a chiral starting material (1)
curly arrow from nucleophile (can come from negative charge) (1)
curly arrow from C-X bond to X (1)
to give correct transition state (1)
attack from opposite side to C-X bond gives inverted product can be
shown on a diagram (1)
Using nucleophilic addition to C= O:
Selection of any aldehyde (other than methanal) or any asymmetric
ketone (1)
Curly arrow from nucleophile (can come from negative charge) to
C of C=O and curly arrow from = to O (1)
Intermediate (1)
+
13
25.
A
[1]
26.
A
[1]
27.
A
[1]
28.
C
[1]
29.
D
[1]
30.
(a)
(b)
1
[2]
31.
C
[1]
32.
D
[1]
33.
A
[1]
14
34.
D
[1]
35.
A
[1]
36.
B
[1]
37.
(a)
(b)
1
[2]
38.
(a)
(b)
(c)
(d)
1
[4]
39.
(a)
(b)
1
[2]
40.
(a)
(b)
2+
1
1
15
(c)
(i)
1.79 10
(ii)
1.79 10
\ mols of
MnO4
mols of Fe
2+
in one tablet
1
4
= 5 1.79 10 (1)
3
4
5
\ 5 1.79 10 in 0.01
= 3.58
3
(iii)
(d)
= 3.6 cm (1)
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]
41.
(a)
(i)
+ B r2
Br
Br
188
16
(ii)
+
B r B r
(1 )
B r B r
(1 )
B r
B r
+
B r
(1 )
B r
(b)
(i)
Br
+ H B r
+ B r2
(ii)
1
+
(c)
(iii)
(i)
QWC
Both attacked by an electrophile (1)
Due to stability of delocalised ring (1)
+
benzene attacked by (stronger electrophilic) Br
d+
rather than Br in Br2 (1)
17
(ii)
QWC
Cyclohexene
(d)
Three / 3
3
1
[17]
42.
(a)
(i)
(ii)
O H
Fe
2+
O H
H 2O
O H
H 2O
O H
O R
H 2O
H 2O
O H
Fe
2+
O H
O H
O H
O R
H 2O
H 2O
Fe
H 2O
O H
2+
H 2O
O H
In s te a d o f d o tte d lin e
18
(iii)
[Fe(H2O)6]
2+
2+
OR
[Fe(H2O)6]
(iv)
(i)
QWC
Emf of cell/ potential difference of cell containing Fe (1)
dipping into a 1 mol dm
2+
Fe
solution (1)
RejectSHE
(ii)
QWC
Emf of hydrogen electrode is zero stated or implied
e.g. if calculate Ecell = +0.44 V (1)
(iii)
1
[10]
43.
(a)
QWC
Many OH groups (1)
which can hydrogen bond to water (1)
19
(b)
(i)
H
O
H
(ii)
O
C
CH
(c)
(i)
N H
N H
or displayed
Reject H2NC4H6NH2
(ii)
H
N
O
(C H 2 ) 4
link(1)
rest of formula (1)
Reject
OC(CH2)4CONHC6H4NH
QWC
Polymers do not form in an unkinked chain OR
chain has bends at ring OR chain not linear OR
strong fibres require straight chain (1)
This polymer has fewer hydrogen bonds between chains (1)
20
(d)
Ethenol: Addition
Fibre: Condensation
1
[10]
44.
(a)
(i)
(ii)
QWC
The water ligands split the d orbitals into one set at lower and
one at higher energy (1)
Light is absorbed (1)
and the electron promoted to a higher level (1)
The correct sequence must be given to score either of the
last two marks
(i)
(ii)
Reject failings
(c)
21
(d)
(i)
QWC
colour
chang
e
reagent
equation
(III)(VI)
(1)
Greenora
ngeyellow
(1)
(1)
(III)(II)
(1)
Greenblue
(1)
Zn+2Cr
+
Zu
2+
+2
Cr
2+
(1)
(1)
(III)complex
(1)
(1)
Reagent
3+
[Cr(NH3)6]
[Cr(OH)6]
[Cr(en)3]
3+
[Cr(edta)]
[Cr2(Cu3CO2)4 (H2O)2]
[Cr(CH3CO2)4]
Reagent and colour change must fit the complex
Score up to 7 marks (from the 9 marking points)
(ii)
Breathalyser
Original contained dichromate/chromate ions which were
reduced to green (chromium(III) by ethanol in breath (1)
Extent going green judgemental / chromium(VI)
compounds carcinogenic (1)
Then
Either
New one consists of a fuel cell (1)
where ethanol oxidised by air (using a platinum
catalyst) / Quantity of electricity proportional to amount of
ethanol in breath (1)
22
Or
New one consists of an IR spectrometer (1)
which measures line in fingerprint region /
Amount of IR absorbed depends on amount of ethanol in breath (1) 4
[20]
23
45.
