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1.

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]

Al khor International School

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]

Al khor International School

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

OK if 6 waters shown on l.h.s.

_
+
+ 2H + e NO2 + H2O

OR
_
NO 3
+
2
+ 4H + 2e 2NO2 + 2H2O (1)
OR

NO 3

_
+
+ 4H + 2e N2O4 + 2H2O (1)

Ignore the full equation if it is given as well


Allow equations written as reverse of above
Ignore state symbols even if wrong
Allow for
(iii)

(electrode potential) values are for standard conditions (1)


nitric acid is concentrated / not 1 mol dm

/ not 1 M (1)

Allow temperature not stated for second mark


NO3 are not 1 mol dm

Any reference to loss of NO2


(b)

(i)

initially a (pale/light) blue precipitate (1)


Allow blue solid
Ignore white precipitate
(re-dissolves in excess to form) a (deep) blue
solution (1) Stand alone mark
Accept any shade of blue except greenish-blue

Any colour (other than blue) precipitate in blue solution

Al khor International School

(ii)

2+

2+

Cu (aq) + 2OH (aq) Cu(OH)2(s) (1)


Zn (aq) + 2OH (aq) Zn(OH)2(s) (1)

Zn(OH)2(s) + 2OH (aq) Zn(OH)4

(aq) (1)

If two previous equations combined correctly

2+
2
then (1) only : Zn + 4OH Zn(OH)4
Allow

2
Zn(OH)2(s) + 2OH (aq) ZnO2 (aq)+ 2H2O(l)
OR

Zn(OH)2(s) + 4OH (aq) Zn(OH)6

(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+

+ 4NH3 etc (1)

Allow any number of ammonias from 1 to 6


Allow balanced equations, ionic or full.
Ligand exchange reaction must start with a complex ion
Note:
If zinc mentioned initially but equation refers to a correct compound
then credit should be given
If equations wrong but words are correct then ignore equations

Reference to zinc ions or zinc metal


Do not allow deprotonation

Al khor International School

(c)

(i)

I2 + 2S2O3

2I + S4O6

Ignore state symbols even if wrong.

Non-ionic equation.
(ii)

QWC
Amount thiosulphate
3

= 0.0331 dm 0.1 mol dm

= 0.00331 mol (1)


3

= amount of copper(II) ions in 25 cm portion (1)


amount Cu = 10 0.00331= 0.0331 mol in total (1)
mass Cu = 0.0331 mol 63.5 g mol1 (1)

= 2.102 g
% copper = (2.102 x 100) 3.00 (1)

= 70.1% (1) to 3 s.f. only


Mark consequentially but if % > 100 then (-1)
If equation in (i) is incorrect but used correctly in part (ii) then all marks
can be scored unless answer > 100%
Correct answer can score 6 marks irrespective of the stoichiometry of
the equation in (c)(i)
If candidates uses 64 for molar mass of Cu final answer will be 70.6;
scores max of 5
6
70.06 or 70.0
(iii)

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]

Al khor International School

22.

(a)

(i)

H2SO4 + HNO3 NO2 + H2O + HSO4

OR
+

H2SO4 + HNO3 H2NO3 + HSO4


+

H2NO3 NO2 + H2O


Both needed
OR
+

2H2SO4 + HNO2 NO2 H2O + 2HSO

(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

Delocalisation mustnt go over C where NO2 is attached

Al khor International School

(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

Reject hydroxide for first mark only


Nucleophilic attack on the ring
Makes it more reactive on its own
(iii)

tin (1) and concentrated hydrochloric acid (1)


Formulae acceptable.
If NaOH is added after HCl then ignore; if implication that HCI and
NaOH are added together then second mark is lost
OR
nd

iron (1) and concentrated hydrochloric acid (1) 2


conditional on a metal

mark

OR
hydrogen (1) and platinum / palladium catalyst (1)

lithium aluminium hydride sodium borohydride


Nickel Raney Nickel
(iv)

ethanoyl chloride OR acetyl chloride OR


CH3COCl OR equivalent displayed formula
OR
ethanoic anhydride OR acetic anhydride OR
(CH3CO)2O OR equivalent displayed formula
Right name but wrong formula does not score
Ignore minor spelling errors if the formula is correct

Al khor International School

(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

Passed over; anything that implies external heating with a


steam bath or water bath
any implication of fractional distillation
any suggestion that separation based on differing boiling
temperature
water-soluble
(c)

Read the whole answer to get the sense


The (ring) hydrogen atoms are on carbon atoms which have one / a hydrogen
on an adjacent carbon atom, so are doublets (1)
All the other hydrogen atoms have no adjacent hydrogen (bearing carbon)
atoms, so are singlets (1)
2
nearby
[14]

23.

(a)

(i)

Any TWO of:


complex ions / complexes (1)
coloured ions / compounds / solutions (1)
catalytic properties (1)
paramagnetic (1)
Allow
coloured complexes (2)
coloured complex compound (1)
If a list appears with 1 or 2 correct properties followed by properties
related to the element, then (1) mark only
Ignore partially filled d-orbitals

complex compounds

Al khor International School

(ii)

ignore absence of charge


clearly octahedral (ignore bonds to the H in H2O) (1) but allow some
latitude in the symbols used to show the 3D structure.
Wedges do not have to be exact if used they are enough to show
3D if the axial bonds are lines
The word octahedral does not salvage a poor drawing
dative (covalent) / coordinate (bond) (1)
not just shown by an arrow
lone pair (of electrons on the oxygen) (1)
can be shown on the diagram
(b)

(i)

(+) 0.34 (V) OR (+) 0,34 V


sign not needed

(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

reaction not feasible since the potential is negative (2


o
for an answer consistent with sign of E ) (1)

mark is
2
[10]

Al khor International School

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.

