Winter 1997 CH6

1
1. Carvone
C
C
C
O
CH
CH
CH
3
CH2 CH2
CH
2
H C
3
O
CH3
CH2 H C 3
which may also
be shown as

is the main flavouring material in spearmint oil.
(a) Draw the structure of the product obtained when carvone reacts with
(i) 2,4-dinitrophenylhydrazine:



(2)
(ii) bromine:



(2)
(b) Explain why carvone does not react with ammoniacal silver nitrate.
....................................................................................................................................
....................................................................................................................................
(1)
(c) Carvone is chiral and shows optical activity.
(i) Explain the meaning of chiral.
..........................................................................................................................
..........................................................................................................................
(1)
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Winter 1997 CH6
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(ii) Circle on the structure of carvone the features of the molecule which makes
it chiral.
(1)
(iii) What is optical activity?
..........................................................................................................................
..........................................................................................................................
(2)
(d) Suggest a synthetic method, including reference to reagents and conditions, by which
carvone could be converted to
Cl
CH3
CH2 H C 3
C

(5)
(Total 14 marks)

2. (a) Propanoic acid dissociates in aqueous solution according to
CH
3
CH
2
CO
2
H(aq) + H
2
O(1) CH
3
CH
2
CO
2

(aq) + H
3
O
+
(aq)
(i) Write the expression for K
a
for propanoic acid.


(1)
(ii) Given that K
a
for this reaction is 1.35 10
5
mol dm
3
at 298 K, calculate the pH of
a 0.100 mol dm
3
solution of propanoic acid at this temperature.



(3)
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(iii) If the solution referred to in (ii) were to be diluted tenfold, it might be expected that
the pH would rise by one unit. In fact it rises by less than this. Explain.
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(3)
(b) During a titration NaOH solution of concentration 0.100 mol dm
3
was added to 30.0 cm
3

of 0.100 mol dm
3
propanoic acid.
(i) What property is shown by the reaction mixture when 15.0cm
3
of NaOH has been
added to the propanoic acid?
..........................................................................................................................
(1)
(ii) Calculate the pH of the reaction mixture at this stage.
Propanoic acid has K
a
= 1.35 10
5
mol dm
3
, pK
a
= 4.87.



(3)
(iii) What criteria must be considered in the selection of an indicator for this titration?
..........................................................................................................................
..........................................................................................................................
(2)
(c) When hydrochloric or nitric acid is reacted with sodium hydroxide solution, the enthalpy
change is 57.1 kJ mol
1
. If propanoic acid is used instead of the other acids, the enthalpy
change is less negative.
(i) Suggest why this is so.
..........................................................................................................................
..........................................................................................................................
(2)
(ii) What would be the effect on the value of H for the reaction of using ammonia
solution instead of sodium hydroxide with propanoic acid?
..........................................................................................................................
(1)
(Total 16 marks)

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3. Propanoic acid dissociates in aqueous solution according to
CH
3
CH
2
CO
2
H(aq) + H
2
O(1) CH
3
CH
2
CO
2
(aq) + H
3
O
+
(aq)
(a) Write the expression for K
a
for propanoic acid.


(1)
(b) Given that K
a
for this reaction is 1.35 10
5
mol dm
3
at 298 K, calculate the pH of a
0.100 mol dm
3
solution of propanoic acid at this temperature.



(3)
(c) If the solution referred to in (ii) were to be diluted tenfold, it might be expected that the
pH would rise by one unit. In fact it rises by less than this. Explain.
........................................................................................................................
........................................................................................................................
........................................................................................................................
(3)
(Total 7 marks)

4. During a titration NaOH solution of concentration 0.100 mol dm
3
was added to 30.0 cm
3
of
0.100 mol dm
3
propanoic acid.
(a) What property is shown by the reaction mixture when 15.0cm
3
of NaOH has been added
to the propanoic acid?
........................................................................................................................
(1)
(b) Calculate the pH of the reaction mixture at this stage.
Propanoic acid has K
a
= 1.35 10
5
mol dm
3
, pK
a
= 4.87.