(a)
24
(c)
(i)
st
1 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)
nd
2 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)
(ii)
46.
(a)
(i)
Accept Al2Cl6
Accept AlBr3 FeBr3
Accept FeCl3
Reject Fe
25
(ii)
C H 3CH CH
Br
+ A lC l 3
CH 3CH CH
H
C H 3C H C H
+
(1 )
C H
(1 )
CH
(1 )
C H
(1 )
CH
CH
( B r A l C l 3 )
H
C H 3
C H
+ A lC l 3 B r
C H
CH
+ ( H + / H B r + A lC l3 )
3
O R
H
CH
B r
CH
(1 )
(1 )
( B r A l C l 3 )
H
C H 3
C H
+
(1 )
A lC l 3
CH
H
+
C H
CH
C H
(1 )
CH
+ B r A lC l
C H
CH
+ ( H + / H B r + A lC l3 )
3
26
OR
C H 3CH C H
+ A lC l 3
Br
CH 3C H CH
+
+
C H 3CH C H
+
H
C H (C H 3)2
+H Br +
A lC l 3
Br
+ B r A lC l 3
A lC l 3
C H (C H 3)2
C H (C H 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)
st
rd
th
(b)
(i)
CH3CH2CH
2+
Accept C2H5CH2
Reject C3H7
(ii)
27
(c)
(i)
First mark
sodium nitrite /sodium nitrate(III)/NaNO2 (1)
Second mark
hydrochloric acid / HCl(aq) (1)
IGNORE concentration of acid
nd
2 mark is conditional on NaNO2 or HNO2
Reject HNO2
Reject HCl/hydrogen chloride
(ii)
O H
N=N link, can be shown linear (1)
IGNORE other atoms
Remainder correct (1)
28
(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)
1
at 1700 cm (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
+
2
H /Cr2O7 does not change from orange to green/stays orange
OR
+
(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)
+
29
(iii)
H 3C
O :
H 3C
C
H 3C
H 3C
:C N
O :
H 3C
C N
C N
H 3C
O H
C
+ :C N
H 3C
CN
H 3C
C N
st
both curly arrows in 1 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
3
[22]
47.
(a)
(i)
Cr: [Ar] 3d 4s
10 1
Cu: [Ar] 3d 4s
Both needed for the mark
1
Accept 4s 3d
1
10
Accept 4s 3d
Accept [Ar] written in full
30
(ii)
(i)
(iii)
[Cr(H2O)6]
3+
+ OH [Cr(H2O)5OH]
2+
+ H2O
OR
3+
+
[Cr(H2O)6] + 2OH [Cr(H2O)4(OH)2] + 2H2O
OR
3+
3+
[Cr(H2O)6] + 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
31
(iv)
2
(v)
acid / acidic
(i)
amount dichromate in 25 cm
1.86 10 3
4
3
=
(1) = 6.2 10 mol
rd
3 mark cq on amount I2
4
(1)
% of Cr = 64.5 % (1)
IGNORE SF unless rounded to 1 SF cq on mass Cr, provided less than 1 g
Accept 64.48 %
32
OR
amount thiosulphate for whole sample
3
3
= 0.0372 dm 0.100 mol dm 10
2
= 3.72 10 mol (1)
amount I2 = 1.86 10
mol (1)
mol (1)
mol 2 52 g mol
(1)
% of Cr = 64.5% (1)
IGNORE SF unless rounded to 1sf Mark consequentially, as above
Note:
Correct answer with no working (3)
(ii)
3+
2
48.
(a)
(i)
Accept E > Ea
Reject to overcome Ea alone
Reject reactants kinetically stable;
reactants thermodynamically stable
(ii)
33
(iii)
Removes acid
Removes water
34
(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
(c)
(i)
Orange green
(ii)
Cr2O7
+ 6e + 14H 2Cr
3+
+ 7H2O (1)
+
(3CH3CH(OH)CH2CH3 3CH3COCH2CH3 + 6H + 6e )
2
3+
+ 7H2O +
(iii)
due to OH (1)
(1)
35
(d)
(i)
49.
