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Winter 2000 CH2 Mark Scheme

1.

(a)

(i)

(ii)

Kc =

NH 3 2
N 2 . H 2 3

moles at
start
moles at eq
[] at eq

N2

H2

NH 3

.........

given

.........

3.0
0.30

9.0
0.90

12
1.2

(1)
(1)

the second mark is to be awarded for correctly dividing by 10 and is consequential


on the candidates answer to the number of moles.
2
(iii)

(iv)
(v)

(b)

(i)

1.22
= 6.6 /6.58 (1)
3
0.3 0.9
mol2 dm6 (1)
Mark (iii) consequentially on the values given for [ ] in part (ii)
Unit mark consequential.

Effect of T increase on K:
lowers its value(1)
Reason: reaction driven in endothermic direction (1)

Effect of P increase on K:
none(1)
Reason: Kc only altered by change in temperature / equilibrium
moves to maintain the value of Kc (1)

Kc =

Hr = Hf(NO(g)) 4 + Hf(H2O(g)) 6 Hf(NH3(g)) 4 (1)


= 4 (+90.4) + 6 (242) 4 (46.2) (1)
= 905.6 (kJmol1) (1)
General points: The first mark is for a correct chemical statement.
The second and third are for a correct consequential calculation.
Thus line 1 could be a correct cycle or Hf =() Hf products ()Hf
reactants
3

Reactants (4NH 3 + 5O 2 )

Enthalpy

Hr or ()905.6 kJ mol 1

Correct levels
consequential on sign of
answer in (i) (1)
Labelled H line (1)

Products (4NO + 6H 2 O)

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Winter 2000 CH2 Mark Scheme

(c)

(i)

(ii)
(iii)

2H2SO4 + HNO3 H3O+ + NO2+ + 2HSO4 (1)


or
H2SO4 + HNO3 H2O + NO2+ + HSO4
or
H2NO3 H2O + NO2+
or
H2NO3+ + H2SO4 H3O+ + NO2+ + HSO4
Answer could be given as two separate equations. In this case,
give the mark for the second part as the first part is listed below in
the question.
acid: H2SO4
base: HNO3

conj base: HSO4 (1) for the pair


conj acid: H2NO3+ (1) for the pair

1
2

Sulphuric acid is stronger / nitric acid is weaker(1)

HSO 4
(1) H
NO 2
(1)

(1) NO 2+

or kekul form
(iv)

NO 2
+
(v)

H /H 2 SO 4

The movement of a pair of electrons (1)

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2.

(a)

(b)

Diagram Reasonable apparatus for the reaction vessel(1)


Gas syringe or upturned gas burette to collect gas (1)
Water bath at 50C (1)
Measurements volume of gas(1)
at intervals of time (1)
OR Diagram with flask in water bath etc. (1)
Remove samples (1)
at timed intervals (1)
Quench by cooling / diluting (1)
Titrate vs alkali (1)
OR if done via pH change measurements
max 3
If done by mass change method max 3
i.e. diagram with water bath-measure-time intervals

k [H2O2] (1)

(i)

Rate =

(ii)

Ea of H2O2 reaction > Ea of benzene diazonium chloride


reaction (1)
k of peroxide reaction < k of benzene diazonium chloride
reaction(1)

speed / energy of molecules increases (1)


more molecules have E Ea(1)
(rate faster) as greater proportion of collisions results in reaction(1)
Note These points could be made on a Maxwell-Boltzmann diagram

(iii)

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Winter 2000 CH2 Mark Scheme

(iv)

(c)

provides (alternative) route (1)


with lower Ea (1)
Note The second mark is consequential on the first it is not stand alone.

order wrt I2 : zero(1)


slope / gradient constant (1)
therefore rate constant (1)
Note There are several ways the last two points could be expressed. e.g. a plot of gradient
vs conc of iodine is horizontal or the line is straight therefore the rate is constant.
But if first order would be curve does not answer the question fully (Max 2)
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3.

(a)

(i)
(ii)

2,4 dinitrophenylhydrazine / Bradys reagent(1)


orange / yellow ppt (1)

ammoniacal silver nitrate ( Tollens reagent )/ Fehlings solution/


Benedicts solution) (1)
silver mirror / red ppt (1)

CH 3

H
C

(1)

CH 3

CH 2

CH 2

H
C

and

(b)

CH 3

CH 3

CHO

H
C

CH 3

CH 2

CH 2

(1)

CHO
C

CH 3

C
H

Note The hydrocarbon residue could be written as C6H11


Reason: no or restricted rotation about double bond (1)
(c)

(i)

Bromine colour goes from brown to colourless (1)

(ii)

Br Br
CH 3

Br Br
CH 2

CH 2

1
1

H
C
O

CH 3 H
(iii)

CH 3 H

Correct identification of 3 chiral centres (2)


Correct identification of 1 or 2 chiral centres (1)

Note If indicate 3 correct chiral centres plus 1 wrong centre max 1


Consequential on (ii)
(d)

(i)

(ii)

NaBH4 (1) in aq or ethanolic solution (1)


Note: not dry ether unless subsequently hydrolysed
OR sodium(1) in ethanol(1)
OR LiAlH 4 (1) dry ethoxyethane / ether (1)

PCl5 (1) steamy/white/misty fumes / valid test for HCl gas (1)
or
Na(1) fizzes / gives gas that burns with a squeaky pop(1)

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Winter 2000 CH2 Mark Scheme

(e)

(i)
(ii)
(iii)

Ka = [H3O+][C9H15COO](1)allow [H+] (1)


[C9H15COOH]

amount = 4.62 / 168 = 0.0275 mol


concentration of acid = 0.0275 4 = 0.11(0) (mol dm3) (1)

pH = 2.91
thus [H+] = 1.23 103 (mol dm3) (1)
Ka = [H+]2/[HA] or Ka = (1.23 103 )2 / 0.11(1)
= 1.38 105 mol dm 3(1)

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