(3)
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Winter 1997 CH6
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(c) What criteria must be considered in the selection of an indicator for this titration?
........................................................................................................................
........................................................................................................................
(2)
(Total 6 marks)

5. When hydrochloric or nitric acid is reacted with sodium hydroxide solution, the enthalpy change
is 57.1 kJ mol
1
. If propanoic acid is used instead of the other acids, the enthalpy change is less
negative.
(a) Suggest why this is so.
........................................................................................................................
........................................................................................................................
(2)
(b) What would be the effect on the value of H for the reaction of using ammonia solution
instead of sodium hydroxide with propanoic acid?
........................................................................................................................
(1)
(Total 3 marks)

6. Alkanes and alkenes differ strikingly in their reactivity, for example with chlorine; this is a
consequence of their structure.
(a) Using a charge-cloud representation of the - and -bonds show the structures of ethane
and ethene.
(2)
(b) (i) Give the equation for the reaction of one mole of ethane with one mole of chlorine.
(1)
(ii) Give the mechanism for this reaction.
(3)
(iii) Butane is a by-product by this reaction. How does it arise?
(1)
(c) (i) Give the mechanism for the reaction of chlorine with ethene.
(3)
(ii) Explain in terms of their structures why the reactions of ethane and of ethene with
chlorine are so different.
(3)
(iii) Why are alkenes not used as fuels?
(1)
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(d) Alkynes such as ethyne
HCCH
are unsaturated compounds and undergo addition reactions in a similar fashion to alkenes.
Under suitable conditions, ethyne will react with water, and the reaction might be
expected to be
HCCH + H
2
O CH
2
==CHOH
ethenol
(i) Using the bond enthalpies given below, suggest why the product of this reaction is
not in fact ethenol, but its structural isomer ethanal, CH
3
CHO.
H/kJ mol
1
: CH 412, C=C 612, CO 360, C=O 743, OH 463
CC 348, CC 837.
(4)
(ii) The catalyst used for the reaction is mercury(II) sulphate. The process was
responsible for a serious pollution incident in Japan in the 1950s, when
mercury(II) sulphate effluent was converted by bacteria in river muds into
methylmercury, (CH
3
)
2
Hg. This then entered the food chain via fish caught locally.
HgSO
4
is a typical inorganic compound, (CH
3
)
2
Hg is typically organic and is very
much more toxic. Suggest a reason why.
(1)
(e) Alkanes are obtained by the fractional distillation of crude oil; this system is complex, but
it does not form any azeotropes. The boiling-point/composition diagram shown is for a
pair of liquids A and B which do form an azeotrope:
0 1
Temperature
Mole fraction of A
X
-
(i) State and explain what would happen if a mixture of composition X was
fractionally distilled.
(4)
(ii) Does this system show a positive or negative deviation from Raoults Law? State
how this deviation arises.
(2)
(Total 25 marks)

7. Alkanes and alkenes differ strikingly in their reactivity, for example with chlorine; this is a
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Winter 1997 CH6
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consequence of their structure.
Using a charge-cloud representation of the - and -bonds show the structures of ethane
and ethene.
(2)

8. (a) Give the equation for the reaction of one mole of ethane with one mole of chlorine.
(1)
(b) Give the mechanism for this reaction.
(3)
(c) Butane is a by-product by this reaction. How does it arise?
(1)
(Total 5 marks)

9. (a) Give the mechanism for the reaction of chlorine with ethene.
(3)
(b) Explain in terms of their structures why the reactions of ethane and of ethene with
chlorine are so different.
(3)
(c) Why are alkenes not used as fuels?
(1)
(Total 7 marks)

10. Alkynes such as ethyne
HCCH
are unsaturated compounds and undergo addition reactions in a similar fashion to alkenes.
Under suitable conditions, ethyne will react with water, and the reaction might be expected to be
HCCH + H
2
O CH
2
==CHOH
ethenol
(a) Using the bond enthalpies given below, suggest why the product of this reaction is not in
fact ethenol, but its structural isomer ethanal, CH
3
CHO.
H/kJ mol
1
: CH 412, C=C 612, CO 360, C=O 743, OH 463
CC 348, CC 837.
(4)
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(b) The catalyst used for the reaction is mercury(II) sulphate. The process was responsible
for a serious pollution incident in Japan in the 1950s, when mercury(II) sulphate effluent
was converted by bacteria in river muds into methylmercury, (CH
3
)
2
Hg.
This then entered the food chain via fish caught locally. HgSO
4
is a typical inorganic
compound, (CH
3
)
2
Hg is typically organic and is very much more toxic. Suggest a
reason why.
(1)
(Total 5 marks)

11. Alkanes are obtained by the fractional distillation of crude oil; this system is complex, but it
does not form any azeotropes. The boiling-point/composition diagram shown is for a pair of
liquids A and B which do form an azeotrope:
0 1
Temperature
Mole fraction of A
X