(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)
Step 1
(electrophilic) substitution (1)
Accept sulphonation
Reject Nucleophilic substitution
Step 2
neutralisation or acid-base (1)
(b)
(i)
Friedel-Craft(s)
Accept phonetic spelling
Accept alkylation
36
(ii)
Reagent
C12H25Cl
OR
C12H25Br (1)
Accept (1-)chlorododecane
C12H25I
Catalyst
AlCl3 (1)
Accept Al2Cl6
Accept Aluminium chloride
Reject AlCl4
Reject AlCl4
[8]
50.
(a)
(b)
+
region of negative charge/ H can attack ( ) C in keto group (1)
nd
37
(c)
1
3
1 g = 216 mol = 4.854 10 mol
mass CO2 produced from 13 C
= 13 44 4.854 10
= 2.78 g (1)
= 0.787 g (1)
OR
(2.78 12)
44
Mass C =
= 0.758g
(0.786)
9
Mass H =
= 0.0873g (1)
(0.758)
Moles C = 12
= 0.0632
Moles H = 0.0873 (1)
Ratio C:H = 0.0632: 0.0873 = 13:18 (1)
(d)
(i)
38
(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]
51.
(a)
(i)
C
H
C
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
39
(ii)
(b)
(i)
O H
C
C
+
N H
H
3
Accept CO2H
OR
+
NH3 Cl
Or NH3Cl
Reject molecular formula
40
(ii)
NH2CH2COO / NH2CH2CO2 /
O
O
C
H
C
N H
H
1
Accept COONa
or
+
COO Na
Reject molecular formula
(iii)
CH3CONHCH2COOH/
O
O H
C
H
Accept CH3CONHCH2CO2H
OR no reaction (1)
Reject molecular formula
(iv)
NH2CH2COOCH3 /
H
O
C O
Accept NH2CH2CO2CH3
41
(c)
(i)
(ii)
(d)
H2N(CH2)6NH2 (1)
ClOC(CH2)4COCl /
O
O
C lC (C H 2 )4 C
C l (1)
Accept NH2(CH2)6NH2
HOOC(CH2)4COOH / HO2C(CH2)4CO2H /
O
O
H O
C (C H 2)4 C
COOH(CH2)4COOH
Or COCl(CH2)4COCl
O H
[13]
42
52.
(a)
(i)
S O 3H
Accept C6H5SO3H
Accept C6H5SO2OH
Reject C6H5HSO3
(ii)
(iv)
SO3/ SO3H
Ignore name if given with formula
Accept HSO3
+
+
(i)
S O 3H
H 3C
CH
S O 3H
CH 3
CH 3
Formula for 2,6-dimethyl benzene sulphonic acid
43
(ii)
(i)
4-chloro-3, 5-dimethylphenol
3,5-dimethyl-4-chlorophenol
53.
(a)
(i)
2+
Zn + 2NO3 + 4H Zn
44
(ii)
hexaaquacopper(II) (1)
2+
O H 2
H 2O C u O H 2
H 2O
O H 2
O H 2
O R
H 2O
H 2O
O H
O H
O H 2
O H
(1)
Both marks stand alone
[IGNORE charge]
[IGNORE how H2O ligand is bonded to central cation]
Accept hexaquacopper(II)
Reject formula
(iv)
[Cu(H2O)6] + 4Cl
OR
2+
[Cu(H2O)6] + 4HCl
CuCl4
CuCl4
+ 6H2O (1)
+ 4H + 6H2O (1)
ALLOW
+
(b)
(i)
+ 4H
E for the reaction is 0.39 (V) (so not feasible) [value is required]. 1
2+
45
(iii)
[Cu(NH3)4]
OR [Cu(NH3)4(H2O)2]
Accept [Cu(NH3)2]
Reject [Cu(NH3)6]
oxidises Cu to Cu
2+
(1)
(i)
starch (1)
blue-black/blue/black to colourless (1)
(iii)
2+
2+
amount of Cu
mol (1)
10 (1)
in 25.0 cm = 1.655 10
in 250 cm = 1.655 10
5
[22]
46
54.
(a)
(b)
Mark independently
(i)
(ii)
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.
47
55.
(a)
10
10
3d 4s and 3d
1
1
10
Accept 4s 3d
(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)
nd
Any mention of light emission loses 2 mark
(ii)
2+
+ Cu (1)
and show that E for this is (+) 0.37 (V) (and as it is positive it is
feasible) (1)
conditional on correct reaction
(i)
CuSO4.Cu(OH)2 (2)
If formula wrong but sulphate/ SO4 is present scores 1 (out of 2)
Accept Cu2SO4(OH)2
Accept Cu2(OH)2SO4
Accept (CuOH)2SO4
Reject HSO4 instead of SO4
48
(iii)
[Cu(NH3)4(H2O)2]
2+
Accept [Cu(NH3)4]
2+
2+
Reject [Cu(NH3)6]
(d)
(iv)
(i)
QWC
(v)
49
56.