Is not optically active


(c)

(C=C): add bromine (water) (1)


decolourises (1)
OR
KMnO4 (1)
purple brown / colourless (1)
(C=O): add 2,4-dnp / 2,4dinitrophenylhydrazine/ Bradys reagent (1)
orange or yellow or orange-red or red ppt (1)
Ignore a negative Fehlings / Tollens test
If a positive Fehlings / Tollens is given in addition to 2,4 DNP
then third and fourth marks are lost
Observation dependent on test

1,4-dnp

Al khor International School

10

(d)

(i)

amount of carvone = (4.5 150) mol = 0.03 mol (1)


amount of hydrogen = (1.44 24) mol = 0.06 mol
st

(allow 1 mark for either of the mole calculations)


so two double bonds are reduced (1)
OR
2 moles H2 : (1 mol carvone)
OR
4 mole H : (1 mol carvone)
If hydrogen is used it must be clear whether they are atoms or molecules
This mark can be salvaged if the structure is correct and both double
bonds are reduced

(1) stand alone


Accept displayed formula if completely correct

Any structure that shows reduction of the C=O bond


(ii)

(a ketone/C=O) absorption / peak / trough / within the range 1680


1
1700 (cm ) (1)
Ignore units
will be seen in carvone but not in limonene / the reduction product (1)
omission of the value for the absorption loses first mark only
1720 - 1740 cm

Al khor International School

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

Any structure retaining C=C bonds


(ii)

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

Al khor International School

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)
+

Arrow from O of intermediate to H (1)


planar molecule attacked from either side to give a racemic mixture
OR
molecule equally attacked from either side to give a racemic
mixture (1)

If H-X used then -1


(ii)

heterogeneous catalysts can be filtered off OR do not appear in any


liquid or gaseous products
OR are easy to separate OR are stereospecific
OR suited to continuous processes rather than batch processes
1
greater surface area
[23]

Al khor International School

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]

Al khor International School

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)

MnO4 needs acid to be reduced to Mn

(b)

Al khor International School

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

0.01 mol in 1000 cm


1
1000 1.79 10 4

4
5
\ 5 1.79 10 in 0.01
= 3.58
3

(iii)

(d)

= 3.6 cm (1)

No, titration value too low


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

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

Al khor International School

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
+

Br2 + FeBr3 Br + FeBr4 / d+ d


Br FeBr4 (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)

(c)

(iii)

FeBr4 + H FeBr3 + HBr

(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)

Al khor International School

17

(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)

(d)

Three / 3

3
1
[17]

42.

(a)

(i)

Fe[Ar] 3d 4s in either order, allowing superscripts to be subscripts


6
6 0
Fe[Ar] 3d or 3d 4s in either order, allowing
superscripts to be subscripts
Letter d must be lower case
1
Reject any other letters

(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

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


IGNORE charge unless incorrect

Al khor International School

18

(iii)

[Fe(H2O)6]

2+

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

2+

+ 2OH Fe(OH)2 + 6H2O

OR
[Fe(H2O)6]
(iv)

Green precipitate/solid Foxy-red/red-brown/


brown/orange
Both colours and precipitate/solid needed

Reject just Darkens


(b)

(i)

QWC
Emf of cell/ potential difference of cell containing Fe (1)
dipping into a 1 mol dm

2+

Fe

solution (1)

And standard hydrogen electrode/half cell


3 +
OR hydrogen electrode and 1 mol dm H and 1 atm
H2
OR description of standard hydrogen electrode (1)
IGNORE temperature

RejectSHE
(ii)

QWC
Emf of hydrogen electrode is zero stated or implied
e.g. if calculate Ecell = +0.44 V (1)

(iii)

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)

High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions

1
[10]

43.

(a)

QWC
Many OH groups (1)
which can hydrogen bond to water (1)

Al khor International School

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

Reject amide link as CONH


(iii)

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)

Al khor International School

20

(d)

Ethenol: Addition
Fibre: Condensation

1
[10]

44.

(a)

(i)

(ii)

An element which forms ions in at least one of its compounds


which have a partly filled shell of d electrons (1)

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

Any mention of light emitted scores zero


(b)

(i)

Red Cu2O (1)

(ii)

Benedicts/Fehlings (solution) (1)


Accept recognisable phonetic spelling eg Felings, Benedicks,
Benedikts
Aldehyde (1)

Reject failings
(c)

FeO is 2+ not 3+ (1)


3+
Os has too large a radius (1)

Al khor International School

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

E for reagent must be more positive than 1.6 V

E for reagent must be more negative than 0.7 V.


Do not allow a reducing agent that reacts with water.
Colour change
Do not penalise lack of green twice.
Complex formation
e.g. formation of

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)

Al khor International School

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]

Al khor International School

23

45.

(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
3

(solutions at) 1 mol dm concentration, (gases at) 1 atm/100 kPa/


105Pa/ 1 Bar pressure and stated temperature (1)
all 3 conditions needed STAND ALONE

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

Reject just electron source and sink


Reject to make comparisons between half cells

Al khor International School

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)

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)
rd

3 mark must be cq on sign of Ecell


(iii)

activation energy of the reaction may be high


OR
reaction too slow to be observed

Reject just Not enough energy to overcome the activation


energy
Reject conditions are non-standard
Reject just kinetically stable
[9]

46.

(a)

(i)

(anhydrous) aluminium chloride


[Name or formulae]

Accept Al2Cl6
Accept AlBr3 FeBr3
Accept FeCl3
Reject Fe

Al khor International School

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 )

Al khor International School

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)

Accept either a delocalised or Kekule ring


+

st

If CH3CHBrCH3 CH3CH CH3 + Br loses 1 mark but


nd

rd

th

can score 2 , 3 and 4 marks

(b)

(i)

CH3CH2CH

2+

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)

Reject any reference to stability of intermediate /product

Al khor International School

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)

below 0 C reaction is too slow (1)


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

Accept HNO2 decomposes


(iii)

O H
N=N link, can be shown linear (1)
IGNORE other atoms
Remainder correct (1)

IGNORE position of OH group.

Accept ONa or O instead of OH


Reject N=NO

Al khor International School

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
+

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)

Al khor International School

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

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]

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

Al khor International School

30

(ii)

all the others are 4s / 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)

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

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

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

3+
+
[Cr(H2O)6] + 2OH [Cr(H2O)4(OH)2] + 2H2O
OR
3+

[Cr(H2O)6] + 3OH Cr(OH)3 + 6H2O


OR

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

Al khor International School

31

(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
nd

2
(v)

mark is conditional on an initial ppt

acid / acidic

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


nd
th
by 2 for 2 mark and not multiplying by 2 for 4 mark
3
3
amount thiosulphate in titre = 0.0372 dm 0.100 mol dm
3
= 3.72 10 mol (1)
3.72 10 3
3
2
amount I2 =
(1) = 1.86 10 mol
nd

mark cq on amount thiosulphate


3

amount dichromate in 25 cm
1.86 10 3
4
3
=
(1) = 6.2 10 mol
rd

3 mark cq on amount I2
4

Total mass Cr = 6.2 10 mol 2 10 52 g mol


= 0.645 g
th
4 mark cq on amount dichromate

(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 %

Al khor International School

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)

amount dichromate = 6.2 10


mass Cr = 6.2 10
= 0.645 g

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)

Colour at the end point would be green which


would prevent the loss of iodine colour being seen
OR
3+
colour change at end point would be disguised by the colour of Cr 1
Accept chromium instead of Cr

3+
2

Reject end point disguised by colour of Cr2O7 /orange


[16]

48.