(a) State and explain what would happen if a mixture of composition X was fractionally
distilled.
(4)
(b) Does this system show a positive or negative deviation from Raoults Law? State how
this deviation arises.
(2)
(Total 6 marks)

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12. Phenylamine, C
6
H
5
NH
2
, can be made in several ways from benzene. The flowchart shows two
of these in outline.
NO
2
2
Step 1
Step 2
Step 3
NH
C H 8 10
C H O
7 6 2
C H OCl
7 5
C H NO
7 7
A
B
C
D
MnO /OH
4

phenylamine
AlCl /C H Cl 3 2 5
-
(a) (i) Give the reagents and conditions needed for step 1.
(2)
(ii) Write the mechanism for this reaction.
(4)
(iii) Give the reagents and conditions for step 2.
(3)
(b) (i) In the alternative pathway identify the compounds A to D inclusive.
(4)
(ii) State the reagents and conditions needed for step 3.
(3)
(iii) Why is the first pathway commercially preferable for the manufacture of
phenylamine?
(1)
(c) Phenylamine reacts with nitrous acid in the presence of concentrated hydrochloric acid at
05C to produce benzenediazonium chloride.
If the temperature of the solution rises, this compound reacts with the solvent water to
give phenol, C
6
H
5
OH, and nitrogen gas. The rate of the reaction can be followed by
measuring the volume of nitrogen produced at various times, pressure and temperature
remaining constant. The amount of benzenediazonium chloride remaining in the solution
is proportional to V

V
t
, where V
t
is the volume of gas at time t and V

is that at the end
of the reaction.
(i) Give the equation for the reaction between benzenediazonium chloride and water.
(2)
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Winter 1997 CH6
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(ii) Some results of this experiment are shown below.
250
200
150
100
50
0
0 500 1000
t/s
(

)
/
c
m
V
V

3
t

Deduce the order of reaction with respect to benzenediazonium chloride from
the graph.
(4)
(iii) Is the reaction necessarily of this order overall? Explain your answer.
(2)
(Total 25 marks)

13. Phenylamine, C
6
H
5
NH
2
, can be made in several ways from benzene. The flowchart shows two
of these in outline.
NO
2
2
Step 1
Step 2
Step 3
NH
C H 8 10
C H O
7 6 2
C H OCl
7 5
C H NO
7 7
A
B
C
D
MnO /OH
4

phenylamine
AlCl /C H Cl 3 2 5

(a) (i) Give the reagents and conditions needed for step 1.
(2)
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Winter 1997 CH6
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(ii) Write the mechanism for this reaction.
(4)
(iii) Give the reagents and conditions for step 2.
(3)
(b) (i) In the alternative pathway identify the compounds A to D inclusive.
(4)
(ii) State the reagents and conditions needed for step 3.
(3)
(iii) Why is the first pathway commercially preferable for the manufacture
of phenylamine?
(1)
(Total 17 marks)

14. Phenylamine reacts with nitrous acid in the presence of concentrated hydrochloric acid at
05C to produce benzenediazonium chloride.
If the temperature of the solution rises, this compound reacts with the solvent water to
give phenol, C
6
H
5
OH, and nitrogen gas. The rate of the reaction can be followed by
measuring the volume of nitrogen produced at various times, pressure and temperature
remaining constant. The amount of benzenediazonium chloride remaining in the solution
is proportional to V

V
t
, where V
t
is the volume of gas at time t and V

is that at the
end of the reaction.
(a) Give the equation for the reaction between benzenediazonium chloride and water.
(2)
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Winter 1997 CH6
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(b) Some results of this experiment are shown below.
250
200
150
100
50
0
0 500 1000
t/s
(

)
/
c
m
V
V

3
t

Deduce the order of reaction with respect to benzenediazonium chloride from the graph.
(4)
(c) Is the reaction necessarily of this order overall? Explain your answer.
(2)
(Total 8 marks)