(a)
(i)
(ii)
methylbenzene/phenylmethane
C H
SO
H
1
SO3 H
Accept multiple substitutions
Accept Displayed Formulae
Reject bonding to ring through H or O atom
(b)
(i)
Accept H2SO4
Reject H2SO4(aq)
Reject incorrect formula in conjunction with name
(ii)
NO2
1
d+
Reject NO2
(c)
(i)
Substitution (1)
Electrophilic / electrophile (1)
50
(d)
Oxidation
1
Accept partial oxidation
Reject redox
Reject full oxidation
(e)
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]
57.
(a)
(i)
(b)
(i)
Substitution (1)
Electrophilic (1)
51
(iii)
(c)
nd
mark
1
at about 17401720 cm /any value within this range (1)
(This is absent in the 2-methoxyphenol IR spectrum)
2
[10]
3d
58.
(a)
4s
[ Ar ]
(1)
3d
4s
[ Ar ]
(b)
(c)
(1)
(i)
(ii)
[Ni(H2O)6]
OR
2+
2+
2+
[Ni(H2O)6] + 2OH Ni(OH)2 + 6H2O
IGNORE state symbols
IGNORE missing square brackets in any formula
(iii)
52
(iv)
(v)
Ligand exchange
OR ligand replacement
OR ligand substitution
2+
+ 2OH + 4H2O
OR
2+
+ 2OH
2+
OR [Ni(NH3)4(H2O)2]
2+
3
[14]
59.
(a)
(i)
(ii)
O H
B r
O H
B r
+3H B r
+ 3 B r2
Br
2,4,6-tribromophenol (1)
rest of equation if for formation of a tribromophenol (1)
C6H5OH + 3Br2 C6H2Br3OH + 3HBr scores (1)
(iii)
O
O
C
C H
53
(iv)
(b)
(c)
(i)
(iii)
N = N
O H
O R O
in s te a d o f
O H g ro u p
(iv)
QWC
5
[17]
54
60.
(a)
(i)
EITHER
2+
greater than E
+
2+
2MnO4 + 16H + 10Cl 2Mn + 8H2O + 5Cl2 (1)
(ii)
(b)
(i)
(ii)
0.0200 20.10
1000
Moles MnO4 =
-
2+
Moles Fe
2+
per 25.0 cm
2+
= 0.00201 mol Fe (1)
= 5 0.000402
200
2+
per 200 cm
= 0.00201 25 mol Fe
2+
= 0.01608 mol Fe (1)
3
4.47
= 6.00 100%
= 74.5% (1) ALLOW 74.7% / 75%
55
(c)
(i)
(ii)
(1)
any of these
the conditions (in the car battery) are not standard (1)
1
[11]
61.
(a)
(i)
(ii)
(iii)
3 +2 = +6
(b)
(i)
(ii)
pipette
ALLOW burette
NOT measuring cylinder
56
(iii)
24.0
2.4(0) 10 4
1000
OR 0.00024 (mol)
(iv)
2.40 10 4
4
2
1.2(0) 10 (mol) OR 0.00012 (mol)
(v)
1.2 10
1
3
1
[12]
62.
(a)
(b)
(c)
Reduction
ALLOW redox
(i)
(ii)
(d)
(i)
O H
2+
(1)
2
O N a
(+ 2 N a O H )
N H CO CH
(+ C H 3 C O 2 N a + H 2 O )
N H
57
(e)
(i)
QWC
(ii)
QWC OR
Hydrogen bonds in water are too strong
ALLOW carbon chain too long / large
ALLOW because of benzene ring
(f)
(g)
(i)
(ii)
C8H9O2N
Fully correct with charge
+
1
+
93C6H5O (1)
IGNORE charges unless both negative, then 1 max if fully correct
ACCEPT semi-structural formulae but NOT
+
O H
2
(h)
1
[20]
58
63.
(i)
or
ACCEPT
A ir
pum p
(ii)
(iii)
8H
4H2O
ACCEPT multiples
0.0004 (0)
1000
(1)
Number of moles of electrons
= 5 0.00040 = 0.002(0) (1)
Number of moles of vanadium ions
10 0.10
0.001
1000
(1)
(as vanadium(V) is formed by loss of 2 moles of electrons)
Oxidation number of vanadium in aerated solution is +3 (1)
(iv)
1
[7]
64.