(a)

(i)

The activation energy for the reaction is high


or to ensure that more molecules have E Ea.

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)

Al khor International School

33

(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)

Accept butyl group


(iv)

Removes acid

Accept neutralises HCl /HBr


Accept neutralises acid
(v)

Removes water

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.

Reject volatile for flammable

Al khor International School

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)

Statement that the reaction is SN1 alone scores zero.

(i)

Orange green

(ii)

Cr2O7

+ 6e + 14H 2Cr

3+

+ 7H2O (1)
+

(3CH3CH(OH)CH2CH3 3CH3COCH2CH3 + 6H + 6e )
2

Cr2O7 + 3CH3CH(OH)CH2CH3 + 8H 2Cr


3CH3COCH2CH3 (1)

3+

+ 7H2O +

No consequential marking on incorrect equations.

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 cm

due to OH (1)

Accept 3230 3550


Reject broad transmission
has disappeared in the product to be replaced by C=O at 1700 cm

(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)

Al khor International School

35

(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

Reject ..so gets more acidic


(ii)

lower pH/pH falls

Reject mixture is more acidic for lower pH


[20]

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)

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)

(b)

(i)

Friedel-Craft(s)
Accept phonetic spelling

Accept alkylation

Al khor International School

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)

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)

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)

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 2
mark)

Al khor International School

nd

37

(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
3
1 g = 216 mol = 4.854 10 mol
mass CO2 produced from 13 C
= 13 44 4.854 10

= 2.78 g (1)

mass H2O from 18 H


= 9 18 4.854 10

= 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)

(Aspirin and ibuprofen) both contain same (types of)


bond(s)(so absorb at same frequency/wavenumber)

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 cm
different type of bond to X and Z)

(so must contain


1

Reject CH in arene = 3030 as present in both


Reject 17001630 (amide)

Al khor International School

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

Accept delocalised carboxylate group with a negative


charge shown
Reject compressed structural formula

Al khor International School

39

(ii)

(H from) COOH (group) protonates the NH2(group)

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

(b)

(i)

NH3CH2COOH / H3NCH2COOH / H3NCH2COOH

OR written right to left


OR
O

O H
C

C
+
N H

H
3

Accept CO2H
OR
+
NH3 Cl
Or NH3Cl
Reject molecular formula

Al khor International School

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

Al khor International School

41

(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

(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

(d)

H2N(CH2)6NH2 (1)
ClOC(CH2)4COCl /
O
O
C lC (C H 2 )4 C

C l (1)

[Monomers can be given in either order]

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]

Al khor International School

42

52.

(a)

(i)

S O 3H

Bond from benzene ring must be to the sulphur atom


Hydrogen atom must be linked to oxygen

Accept C6H5SO3H
Accept C6H5SO2OH
Reject C6H5HSO3
(ii)

Fuming sulphuric acid / oleum / sulphur trioxide / SO3 / sulphur


trioxide or SO3 in sulphuric acid

Accept concentrated sulphuric acid / H2S2O7


Reject H2SO4 / H2SO4(aq) / sulphuric acid / dilute
sulphuric acid
(iii)

(aromatic) Electrophilic substitution

Accept Electrophillic / Electrophylic / Eletrophilic


substitution
Reject Electrophic substitution

(iv)

SO3/ SO3H
Ignore name if given with formula
Accept HSO3

+
+

Reject sulphur trioxide / SO3 / SO3


(b)

(i)

S O 3H

H 3C

CH

Allow TE from (a)(i)


Accept

S O 3H

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

Al khor International School

43

(ii)

Reagent X: CH3Cl (1)


Catalyst Y: AlCl3 (1)
Allow TE from (b)(i) e.g. CH3CH2Cl if an ethylbenzene

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

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


Reject hydrochloric acid
(c)

(i)

4-chloro-3, 5-dimethylphenol
3,5-dimethyl-4-chlorophenol

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

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]

53.

(a)

(i)

uses E values to find Ereaction = (+) 1.57 (V) (1)


Reject 1.57

2+

Zn + 2NO3 + 4H Zn

+ 2NO2 + 2H2O (1)

Accept equation with equilibrium sign


Rejection equation with Zn on the right

Al khor International School

44

(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)


(iii)

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)

ligand exchange/replacement/substitution (1)


2+

[Cu(H2O)6] + 4Cl
OR
2+
[Cu(H2O)6] + 4HCl

CuCl4

CuCl4

+ 6H2O (1)

+ 4H + 6H2O (1)

ALLOW
+

Accept H2CuCl4 + 2H for CuCl4

(b)

(i)

+ 4H

E for the reaction is 0.39 (V) (so not feasible) [value is required]. 1
2+

Accept Cu 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)

Reject just conditions not standard

Al khor International School

45

(iii)

[Cu(NH3)4]

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

Accept [Cu(NH3)2]

Reject [Cu(NH3)6]

Reject any 2+ complex


(iv)

(atmospheric) oxygen (1)


+

oxidises Cu to Cu

2+

(1)

Reject air for oxygen


(c)

(i)

starch (1)
blue-black/blue/black to colourless (1)

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.

(iii)

Amount thiosulphate = 0.01655 dm 0.1 mol dm (1)


= amount Cu

2+
2+

amount of Cu

mol (1)

10 (1)

in 25.0 cm = 1.655 10
in 250 cm = 1.655 10

mass of Cu (in sample) = 1.655 10

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]

Al khor International School

46

54.

(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

(b)

Mark independently

(i)

(free) radical substitution

(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.

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]

Reject just heat, Bunsen


[10]

Al khor International School

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+

combine the halfreactions to get 2Cu Cu


IGNORE state symbols

+ 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

Reject just > 0.3 (V)


(iii)

activation energy (for the disproportionation) is high


OR
+
Cu is kinetically stable

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)

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)

Accept Cu2SO4(OH)2
Accept Cu2(OH)2SO4
Accept (CuOH)2SO4
Reject HSO4 instead of SO4

Al khor International School

48

(iii)

[Cu(NH3)4(H2O)2]

2+

Accept [Cu(NH3)4]

2+

2+

Reject [Cu(NH3)6]

(d)

(iv)

ligand exchange / ligand substitution

(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

Reject any identification method based on IR, NMR or


mass for last 2 marks
(ii)

the aldehyde is distilled off as it is formed

Reject any mention of reflux


Reject just the aldehyde is distilled off
(iii)

propanoic acid OR CH3CH2COOH OR CH3CH2CO2H

Accept C2H5 for CH3CH2


(iv)

(v)

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

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


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

Accept reverse argument for low pressure


[20]

Al khor International School

49

56.

