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Winter 1996 CH4 Mark Scheme

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1. Many insects communicate using chemical compounds called pheromones. Such compounds
may be quite simple, and the organism is extremely sensitive to their presence. Insect alarm
pheromones have been studied as potential insecticides. using the information which follows,
deduce the formula for an alarm pheromone, P, in ants.
(a) P contains 73.47% carbon and 10.20% hydrogen by mass, the remainder being oxygen.
The mass spectrum shows a significant peak at m/e = 98, but none higher than this. / find
the empirical and molecular formula for P.
C
73.47/12
H
10.20/1
O
16.33/16
= C
6.12
H
10.2
O
1.02
(1)
= C
6
H
10
O (1)
This has mass of 90 (1) highest peak is molecular ion (1) ef = mf (1)
(5)
(b) P decolorises bromine readily at room temperature. 0.735 of P dissolved in
tetrachloromethane reacts with 30.0 cm
3
of a 0.250 mol dm
3
solution of bromine in the
same solvent. Use this information to find the nature and number of one of the types of
functional group in the molecule.
mol P used = 0.735 g / 98 g mol
1
= 7.5 10
3
mol (1)
mol Br
2
used = 30/1000 0.25 mol = 7.5 10
3
mol (1)
Br
2
reaction (in cold) suggests C=C / alkene (not just double bond) (1)
and 1:1 reaction shows one is present (1)
(3)
(c) P gives a precipitate with 2,4-dinitrophenylhydrazine, and reduces ammoniacal silver
nitrate solution on warming. What is the second functional group in P?
Give your reason.
2,4-dinitrophenylhydrazine: aldehyde or ketone (the possibility of a
ketone must be mentioned (1)
Tollens / silver mirror shows: aldehyde (1)
There must be an indication of both reacting with 2,4-DNPH and only one with
ammoniacal silver nitrate
(2)
(d) P can be reduced by hydrogen / platinum at room temperature, or by sodium borohydride
in ether. In case 1 mol of P adds on 1 mol of hydrogen, but the produces are not the same.
Explain these observations.
H
2
reduces C=C (1) NaBH
4
C=O (1)
H
2
will not reduce C=O / NaBH
4
not reduce C=C under conditions stated (1)
any comment about specificity
(3)
(e) The carbon chain in P is unbranched, and the functional groups are adjacent on the chain.
P has two stereoisomers. Draw the possible structures of P.
H CHO
CH CH CH H
C C
3 2 2
H
(1)
and cis (1)

if functional groups not adjacent but cis-trans shown then (1)
allow consequential marking from identification of the carbonyl in (c)
(2)
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Winter 1996 CH4 Mark Scheme
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(f) Only one of these steriosomers is effective at persuading ants to disappear elsewhere.
Suggest why this is so.
receptors on ants sterospecific (any words to that effect)
(1)
(Total 16 marks)

2. Phenylethene (styrene),
CH CH
2

is used in large quantities to make poly(phenylethene). A possible synthetic route from benzene
to phenylethene is shown below.
CH CH
2
+ CH Br A
Step 1
Step 6
Step 2 Step 3
Step 4 Cr O /H
Step 5
Cl , u.v.
2
3
CH Cl CH OH
CHO
2 2
B
Conc H SO
heat
2 4
(1) CH MgBr
(2) H
3
+
2 7
2 +
phenylethene

(a) (i) Give the name of a suitable catalyst for step 1 and give the structure of compound A.
aluminium chloride / aluminium bromide / iron(III) bromide (or any that is used) (1)
CH3
(1)

(ii) Why is ultraviolet light necessary in step 2?
to split the chlorine or homolysis (1) generation of free radicals (1)
(iii) Suggest a suitable reagent and conditions for step 3.
aqueous KOH / NaOH (1) heat (1)
(correct reagent but no heat (1) heat but incorrect reagent (0))
(iv) The oxidation step 4 has to be done with care to obtain a\ good yield of aldehyde.
Suggest how this is achieved.
avoid excess oxidising agent (1) add oxidising agent to organic
compound and not the other way round (1)
(recognition of avoiding the second stage if neither first point scored (1))
(v) How would you prepare the Grignard reagent, methylmagnesium bromide,
CH
3
MgBr used in step 5?
Mg + CH
3
Br (1) in dry ether (1) OR with iodine catalyst (1) (max 2)
(vi) Give the structural formula of B.
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Winter 1996 CH4 Mark Scheme
3
3
CHCH
OH
all hydrogen atoms must be shown except ring (1)
(10)
(b) (i) What type of polymerisation does phenylethene undergo?
addition (1) OR free radical (1)
(ii) Draw the structure of the polymer chain showing at least TWO monomer units.
C C C C
H
C H C H
H
H H H H
n
6 6 5 5