(a)
The emf of a half-cell measured relative to the standard hydrogen electrode (1)
3
all solutions at 1 mol dm concentration and gases at 1 atm pressure / 101 kPa
and at a stated temperature / 298K (1)
Standalone mark
ALLOW pressure of 100 kPa
2
59
(b)
(c)
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
(i)
2+
OR
2Fe(s) + O2(g) + 2H2O(l) 2Fe(OH)2 (s)
Species (1)
balancing (1)
(ii)
QWC
(iii)
2+
E Zn / Zn more positive than for Fe
OR
q
E cell for Zn being oxidised by O2 is more positive than for Fe
being oxidised by O2
OR
65.
(a)
60
(b)
st
(c)
2 Step: Tin / iron and conc HCl (followed by addition of alkali) (1)
disallow Sn or Fe as catalyst
(i)
(ii)
+
AlBr3 + CH3CH2Br CH3CH2 + AlBr4 (1)
2
3
(1 ) fo r a rro w
H
In te rm e d ia te (1 )
CH 2C H
B r A lB r3
C H 2C H
+ H B r + A l B r3
(1 ) fo r a rro w fro m C H b o n d
O R
+
CH 2CH
(1 ) fo r a rro w
CH 2C H
CH 2CH
H
In te rm e d ia te (1 )
3
C H 2C H
H
(1 ) fo r a rro w
Arrows
+
Do not allow to C2H5
ALLOW to point / go to + charge
(3)
4
Electrophilic substitution
1
[13]
66.
(a)
(i)
61
(b)
(ii)
(i)
Fe
2+
Mn
2+
3+
(ii)
6
5
Fe
Mn
(c)
[Ar] 3d
2+
Shape (1)
Bonding to correct atoms (1)
(4)
(4)
CN
CN
N C
C N
N C
CN
Fe
Fe
O R
N C
CN
N C
CN
CN
CN
2
(d)
(loss of 4e ) (1)
\if 5 moles oxidised, total 20e Lost / change in oxidation no. = 20 (1)
(e)
2+
(i)
(ii)
(iii)
2+
2+
(1)
/ [V(H2O)6 ]
2+
/ [V(H2O)6 ] , (1)
3+
(1)
3
[16]
62
67.
(a)
(b)
(i)
(ii)
2
3
no. moles S 2 O 3 used = 12.5 0. 1 / 1000 = 1. 25 10 (1)
/ 2 = 6.25 10
(1)
(1)
(c)
QWC
(d)
(1) = 0.625
2
[14]
68.
(a)
(b)
C10H8
ALLOW (C5H4)2
NOT (C6H4)2
(i)
600
NOT + 600
NOT 600
63
(ii)
(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
(ii)
electrophilic (1)
substitution (1)
Can be given in any order
Mark independently
2
[9]
64
69.
(a)
(i)
Fe [Ar]
6 2
3d 4s
or 3d64s2
or 3d64s2
2
6
or 4s 3d (1)
2+
Fe
[Ar]
6
3d
or 3d6
6
or 3d 4s (1)
Letter d must be lower case
Any additional letters of numbers (0)
(ii)
(iii)
[Fe(H2O)6]
2+
OR
2+
65
(iv)
66
(v)
N2 + 3H2 /
2NH3
67
(b)
(i)
2+
2+
1 mol dm
Fe
IGNORE temperature
68
QWC*(ii)
2+
69
(iii)
70
(c)
2Fe
3+
2+
+ 2I 2Fe
3+
I will reduce Fe
3+
3+
/ Fe
2
[15]
71
70.
(a)
(i)
(ii)
1
No other Isomer allowed
OR
IGNORE bond to H of OH
72
(iii)
1
No ring substitution allowed
73
(b)
(i)
74
(ii)
75
(iii)
76
71.
(a)
(i)
77
(ii)
Substitution (1)
Electrophilic (1)
In any order
1 for each extra incorrect type eg addition as well as substitution
78
(iii)
79
(b)
(i)
80
(ii)
81
(c)
(i)
Substitution (1)
Nucleophilic (1)
IGNORE hydrolysis
NOT SN1
NOT hydrogenation
82
(ii)
second order
because the halogenoalkane is a primary one / two particles/both
reactants are involved in RDS (1)
83
(d)
84
(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]
85
72.
(a)
(i)
C3H5 (1)
7.2 / 24 = 0.3mol CO2 / 0.3 mol C (1)
4.5 2
4.5/18 = 0.25mol H2O / 18 = 0.5 mol / g H (1)
ALLOW deductions based on one calculation
3 .6
e.g. 0.5g H \ 3.6g C \ 12 = 0.3 mol C.