(a)

(i)
(ii)

methylbenzene/phenylmethane
C H

SO

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
(b)

(i)

(conc.) nitric acid (1)


Accept HNO3
Reject dilute, HNO3 (aq)
(conc.) sulphuric acid (1) Mark independently

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)

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)

Al khor International School

50

(d)

Oxidation

1
Accept partial oxidation
Reject redox
Reject full oxidation

(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)

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)

Conc(entrated) / fuming sulphuric acid / sulphur trioxide / SO3 (1)

Accept oleum (1)


Reject sulphuric acid / H2SO4
(ii)

(b)

(i)

Substitution (1)
Electrophilic (1)

To avoid losing too much vanillin (in the filtrate when


crystallisation occurs) OWTTE

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)

Al khor International School

51

(iii)

Measure mpt (1)


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

(c)

nd

mark

Vanillin is likely to be a product since ..


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

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)

Allow instead of and instead of

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


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

(i)

Dative (covalent) OR co-ordinate (1)


Covalent (1)

(ii)

[Ni(H2O)6]
OR

2+

+ 2NH3 [Ni(OH)2(H2O4)] + 2NH 4

2+

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


OR
2+

[Ni(H2O)6] + 2OH [Ni(OH)2(H2O4)] + 2H2O


OR

2+
[Ni(H2O)6] + 2OH Ni(OH)2 + 6H2O
IGNORE state symbols
IGNORE missing square brackets in any formula

(iii)

H removed (by NH3 OR OH ) (1)


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

Al khor International School

52

(iv)

(v)

Ligand exchange
OR ligand replacement
OR ligand substitution

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

2+

+ 2OH + 4H2O

OR
2+

+ 2OH

2+

OR [Ni(NH3)4(H2O)2]

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

2+

Allow formation of [Ni(NH3)4]


cation formed (1)
balancing equation (1)
(d)
QWC

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


ALLOW d-sublevel
absorbs light (in visible region) (1)
NOT uv light
electron is promoted OR electron moves to a higher energy level (1)
st

Any mention of emission of light can only score 1 mark

3
[14]

59.

(a)

(i)

White precipitate OR white suspension OR white solid

(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

C = O in ester must be shown

Al khor International School

53

(iv)

(b)

(c)

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

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

(i)

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


NOT JUST HNO2

Hydrochloric acid OR dilute sulphuric acid OR aqueous


sulphuric acid

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)
NOT HNO2 decomposes

(iii)
N = N

O H
O R O
in s te a d o f
O H g ro u p

(iv)
QWC

Dissolve in minimum volume of boiling solvent OR dissolve in


minimum volume of hot solvent (1)
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]

Al khor International School

54

60.

(a)

(i)

EITHER

2+

E = (+) 0.15 (V) OR E (MnO4 / Mn ) 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

+
2+
2MnO4 + 16H + 10Cl 2Mn + 8H2O + 5Cl2 (1)

(ii)

(b)

(i)

(ii)

E = (+) 0.15(V) (1)

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
2+
IGNORE references to Mn

(Multiply iron half-equation by five to) cancel out electrons


OR balance electrons

0.0200 20.10
1000
Moles MnO4 =
-

= 0.000402 mol MnO4 (1)


Moles Fe

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

Mass of FeSO4 . 7H2O


= 0.01608 278
= 4.47g or via concentrations (1)
Percentage purity

4.47
= 6.00 100%
= 74.5% (1) ALLOW 74.7% / 75%

Correct answer + working (5)


ALLOW 2 or more sig figs
6.00
If start by dividing 278 , and final answer is incorrect, candidate can
access first three marks only.
If third step omitted, answer 9.3% OR 9.33% OR 9.4%

Al khor International School

55

(c)

(i)

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


Correct answer alone (1)

PbSO 4 precipitated (1)


[H

( aq) ] not 1 mol dm

(ii)

(1)

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]

61.

(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)
nd
st
2 mark is dependent on 1
2

(ii)

(iii)

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
1 6 = 6,

3 +2 = +6

ALLOW TE from (ii)

OR total change in oxidation number of +6 for S, 6 for I

(b)

(i)

(ii)

ACCEPT justification in terms of electrons

pipette
ALLOW burette
NOT measuring cylinder

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

Al khor International School

56

(iii)

24.0
2.4(0) 10 4
1000

OR 0.00024 (mol)

The mark is for the answer

(iv)

2.40 10 4

4
2
1.2(0) 10 (mol) OR 0.00012 (mol)

ALLOW TE from (iii)


The mark is for the answer

(v)

1.2 10

1
3

100 = 0.012(0) (mol dm )

ALLOW TE from (iv)


The mark is for the answer

1
[12]

62.

(a)

(b)

(c)

Nitric acid / HNO3 (1)


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

Reduction
ALLOW redox

(i)

(ii)

(d)

(i)

4() aminophenol / 4()hydroxyphenylamine


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

O H

2+

(1)
2

O N a
(+ 2 N a O H )

N H CO CH

Organic formula fully correct (2)


Only one group reacting (1)
(ii)

(+ C H 3 C O 2 N a + H 2 O )
N H

No because, phenol is not a strong enough acid to react with sodium


carbonate (1)
NOT because phenol is a weak acid
1

Al khor International School

57

(e)

(i)

QWC

Van der Waals and (permanent) dipole (permanent) dipole, and


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
(f)

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


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

(g)

(i)

(ii)

C8H9O2N
Fully correct with charge
+

43CH3CO / C2H3O / CHNO

1
+

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

+
O H
2
(h)

No gastric / internal bleeding / suitable for younger children

1
[20]

Al khor International School

58

63.

(i)

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


through stopper into solution
eg
pum p
pum p

or

ACCEPT
A ir
pum p

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

(ii)

(iii)

8H
4H2O
ACCEPT multiples

Number of moles of manganate(VII) ion


20 0.020

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)

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


OR
It is self-indicating

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

Al khor International School

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)

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

2+

(aq) + 4OH (aq) or multiples

OR
2Fe(s) + O2(g) + 2H2O(l) 2Fe(OH)2 (s)
Species (1)
balancing (1)

(ii)

QWC

(iii)

Do not allow species mark if electrons still in equation, but allow


balancing mark if 4e on both sides

DE react = (+) 0.84 (V) (1)


Greater than zero therefore feasible (1)

Zn oxidises preferentially to Fe / Zinc acts as sacrificial (anode) (1)


If Sn used (and damaged), Fe oxidises; preferentially (1)
Disallow oxidises more readily
2+
E Zn / Zn more negative than for Fe
OR

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

similar E arguments related to preferential oxidation with Sn (1)


3
disallow higher or bigger for more negative or more positive
[10]

65.