(open ends but no [ ]
n
(1))
(2)
(4)
(c) Commercially, pheynylethene is made by the series of reactions:
AlCl
3
900 K
Fe O
2 3
CH CH
2 3
2
CH CH
2
CH CH
2
2
+ + H

Suggest two reasons why this method id better than the route given earlier.
better yield / shorter cheaper / useful by product H
2
/ no Grignard reagent
not cheaper on its own
(2)
(Total 16 marks)

3. (a) State Raoults Law for an ideal binary liquid mixture.
p(A) = p
o
(A) (A) (1) definition of symbols (1) (or words to that effect)
(2)
(b) Liquid oxygen and liquid nitrogen form an ideal liquid mixture. At 70 K the vapour
pressures are 38.3 kPa for N
2
and 6.40 kPa for O
2
. Find the composition of the vapour in
equilibrium with a liquid mixture which at equilibrium is an equimolar mixture of the
two elements.
p(N ) = 38.3 x 0.5 = 19.15 kPa
p(O ) = 6.4 x 0.5 = 3.2 kPa
(N ) = 19.15/22.35 = 0.857
(O ) = 0.143 (by any method)
x
x
P = 22.35kPa
OR recognition of ratio 6:1
(1)
(1)
tot
OR 6/7 and 1/7 of final composition (1)
(1)
(1)
2
2
2
2

Answer must be quoted to 2 or more significant figures but penalise 6 or
more significant figures once only on the paper
(3)
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(c) Show by means of sketches of boiling point / composition diagrams and a brief comment
why ideal mixtures of liquids of similar boiling temperature are more difficult to separate
by fractional distillation than those with boiling temperatures more widely separated.

diagrams to show wider difference between b.p. (1) if b.p's close v.p's each
component close effective separation more difficult more stages in the
fractionating column necessary (or words to that effect) (2)
(3)
(d) The vapour pressure / composition diagram at constant temperature for a mixture of two
liquids A and B which shows a strong deviation from Raoults Law is shown below.
(x(A) = mole fraction of A.
x( ) = 1 A
vapour
pressure
x( ) = 0 A
mole fraction
(i) Sketch on the axes below the boiling point / composition diagram for this system,
showing the curves for both liquid and vapour.
x x (A)=1 composition (A)=0

b
b b
b
(A) < (B) azeotrope in
more or less correct % position
azeotrope is minimum
liquid/vapour lines correct and labelled
(labels need only show vap. and liq. once)
(1)
(1)
(1)
(1)

(ii) consider a mixture for which the mole fraction of A is initially 0.75. Use your
diagram to explain what happens when this mixture is fractionally distilled, making
clear the nature of the distillate and of the residue.
distillate is azeotrope (1) residue is A (1) suitable discussion (1)
referred to diagram (1) (eg use of tie lines)
(8)
(Total 16 marks)

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Winter 1996 CH4 Mark Scheme
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4. State Raoults Law for an ideal binary liquid mixture.
p(A) = p
o
(A)x(A) (1) definition of symbols (1) (or words to that effect)
(Total 2 marks)

5. Liquid oxygen and liquid nitrogen form an ideal liquid mixture. At 70 K the vapour pressures
are 38.3 kPa for N
2
and 6.40 kPa for O
2
. Find the composition of the vapour in equilibrium with
a liquid mixture which at equilibrium is an equimolar mixture of the two elements.
p(N ) = 38.3 x 0.5 = 19.15 kPa
p(O ) = 6.4 x 0.5 = 3.2 kPa
(N ) = 19.15/22.35 = 0.857
(O ) = 0.143 (by any method)
x
x
P = 22.35kPa
OR recognition of ratio 6:1
(1)
(1)
tot
OR 6/7 and 1/7 of final composition (1)
(1)
(1)
2
2
2
2

Answer must be quoted to 2 or more significant figures but penalise 6 or
more significant figures once only on the paper
(Total 3 marks)