Follow through their reasoning if it logically arrives at the
correct ratio (2)
4 .1
4.1
4.1
3
e.g. 82 mol A 82 6 mol C 82 6 24 dm CO2 etc
86
(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
87
(iii)
88
(b)
89
73.
(a)
(i)
QWC*(ii)
1s 2s 2p 3s 3p 4s 3d
OR
2 2
6 2
6
5 1
1s 2s 2p 3s 3p 3d 4s
90
QWC*(b)
3+
2+
91
QWC*(c)
(i)
(ii)
Bidentate/chelate/bridging
92
93
94
(d)
(i)
(ii)
(iii)
ACCEPT multiples
Orange to green
ALLOW qualified green e.g. blue-green
NOT green to orange
1
[17]
Mark Scheme
95
74.
(a)
(i)
(ii)
SO3/ SO3H
2
1
96
(b)
(i)
OR C6H5Br
(ii)
(iii)
As oxygen lone pair is delocalised into ring / interacts with e in ring (1)
97
(c)
(i)
Ethylbenzene/Phenylethane
(ii)
98
(d)
(i)
UV/sun light
(ii)
1,2,3,4,5,6-(hexa)chloro cyclohexane
1
[13]
99
75.
(a)
(i)
(ii)
(iii)
100
(b)
(c)
101
(d)
(i)
(ii)
(iii)
(iv)
H
N
C H
C
3
CH
CH
C
3
2
[16]
102
76.
(a)
(i)
(ii)
(iii)
103
(b)
(i)
(ii)
B r 2 + A lB r 3
B r + A lB r 4
(1 )
B r
Br
Br
(1)
+H
(1) structure
(1) arrow
B rA lB r 3
(iii)
Br
H
Electrophilic substitution
1
[11]
104
77.
(a)
(b)
(c)
10
10
(i)
1s 2s 2p 3s 3p 3d 4s
(ii)
1s 2s 2p 3s 3p 3d
105
(d)
(i)
(ii)
2+
[Zn(H2O)6] + 2OH Zn(OH)2 + 6H2O
Or
2+
+
[Zn(H2O)6] + 2NH3 Zn(OH)2 + 2NH4 + 4H2O (1)
2+
2+
Zn(OH)2 + 4NH3 [Zn(NH3)4] + 2OH
(1) for cation formed
(1) for balancing equation with the correct species (2)
106
(e)
10
(i)
(ii)
is
1
[16]
107
78.
(a)
(i)
(ii)
One from:
Can only measure a potential difference
Or
So that comparisons can be made between any half cells
108
(b)
(i)
2+
109
(ii)
(iii)
Fizzing/bubbles (1)
(pink) colour lost / stays colourless (1)
(end point) solution remains pink / pale purple (1)
3
[12]
110
79.
(a)
6
solution
Sodium
carbonate
Bradys reagent (2,4-dinitro
phenyl hydrazine)
Potassium
dichromate +
sulphuric acid
X
fizzing/
effervescenc
e/ bubbles (1)
no change/
(stays)
yellow/orange
(1)
no change
/(stays)
orange (1)
Y
no reaction /
no bubbles (1)
yellow /orange / orangered or
yellow-orange
precipitate /
(crystalline) solid
(1)
Goes from orange to
green/
brownish
green/dull green
(1)
111
(b)
(i)
112
(ii)
113
(iii)
(iv)
(v)
114
(c)
(i)
Electrophiles / electrophilic
(ii)
Br / Br / Br Br
(iii)
(iv)
d+
d+
1
1
[17]
115
80.
(a)
116
(b)
(i)
Ni(CO)4
(ii)
117
(c)
(i)
2+
Ni(H2O)6
2+
(aq) + H2O(I)
118
(d)
(+)
()
(i)
(ii)
119
(iii)
(iv)
59 + 18 x + 17 (6 x) +71 = 234
232 + x = 234
x=2
([Ni(H2O)2(NH3)4]Cl2) Formula NOT needed for mark
2
[14]
120
81.
(a)
(i)
1s 2s 2p 3s 3p 3d 4s
(ii)
1s 2s 2p 3s 3p 3d
1
1
121
(b)
H 2O
O H
O H
O H
N i
H 2O
O H
(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
122
(c)
(i)
[Ni(H2O)4(OH)2]
ALLOW Ni(OH)2
123
(ii)
Deprotonation (1)
two successive deprotonations / neutral species producing insoluble
compound (1)
2
124
(iii)
2
[10]
125
82.