(a)

Delocalisation / p-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 p / double bonds / cyclohexatriene,
Kekule structure (1)
Standalone mark
3

Al khor International School

60

(b)

st

1 step: sulphuric and nitric acid (1)


concentrated (1)
Intermediate: Nitrobenzene /C6H5NO2 (1)
nd

(c)

2 Step: Tin / iron and conc HCl (followed by addition of alkali) (1)
disallow Sn or Fe as catalyst

(i)

AlBr3 / FeBr3 / AlCl3 / Al2Cl6 / FeCl3 / Fe2Cl6

(ii)

+
AlBr3 + CH3CH2Br CH3CH2 + AlBr4 (1)

ALLOW C2H5 in this equation only


+
CH 2CH

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

ALLOW C2H5 in intermediate


(iii)

Electrophilic substitution

1
[13]

66.

(a)

(i)

Forms ions which have partially filled d-orbitals


OR
Forms ions which have a partially filled d-subshell

Al khor International School

61

(b)

(ii)

Scandiurn / Sc and Zinc / Zn

(i)

Fe

2+

Mn

2+

3+

(ii)

6
5

[Ar] 3d (1) for both correct

Fe

Mn
(c)

[Ar] 3d

is 3d / half filled d-subshell which is more stable than 3d (1)

2+

is (already) 3d (which is more stable than 3d ) (1)

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)

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) / Mn

(e)

2+

(1) NOT standalone mark


+

(i)

VO3 + 2H / 2H3O VO2 + H2O / 3H2O

(ii)

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


unchanged (at +5)

(iii)

First green colour : VO2 and VO


3+

Second green colour : V


Violet colour : V

2+

2+

(1)

/ [V(H2O)6 ]
2+

/ [V(H2O)6 ] , (1)

3+

(1)
3
[16]

Al khor International School

62

67.

(a)

3OCl 2Cl + ClO3 (1)

(b)

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)

(i)

blue / black to colourless

(ii)

2
3
no. moles S 2 O 3 used = 12.5 0. 1 / 1000 = 1. 25 10 (1)

no. moles I2 = 1.25 10

/ 2 = 6.25 10

(1)

no. moles ClO = no. moles 12 (1)


3

no. moles ClO in original 10 cm = 10 6.25 10


= 6.25 10

(1)

no. moles ClO in 1 dm = 100 6.25 10


(iii)

(c)

QWC

(d)

(1) = 0.625

mass Cl2 = 0.625 71


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

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)

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


ll2 reacts with starch / paper to give blue / black (1)

2
[14]

68.

(a)

(b)

C10H8
ALLOW (C5H4)2
NOT (C6H4)2

(i)

600
NOT + 600
NOT 600

Al khor International School

63

(ii)

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


st
Must be a comparison for the 1 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)

(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)

If both correct but wrong way round 1 (out of 2)

electrophilic (1)
substitution (1)
Can be given in any order
Mark independently

2
[9]

Al khor International School

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)

The mark is for the shape

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


IGNORE charge unless incorrect

(iii)

[Fe(H2O)6]

2+

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

OR
2+

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


+

OR equations with 2NaOH as reactant and 2Na as product


IGNORE state symbols

Al khor International School

65

(iv)

Green precipitate / solid foxy-red / red-brown / brown / orange


Both colours and precipitate / solid needed
NOT darkens

Al khor International School

66

(v)

N2 + 3H2 /

2NH3

OR equation with Cl2

Al khor International School

67

(b)

(i)

2+

Emf of cell / potential difference of cell containing Fe and Fe (1)


and standard hydrogen electrode / half cell NOT SHE
3 +
OR hydrogen electrode and 1 mol dm H and 1 atm H2 (1)
3

2+

1 mol dm
Fe
IGNORE temperature

Al khor International School

68

QWC*(ii)

Emf of hydrogen electrode is zero stated or implied (e.g. if


calculate Ecell = +0.44(V)) (1)
+

2+

Fe + 2H Fe + H2 (1) equation stand alone


Potential for the reaction is positive so reaction is feasible (1)
OR
+
2+
H and ()H2 has a more +ve electrode potential than Fe and Fe (1)
+

H will oxidise Fe / H is an oxidising agent / Fe is a reducing


+
agent for H / other correct redox statement (1)
+
2+
Fe + 2H Fe + H2 (1) stand alone

Al khor International School

69

(iii)

High Ea so slow reaction / reactants are kinetically stable


IGNORE any mention of non-standard conditions

Al khor International School

70

(c)

2Fe

3+

2+

+ 2I 2Fe

+ I2 or words E = (+) 0.23V (1)


3+

3+

So I would reduce Fe / Fe would oxidise I / E positive so reaction


L R (1)
OR reverse argument (2)
OR
3+
2+

Fe and Fe has a more positive electrode potential than I2 and I (1)

I will reduce Fe

3+

3+

/ Fe

will oxidise I (1)

2
[15]

Al khor International School

71

70.

(a)

(i)

C6H5O Na / C6H5ONa / C6H5O


Do not allow covalent O-Na

(ii)

1
No other Isomer allowed
OR

IGNORE bond to H of OH

Al khor International School

72

(iii)

1
No ring substitution allowed

Al khor International School

73

(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

Al khor International School

74

(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

Al khor International School

75

(iii)

Alkaline / alkali / sodium hydroxide / NaOH / KOH / potassium hydroxide /


sodium carbonate / sodium hydrogencarbonate
IGNORE temperature
1
[9]

Al khor International School

76

71.

(a)

(i)

Chloromethane / bromomethane (1)


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

Al khor International School

77

(ii)

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

Al khor International School

78

(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

Al khor International School

79

(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

Al khor International School

80

(ii)

Chlorine (in an inert solvent) (1)


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

Al khor International School

81

(c)

(i)

Substitution (1)
Nucleophilic (1)
IGNORE hydrolysis
NOT SN1
NOT hydrogenation

Al khor International School

82

(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

Al khor International School

83

(d)

(Full) oxidation /redox


NOT reduction
NOT partial oxidation

Al khor International School

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]

Al khor International School

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

Al khor International School

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

Al khor International School

87

(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))

Al khor International School

88

(b)

ACCEPT any multiples / partial multiples


ALLOW allowed TE from (iii)
IGNORE ns

Condensation (polymerisation) (1)


[11]

Al khor International School

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

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)

Al khor International School

90

QWC*(b)

3+

2+

Cr (aq), Cr (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
2+

by application of the anti-clockwise rule oxygen will oxidise Cr


OR
0
E cell = (+) 0.81(V) and this is greater than (+) 0.6 (V)
OR
2+
Cr has more negative electrode potential so will reduce oxygen /
oxygen more positive etc. (1)

Al khor International School

91

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

Al khor International School

92

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

Al khor International School

93

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

Al khor International School

94

(d)

(i)

3C2H6O to 3C2H4O provided 1 Na2Cr2O7 (1)


4H2SO4 and 7H2O (1)

(ii)

(iii)

ACCEPT multiples

Orange to green
ALLOW qualified green e.g. blue-green
NOT green to orange

(Sodium dichromate(VI)) is a carcinogen / toxic / irritant


In any combination
Lose mark for anything else with these.