6. Show by means of sketches of boiling point / composition diagrams and a brief comment why
ideal mixtures of liquids of similar boiling temperature are more difficult to separate by
fractional distillation than those with boiling temperatures more widely separated.

diagrams to show wider difference between b.p. (1) if b.p's close v.p's each
component close effective separation more difficult more stages in the
fractionating column necessary (or words to that effect) (2)
(Total 3 marks)

7. The vapour pressure / composition diagram at constant temperature for a mixture of two liquids
A and B which shows a strong deviation from Raoults Law is shown below. (x(A) = mole
fraction of A.
x( ) = 1 A
vapour
pressure
x( ) = 0 A
mole fraction
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Winter 1996 CH4 Mark Scheme
6

(i) Sketch on the axes below the boiling point / composition diagram for this system,
showing the curves for both liquid and vapour.
x x (A)=1 composition (A)=0

b
b b
b
(A) < (B) azeotrope in
more or less correct % position
azeotrope is minimum
liquid/vapour lines correct and labelled
(labels need only show vap. and liq. once)
(1)
(1)
(1)
(1)

(ii) Consider a mixture for which the mole fraction of A is initially 0.75. Use your diagram to
explain what happens when this mixture is fractionally distilled, making clear the nature
of the distillate and of the residue.
distillate is azeotrope (1) residue is A (1) suitable discussion (1)
referred to diagram (1) (eg use of tie lines)
(Total 8 marks)

8. The following is adapted for a textbook of practical chemistry which gives practical details for
the preparation of the azo dye phenylazo-2-naphthol.
Dissolve 2.5 g of phenylamine in a mixture of 8 cm
3
of concentrated hydrochloric acid and 8
cm
3
of water in a small beaker. Place in an ice bath; ignore any crystals that may appear. When
the temperature is between 0 C and 5 C, add drop by drop a solution of 2 g of sodium nitrite
dissolved in 10 cm
3
of water, not allowing the temperature to rise above 5 C. Addition of the
sodium nitrite solution should continue until, after a wait of 3-4 minutes, a drop of the reaction
mixture given an immediate blue colouration with starch-iodine paper.
Prepare a solution of 3.9 g of 2-naphthol in 10% aqueous sodium hydroxide solution in a 250
cm
3
beaker, and cool in ice bath to below 5 C; add 10-15 g of crushed ice to this solution. Stir
the mixture, and add the diazonium salt prepared as above very slowly; red crystals of the azo
compound will separate. When addition is complete, allow the mixture to stand in ice for 10
minutes and then filter the product, using gentle suction on a Buchner funnel. Wash with water;
the product may be recrystallised from glacial ethanoic acid. it has a melting point of 131 C.
(a) Phenylamine is toxic by inhalation and skin absorption; concentrated hydrochloric acid is
corrosive and gives harmful fumes. What specific precautions would you therefore take
when doing this experiment?
fume cupboard (1) gloves (1)
(safety requirements must be specific to question)
(2)
(b) Write the equation for the reaction between phenylamine and hydrochloric acid.
C
6
H
5
NH
2
+ HCI C
6
H
5
NH
3
+
CI

must have correct charges


ignore CI

if H
+
on the L.H.S.
(1)
(c) (i) Why should the reaction mixture be kept between 0 C and 5C?
< 0 C too slow (1) > 5 C product decomposes (1)
(ii) Is the diazotisation reaction exothermic or endothermic? How do you know?
exothermic (1) have to keep temperature below 5 C (1)
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Winter 1996 CH4 Mark Scheme
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(iii) Why should you wait before testing with starch-iodide paper for the presence of
excess nitrite ions?
reaction slow so NO
2

needs time to be used (1)


(5)
(d) Give the equation, using structural formulae, for the diazo coupling reaction between
benzene diazonium chloride and 2-naphthol.
N Cl + N=N
OH
ignore HCl
+
2
reactants (1) products (1)
+ HCl

allow N
+
N or N N
+

but not N
+
=N or N=N
+

CI

not essential
(2)
(e) The aqueous solution of the diazo compound prepared as in the first paragraph will, if
allowed to warm up, turn from very pale yellow to a turbid orange-red, and will evolve
nitrogen. Why is this?
diazo compound gives phenol (1)
which reacts with diazo compound to give dye (1)
(2)
(Total 12 marks)


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