(a)
(i)
and Fe
to Fe by Zn (E
cell
3+
2+
to Fe
by Zn (E
cell
= + 1.53V) (1)
= +0.32V)(1)
126
(ii)
Reduction of Fe
2+
127
(b)
(i)
2+
2+
Mn O4 + 5Fe + 8H Mn
Species (1)
Balance (1)
Any state symbols ignored.
+ 5Fe
3+
+ 4H2O
2
128
(ii)
129
(c)
st
mol (1)
2+
2+
in 2
= 3.64 10
Amount Fe
Amount Fe
nd
titration = amount of Fe
2+
3+
3+
and Fe
3
mol (1)
mol
mol (1)
3+
nd
2+
3+
(1)
130
OR
3+
rd
Volume MnO4 for Fe , which has been reduced by zinc (1) 3 point
3
th
Amount Fe
point
= 1.42 10
st
mol (1) 1
nd
mol (1) 2
131
(d)
(i)
[Fe(H2O)6]
2+
132
(ii)
[Fe(H2O)6]
3+
3+
2+
2+
(1)
(1)
3
[20]
133
83.
(a)
[If reagents wrong way round, end point must be pink to colourless]
134
(b)
(i)
2+
Fe
Fe
3+
+e
1
2+
MnO4 + 8H + 5e Mn
(ii)
MnO4 + 8H + 5Fe
2+
+ 4H2O
Mn
2+
1
3
+ 4H2O + 5Fe
135
(iii)
Amount MnO4
2+
Amount Fe
= 0.0200
136
(c)
3+
2+
3+
Therefore can oxidise iron, the reduced form of other redox couple (1)
3
[14]
137
84.
(a)
(i)
(ii)
1
Allow single headed arrows or other suitable notation
[Mark (ii) consequentially on (i)]
138
(b)
(i)
Covalent (1)
Coordinate or dative (1)
(ii)
Deprotonation or acid-base
(iii)
[Cr(H2O)3(OH)3] or Cr(OH)3
(iv)
(v)
[Cr(NH3)6]
3+
or [Cr(OH)x (H2O)y(NH3)z]
charge
139
(c)
140
85.
(a)
(i)
141
(ii)
+
HNO3 + 2H2SO4 H3O + 2HSO4 + NO2 (1)
N O 2+
N O
+
(1 )
(1 ) fo r in te r m e d ia te
H
(1 )
N O
(+ 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)
142
(iii)
Electrophilic substitution
143
(b)
3
N O
N O
N O
N O
(1 )
N O
N O
N O
(1 )
O 2N
N O
(1)
144
(c)
(1)
2
145
H
N
(d)
(i)
H
C
H
N H
Allow:
H
1
C
C H
146
(ii)
147
86.
(a)
(i)
[Ar]3d (1)
2
allow 1s etc
148
(b)
(i)
149
(ii)
150
(c)
2+
(i)
Co(H2O)6
(1)
(ii)
Example:
2+
2Co(H2O)6 + 4Cl CoCl4 + 6 H2O
Any valid equation that shows a ligand exchange but begins with
2+
Co(H2O)6 (1)
ligand exchange correctly balanced (1)
2
[9]
151
87.
(a)
An element that has at least one of its ions has an incomplete d shell (1) 1
152
(b)
(i)
153
(ii)
2+
Cr(H2O)6
Not Cr
2+
or Cr(II).
154
(c)
(i)
C r
C l
1 9 .5 / 5 2
4 0 / 3 5 .5
0 .3 7 5
1 .1 2 7
0 .3 7 5 /0 .3 7 5
1 .1 2 7 /0 .3 7 5
1
3
NB 2 method marks
H 2O
4 0 .5 / 1 8 ( 1 )
2 .2 5
2 .2 5 / 0 .3 7 5 ( 1 )
6
155
(ii)
3+
[8]
156
88.
(a)
(i)
157
C H 3CO C l
CH 3C O
A lC l 3
C H 3C O
C O CH
(1 )
+
A lC l 4 (1 )
H
(1 )
( A lC l 4)
(1 )
C O CH
+ H C l (+ A lC l 3 )
(ii)
Marks:
formation of electrophile
attack on electrophile from ring
intermediate
removal of proton
158
(b)
O
(1)
159
O H
O H
O H
O H
O H
(c)
O H
(i)
160
O
O
O
CH
(ii)
Ester link (1)
polymer / with correct benzene ring links (1)
161
(d)
162
89.