1
[17]

Mark Scheme

Al khor International School

95

74.

(a)

(i)

(ii)

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)
+

SO3/ SO3H

Al khor International School

2
1

96

(b)

(i)

OR C6H5Br

(ii)

Substitution (1) Electrophile (1)

(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)

Al khor International School

97

(c)

(i)

Ethylbenzene/Phenylethane

(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)

Al khor International School

98

(d)

(i)

UV/sun light

(ii)

1,2,3,4,5,6-(hexa)chloro cyclohexane

1
[13]

Al khor International School

99

75.

(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)

product is an equimolar mixture/racemic mixture (1)


so rotations cancel (1)

(iii)

Al khor International School

100

(b)

(c)

NH3 Cl on the amino group (1)


+

COO Na on the carboxyl group (1)

Zwifterions structure (1)


There is ionic attraction between adjacent zwitterions (1)

Al khor International School

101

(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)

(iii)

structure consequential on answer to (ii) showing amide link (1)


and extension of the chain (1)

(iv)

H
N

C H

C
3

CH

CH

C
3

CONH drawn out (1)


Show 3 units (1)

2
[16]

Al khor International School

102

76.

(a)

(i)

240 (kJ mol )

(ii)

360 (kJ mol )


Penalise incorrect units once only

Overlap of p-orbitals / p (system) (1)


(results in) delocalisation (1)
1
makes benzene (more) stable (by 152 kJ mol ) (1)
QWC*

(iii)

Al khor International School

103

(b)

(i)
(ii)

AlBr3/ AIC13 / FeBr3 / Fe


Formula must be correct; no names

Ignore curly arrows in this first step; mark species only


(consistent with catalyst)
+

B r 2 + A lB r 3

B r + A lB r 4

(1 )

B r

Br

Br

(1)

+H

(1) structure
(1) arrow

Alternative way of showing part played by catalyst


Br

B rA lB r 3

Allow Kekul intermediate


+

(iii)

Br
H

Electrophilic substitution

1
[11]

Al khor International School

104

77.

(a)

(b)

(c)

10

10

(i)

1s 2s 2p 3s 3p 3d 4s

(ii)

1s 2s 2p 3s 3p 3d

accept any order

Conseq on (a) (i)

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)

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.
2+
Shows dative covalent bond from water to central Zn (1)
Labels a 90 angle (1)
Ignore absence of charge on ion

Al khor International School

105

(d)

(i)
(ii)

White precipitate /solid /suspension (1) NOT powder


Colourless solution (in excess ammonia) NOT clear (1)
2+

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


Or
2+

[Zn(H2O)6] + 2OH [Zn(OH)2(H2O)4]+ 2H2O


Or

2+
[Zn(H2O)6] + 2OH Zn(OH)2 + 6H2O
Or
2+
+
[Zn(H2O)6] + 2NH3 Zn(OH)2 + 2NH4 + 4H2O (1)
2+

[Zn(OH)2(H2O)4] + 4NH3 [Zn(NH3)4(H2O)2] + 2OH + 2H2O


Or

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

Al khor International School

106

(e)

10

(i)

d-(sub) shell / orbitals are full / 3d 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 /CrO4


yellow / Cr(+6) or Cr(VI) is yellow

is
1
[16]

Al khor International School

107

78.

(a)

(i)

(ii)

The potential (difference) / e.m.f. (of a halfcell) relative to the


standard hydrogen electrode (1)
3
Concentrations (of all ions) 1 mol dm and
(any gases at) pressure 1 atm (1)
Ignore any references to temperature

One from:
Can only measure a potential difference
Or
So that comparisons can be made between any half cells

Al khor International School

108

(b)

(i)

2+

5H2O2 + 2MnO4 + 6H 5O2 + 2Mn + 8H2O (2)


(1) for species
(1) for balancing the correct species

DE reaction = + 0.84 (V) (1)


or if just states 0.84, must mention that this is a positive value

Al khor International School

109

(ii)

(iii)

Fizzing/bubbles (1)
(pink) colour lost / stays colourless (1)
(end point) solution remains pink / pale purple (1)

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]

Al khor International School

110

79.

(a)

6
solution
Sodium
carbonate
Bradys reagent (2,4-dinitro
phenyl hydrazine)

Potassium
dichromate +
sulphuric acid

Al khor International School

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)

Do not allow if bond is obviously to wrong atom from


benzene
ring

Al khor International School

112

(ii)

Al khor International School

113

(iii)

Undisplayed ester + unchanged CHO (1)


Correctly displayed for both groups (1)

(iv)

sulphuric acid / hydrochloric acid

(v)

Cl (and O) electronegative/electron withdrawing (1)


d+
So C is more/ very susceptible to nucleophilic attack/ more d+/
more electrophilic (1)

Al khor International School

114

(c)

(i)

Electrophiles / electrophilic

(ii)

Br / Br / Br Br

(iii)

Any substitution product with Br on benzene ring, and other


groups unchanged

(iv)

lone pairs / electrons on phenolic group make ring more


negative than in benzene / lone pairs on OH donated to ring

d+

d+

1
1

[17]

Al khor International School

115

80.

(a)

1s 2s 2p 3s 3p 3d 4s /4s 3d OR 3d (4s ) (1)


Incomplete d shell (in the ion) (1)

Al khor International School

116

(b)

(i)

Ni(CO)4

(ii)

Al khor International School

117

(c)

(i)

2+

Ni(H2O)6

2+

(aq) + NH3(aq) Ni(H2O)5(NH3)

(aq) + H2O(I)

QWC* (ii) DS 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)

Al khor International School

118

(d)

(+)

()

(i)

Ag (aq) + Cl (aq) Ag Cl (s)

(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

Al khor International School

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

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]

Al khor International School

120

81.

(a)

(i)

1s 2s 2p 3s 3p 3d 4s

(ii)

1s 2s 2p 3s 3p 3d

Al khor International School

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

Al khor International School

122

(c)

(i)

[Ni(H2O)4(OH)2]
ALLOW Ni(OH)2

Al khor International School

123

(ii)

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

Al khor International School

124

(iii)

Ligand exchange (1)


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

2
[10]

Al khor International School

125

82.

(a)

(i)

Use E values for reduction of Fe


2+

and Fe

to Fe by Zn (E

cell

3+

2+

to Fe

by Zn (E

cell

= + 1.53V) (1)

= +0.32V)(1)

They have positive E so are feasible (1) NOT will happen


OR
2+
3+
2+
2+
ALLOW Zn /Zn is more negative than both Fe /Fe and Fe /Fe (1)
so zinc is a stronger reducing agent (1)
so zinc reducing both is feasible (1)
3

Al khor International School

126

(ii)

Reduction of Fe

Al khor International School

2+

has high activation energy / kinetically stable

127

(b)

(i)

2+

2+

Mn O4 + 5Fe + 8H Mn
Species (1)
Balance (1)
Any state symbols ignored.

Al khor International School

+ 5Fe

3+

+ 4H2O
2

128

(ii)

purple colour of MnO4 lost (1)


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

Al khor International School

129

(c)

st

Amount MnO4 in 1 titration = 0.0182 dm 0.0200 mol dm


4

mol (1)

2+

in original solution = 5 above value = 1.82 10

2+

in 2

= 3.64 10
Amount Fe
Amount Fe

nd

titration = amount of Fe

2+

= 0.0253 dm 0.0200 mol dm 5 = 2.53 10


Amount of Fe

3+

3+

and Fe
3

mol (1)

original solution (1)

mol

in original solution = 0.00253 0.00182 = 7.10 10

mol (1)

3+

Amount zinc needed to reduce Fe = 0.000710 = 0.000355 mol


1
Mass of zinc = 0.000355 mol 65.4 g mol = 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 Fe
Realising that 2

nd

2+

by multiplying either moles of MnO4 by 5 (1)

titration measures total number of moles of iron (1))

Subtracting to get original moles Fe

3+

(1)

Going to moles Zn then mass Zn (1)

Al khor International School

130

OR

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

th

= 25.3 cm 18.2 cm = 0.0253 dm 0.0182 dm = 0.0071 dm (1) 4


point

Amount of MnO4 = 0.0071 dm 0.0200 mol dm


point
3+

Amount Fe
point

= 1.42 10

reduced by zinc = 5 above value = 7.10 10


4

st

mol (1) 1
nd

mol (1) 2

Amount zinc needed = 7.10 10 = 3.55 10 mol


4
1
th
mass of zinc needed = 3.55 10 mol 65.4 g mol = 0.00232 g (1) 5
point

Al khor International School

131

(d)

(i)

[Fe(H2O)6]

2+

+ H2O [Fe(H2O)5OH] + H3O

H3O in equation (1)


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

Al khor International School

132

(ii)

[Fe(H2O)6]
3+

3+

more acidic than [Fe(H2O)6]

Fe higher charge density than Fe


3+
Fe ion if more polarising (1)

2+

2+

(1)

(1)
3
[20]

Al khor International School

133

83.

(a)

KMnO4 (aq) in burette (1)

Pipette known volume (e.g. 25.00 cm ) of FeSO4(aq) into conical


flask (1)

[Max 1 out of 2 if KMnO4 in flask]

Add (dilute) sulphuric acid (to flask) (1)

Add KMnO4 until (faint) pink colour persists (1)

[If reagents wrong way round, end point must be pink to colourless]

Record volume of KMnO4 (aq) added and repeat to


3

concordance/within 0.20cm (1)

[Not just repeat three times]

Al khor International School

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

[Mark not awarded if e- left in final equation]

Al khor International School

135

(iii)

Amount MnO4
2+

Amount Fe

= 0.0200

0.0225 = 0.00045 mol (1)

= 5 0.00045 = 0.00225 mol (1) (consequential on (b)(ii))


3

conc. of FeSO4(aq) = 0.00225 / 0.025 = 0.0900 mol dm (1)


(consequential on (b)(ii))

Must be 2 to 4 sig fig

Al khor International School

136

(c)

3+

2+

2Fe + Fe 3Fe (1)


3+
2+
(Accept 2Fe + 3Fe 3Fe + 2Fe)
Either E (cell) = 0.04 (-0.44) = + 0.40 V (1)
i.e. positive therefore feasible (or answer consequential on E (cell)) (1)
Or
Equation (1)
Fe

3+

is the oxidised form of a redox couple with more positive EP (1)

Therefore can oxidise iron, the reduced form of other redox couple (1)

3
[14]

Al khor International School

137

84.

(a)

(i)

(ii)

1
Allow single headed arrows or other suitable notation
[Mark (ii) consequentially on (i)]

Al khor International School

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)

Ligand exchange or ligand substitution

(v)

[Cr(NH3)6]

3+

or [Cr(OH)x (H2O)y(NH3)z]

charge

x + y + z = 6, z at least one, correct charge will be between 0 and +3, x = max 3

Al khor International School

139

(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)

If imply or state that emission is occurring, only the first


marking point is available
[11]

Al khor International School

140

85.

(a)

(i)

Conc. sulphuric acid(1)


Conc. nitric acid (1)

[Conc. must be stated, or implied, for both acids]

Al khor International School

141

(ii)

HNO3 + H2SO4 H2O + HSO4 + NO2 (1)


Can be shown in two stages
Or
+

+
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)

Al khor International School

142

(iii)

Electrophilic substitution

Al khor International School

143

(b)

3
N O

N O

N O

N O

(1 )

N O

N O
N O
(1 )

O 2N

N O

(1)

Vertical/right hand substituents must be shown with C to N bond


[Mark consequentially on structural formula given for
nitrobenzene in (a)(ii)]

Al khor International School

144

(c)

Tin / iron and concentrated hydrochloric acid/conc. HCl


Heat (under reflux) (1)

(1)
2

Second mark consequential on correct / near miss


reagents

Al khor International School

145

H
N
(d)

(i)

H
C

H
N H

Allow:

Al khor International School

H
1
C

C H

146

(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)

NB If no solvent used, no marks available at all in part (d)


(ii)
[19]

Al khor International School

147

86.

(a)

(i)

[Ar]3d (1)
2
allow 1s etc

Al khor International School

148

(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

Al khor International School

149

(ii)

rate too slow / activation energy too high / kinetically stable /


allow oxide layer if metal electrode specified (1)

non-standard conditions (1)

Al khor International School

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]

Al khor International School

151

87.