(a)
H
O
H
H
Fully displayed showing all C, H and circle or kekul structure.
163
(b)
164
(c)
O CH
N O
165
(d)
C7H7OBr
C7H6OBr2
C7H5OBr3
HBr
)
) Any two
)
)
166
(e)
(i)
Methoxybenzenesulph/fonic acid
(ii)
Detergents/drugs/dyes
167
(f)
(i)
(ii)
D
E
hydrogen / H2 (1)
(Raney) nickel / nickle / Ni /Platinum /Pt (1)
Addition (1)
Reduction (1)
2
2
168
(g)
(i)
Petroleum/crude oil/coal
(ii)
1
[14]
169
90.
(a)
Sc
[A r]
Cr
[A r]
Cr
3+
[A r]
Cr
3+
170
(b)
171
[A r]
(c)
L ig a n d e le c tro n s
(i)
2
Correct electron structure for complex ion (1)
ligand electrons identified (1) 6 pairs identified stand alone mark
3+
Consequential on structure of Cr
172
H 2O
H 2O
(ii)
O H
3
2
C r
O H
O H
O H
173
(iii)
174
(d)
(i)
175
(ii)
1
[14]
176
91.
(a)
2-
2S2O3 + l2 S4O6+
177
(b)
178
(c)
(i)
179
(ii)
180
N (C l) +
O H
O H + H
(C l
o r H C l)
(iii)
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)
181
C onc H N O 3+
conc H 2SO 4
3 0 to
5 5 C
(d)
(1 )
S n (1 ) + c o n c
H C l (1 )
(1 )
N O
heat
(1 )
(1 )
N H
182
92.
(a)
(i)
(ii)
Fluorine or F2 (1)
183
(b)
(i)
all/listed (1)
(ii)
(iii)
2
[7]
184
93.
(a)
CH3CO (1)
Candidate may not identify electophile but may score this mark if they use
the correct electrophile in the mechanism
+
O C CH
A l C l 4H
CO CH
(1 )
(1 )
C O CH
3
+
H C l
CH3CO Cl AlCl3
185
(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.
(1 )
+
O C CH
A l C l 4H
CO CH
(1 )
(1 )
CO CH
3
+
H Cl
186
(c)
There are several routes through this; all can score full marks
C H
C N
C H
O H
(1 )
(1 )
+ H C N
D ilu te H C l ( 1 ) H e a t 9 u n d e r
r e f lu x ) (1 )
or
D ilu te N a O H (1 ) f o llo w e d
b y a c id (1 )
C O 2H
C H
O H
5
[10]
187
3d
M n
94.
(a)
M n
4s
[A r]
2+
[A r]
188
(b)
2+
(i)
[Mn(H2O)6]
(ii)
[Mn(H2O)6]
2+
2+
2+
2+
or
[Mn(H2O)6]
or
[Mn(H2O)6]
or
[Mn(H2O)6]
Any of above score 2 marks as follows:(1) mark for species (1) mark
for balance
Deprotonation or Acid /base (1)
189
(iii)
(c)
(i)
from +4 to +6/ up by 2 / +2
(ii)
= 4.925 10 mol
190
(iii)
Amount of SO3
= 1.231 x 10
(iv)
mol
2
Amount of SO3
in 250cm = 10 1.231 10
mol (1)
= 1.231 10 mol
2
Mass of pure Na2SO3 = 126 x 1.231 10 g (1)
= 1.551g
(v)
1
[16]
191
95.
(a)
(i)
(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
192
6C + 3H
C 6H
H 1
(b)
H 2
6C O
+ 3H 2O
193
(c)
Benzene has p electrons delocalised (1) Therefore bond energy NOT that of C
C or C=C
lo c a lis e d (1 )
E n e rg y
+215
D e lo c a lis e d (1 ) c o n s e q u e n tia l
+51
6 C (s) + 3 H 2(g )
4
194
(d)
(i)
rate = k[benzene][bromine]
(ii)
195
96.
(a)
(i)
*CH(CH3) (1)
(ii)
196
C H 2 C H (C H 3 )N H
(b)
(C l )
(i)
1
Can use R in place of C6H5CH2CH(CH3) in both (i) and (ii)
197
(ii)
C H 2 C H (C H 3 )N
C H
(1 )
198
O
CH
C
O
(iii)
C H 2 C H (C H 3 )
C H
199
N H CH
C
(d)
H
C
C
N H C H
200
(e)
(i)
(CH(CH3)NH2)
(ii)
(1)
1
+
1
[11]
201