(a)

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

Al khor International School

152

(b)

(i)

Coloured ions / compounds/ complexes/ solutions (1)


variable oxidation states (1)

Al khor International School

153

(ii)

2+

Cr(H2O)6
Not Cr

Al khor International School

2+

/ hexa aqua chromium (II) ion (1)

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

Al khor International School

H 2O
4 0 .5 / 1 8 ( 1 )
2 .2 5
2 .2 5 / 0 .3 7 5 ( 1 )
6

155

(ii)

3+

Violet Cr(H2O)6 .3Cl (1)


2+

Green is [Cr(H2O)5Cl] 2Cl .H2O (1)


NB for 2 marks must make clear which is which and must be a
salt which adds up to Cr(H2O)6Cl3

[8]

Al khor International School

156

88.

(a)

(i)

Aluminium chloride or AICl3 or iron(III) chloride or FeCl3 (1)


catalyst (1)

Al khor International School

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

Al khor International School

158

(b)

Esterification / condensation (1)


O
CH

O
(1)

Al khor International School

159

O H

O H

O H

O H
O H
(c)

O H

(i)

Three correct 2 marks. 2 correct 1 mark

Al khor International School

160

O
O

O
CH

(ii)
Ester link (1)
polymer / with correct benzene ring links (1)

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161

(d)

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


Sodium nitrite and hydrochloric acid (1)
0-10C (1)
alkaline solution (of phenol) (1)
[16]

Al khor International School

162

89.

(a)
H
O
H

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

Al khor International School

163

(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)

Al khor International School

164

(c)
O CH

N O

Must contain a hexagon (with ring or kekul inside)


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

Al khor International School

165

(d)

C7H7OBr
C7H6OBr2
C7H5OBr3
HBr

Al khor International School

)
) Any two
)
)

166

(e)

(i)

Methoxybenzenesulph/fonic acid

(ii)

Detergents/drugs/dyes

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167

(f)

(i)
(ii)

D
E

hydrogen / H2 (1)
(Raney) nickel / nickle / Ni /Platinum /Pt (1)

Addition (1)
Reduction (1)

Al khor International School

2
2

168

(g)

(i)

Petroleum/crude oil/coal

(ii)

Not carcinogenic / (cumulative) poison / toxic use of benzene in


schools is illegal

1
[14]

Al khor International School

169

90.

(a)

Sc

[A r]

Cr

[A r]

Cr

3+

[A r]

Cr

3+

consequential on structure for Cr

Al khor International School

170

(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)

Not highest energy shell is the d-shell


outer electron in d shell

Al khor International School

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

Al khor International School

172

H 2O
H 2O
(ii)

O H

3
2

C r
O H

O H

O H

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


Octahedral could rescue a poor diagram

Al khor International School

173

(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)

Al khor International School

174

(d)

(i)

Green precipitate (1)


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

Al khor International School

175

(ii)

Deprotonation / acid base (1)

1
[14]

Al khor International School

176

91.

(a)

2-

2S2O3 + l2 S4O6+

+ 2I or clearly stated (1)


-3

amount of thio = 26.8 0.1 / 1000 = 2.68 10 mol (1)


ratio of copper to thio is 1:1 (1)
-3
-2
total amount of copper = 2.68 10 mol 10 = 2.68 10 mol (1)
2
-1
mass of copper = 2.68 10 mol 63.5 g mol = 1.70g (1)
purity = 1.70 100 / 1.74 = 97.8 / 97.7 % (1)
allow 2 to 4 sig figs in final answer mark consequentially

Al khor International School

177

(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)

Al khor International School

178

(c)

(i)

Sodium nitrite + aq / conc / dilute HCl / hydrochloric acid (1)


any temperature between 0 and 10 C or a range between 0 &
10 C (1)

Al khor International School

179

(ii)

If too cold reaction too slow (1)


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

Al khor International School

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)

Al khor International School

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

Condition mark depends on reasonable reagents


If give alternative route then 1 for each error
Name of nitrobenzene acceptable
[25]

Al khor International School

182

92.

(a)

(i)

The potential difference between a standard hydrogen electrode


and the (half-) cell (1)
3
all concentrations measured at 1 mol dm and any gases are at
1 atm pressure (1)
2

(ii)

Fluorine or F2 (1)

Al khor International School

183

(b)

(i)

all/listed (1)

(ii)

iodine and bromine (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]

Al khor International School

184

93.

(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
(1 )
+

O C CH

A l C l 4H
CO CH

(1 )

(1 )

C O CH

3
+

H C l

In the mechanism the electrophile can be shown as


d+
d

CH3CO Cl AlCl3

Al khor International School

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

Al khor International School

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 )

S lig h tly a c id ic / s lig h tly a lk a lin e /


b u ffe re d a t n a m e p H b e tw e e n 5
a n d 9 / m ix tu re o f K C N a n d a c id . /
H C N p lu s K C N (1 )

C O 2H
C H

O H

5
[10]

Al khor International School

187

3d
M n
94.

(a)

M n

4s

[A r]
2+

[A r]

Al khor International School

188

(b)

2+

(i)

[Mn(H2O)6]

(ii)

[Mn(H2O)6]

2+

+ 2NH3 Mn(OH)2 + 2NH4 + 4H2O

2+

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

2+

+ 2OH Mn(OH)2 + 6H2O

2+

+ 2OH [Mn(OH)2(H2O)4] + 2 H2O

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)

Al khor International School

189

(iii)

(c)

(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)

(i)

from +4 to +6/ up by 2 / +2

(ii)

Amount of KMnO4 = 0.0228 0.0216 mol

= 4.925 10 mol

Al khor International School

190

(iii)

Amount of SO3
= 1.231 x 10

(iv)

in 25cm = 5/2 4.925 10 mol

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)

Purity of sample = (1.551g/ 1.75g) x 100%


= 88.6%

1
[16]

Al khor International School

191

95.

(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

Al khor International School

192

6C + 3H

C 6H

H 1
(b)

H 2
6C O

+ 3H 2O

For correct cycle shown (1) or equivalent equations


DH1 = 6 (394) + 3 (286) = 3222 kJ (1) for either showing calculation or
answer
1
DHf = 3222 (3273) = +51 kJ mol (1)
3

Al khor International School

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

Al khor International School

194

(d)

(i)

rate = k[benzene][bromine]

(ii)

rate would be decreased (1)


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

Al khor International School

195

96.

(a)

(i)

*CH(CH3) (1)

(ii)

(the three) OH groups (1)


allow adrenalin to form more hydrogen bonds with water
(than does benzedrine) (1)

Al khor International School

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)

Al khor International School

197

(ii)

Al khor International School

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 )

substitution(s) in ring at any position(s) (1)


production of amide (1)

Al khor International School

C H

199

N H CH
C

(d)

Al khor International School

H
C

C
N H C H

200

(e)

(i)

(CH(CH3)NH2)

(ii)

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

(1)

1
+

max 1 for (e) if no charges shown


must show some structure in answers ie. C2H5N(0)

1
[11]

Al khor International School

201