15. The elements in Group 4 of the periodic table show a trend from non-metallic to metallic
behaviour as atomic number increases. At the same time oxidation state + 2 becomes more
stable compared with oxidation state + 4.
(a) Explain why metallic character increases with increasing atomic number in Group 4.
(4)
(b) Lead forms oxides in the +2 and +4 oxidation state.
(i) State the acid-base character of lead(II) oxide, illustrating your answer
with equations.
(3)
(ii) Write an equation for the reaction of lead(IV) oxide with concentrated HCl at room
temperature, and explain the difference between this reaction and that in part (b)(i).
(4)
(c) Tetrachloromethane does not react with cold water, whereas silicon tetrachloride
hydrolyses rapidly. In contrast, in Group 3 both boron trichloride and aluminium
trichloride hydrolyse rapidly.
(i) State the shape of a molecule of boron trichloride and justify it in terms of
electron structures.
(2)
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Winter 1997 CH6
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(ii) Write the equation for the reaction of boron trichloride with water. Explain why
boron trichloride reacts with water whereas tetrachloromethane, CCl
4
, does not.
(3)
(iii) Explain how you would use solutions of silver nitrate and ammonia to show that the
reaction product from boron trichloride and water contains chloride ions.
(3)
(d) Silver nitrate can also be used to show the presence of iodide ions in solution. Silver
iodide is sparingly soluble in water.
(i) Given the thermochemical data below, suggest why silver iodide is so insoluble.
lattice enthalpy of AgI 876 kJ mol
1
hydration enthalpies: Ag
+
464 kJ mol
1

I

293 kJ mol
1

(2)
(ii) Explain why your result from (i) only suggests why AgI is so insoluble.
(1)
(iii) The following equilibrium is established when excess solid silver iodide is in
contact with a saturated solution of silver iodide:
AgI(s) Ag+(aq) + I

(aq)
Silver nitrate is used to precipitate halides in quantitative analysis, where the
precipitate is weighed to find the amount of halide. Why, in such experiments, is
an excess of silver nitrate added to the test solution?
(3)
(Total 25 marks)

16. What is
(i) a d-block element
(ii) a transition element?
(2)
(b) Transition elements characteristically have several oxidation states; iron commonly has
oxidation states of +2 and +3, but these are not the only ones.
(i) Explain why, in normal conditions, iron(III) is more stable than iron(II).
(2)
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Winter 1997 CH6
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(ii) Oxidation of iron with potassium nitrate in alkaline solution gives a red compound,
R which contains potassium, iron and oxygen only. R is a powerful oxidising
agent, and will oxidise iron(II) to iron(III).
25.0 cm
3
of a 0.100 mol dm
3
solution of R oxidised 37.5 cm
3
of a solution of
iron(II) containing 55.6 g dm
3


of FeSO
4
.7H
2
O.
Calculate the oxidation state of the iron in R.
(5)
(iii) Suggest a formula for R.
(1)
(c) (i) It is claimed that the cyanide complex of iron(II) is more easily oxidised by air, in
acidic solution, than the hydrated complex. What information would you seek from
a data book, or reference book, to consider this claim, and what relative numerical
values would you expect to find if the claim was justified? Write ionic half
equations appropriate.
(5)
(ii) Predictions from E values concerning the feasibility of a reaction are not always
realised in practice. Suggest reasons for this.
(2)
(d) Rusting of iron is commercially very important, both to those who lose articles to rust and
those who manufacture their replacements.
(i) Show how rusting occurs at a wet iron or steel surface, making clear its
electrochemical nature.
(6)
(ii) Explain why rusting is usually faster in marine or industrial environments.
(2)
(Total 25 marks)

17. What is
(a) a d-block element
(b) a transition element?
(Total 2 marks)

18. Transition elements characteristically have several oxidation states; iron commonly has
oxidation states of +2 and +3, but these are not the only ones.
(a) Explain why, in normal conditions, iron(III) is more stable than iron(II).
(2)
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Winter 1997 CH6
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(b) Oxidation of iron with potassium nitrate in alkaline solution gives a red compound, R
which contains potassium, iron and oxygen only. R is a powerful oxidising agent, and
will oxidise iron(II) to iron(III).
25.0 cm
3
of a 0.100 mol dm
3
solution of R oxidised 37.5 cm
3
of a solution of iron(II)
containing 55.6 g dm
3


of FeSO
4
.7H
2
O.
Calculate the oxidation state of the iron in R.
(5)
(c) Suggest a formula for R.
(1)
(Total 8 marks)

19. (a) It is claimed that the cyanide complex of iron(II) is more easily oxidised by air, in
acidic solution, than the hydrated complex. What information would you seek from a data
book, or reference book, to consider this claim, and what relative numerical values would
you expect to find if the claim was justified? Write ionic half equations appropriate.
(5)
(b) Predictions from E values concerning the feasibility of a reaction are not always realised
in practice. Suggest reasons for this.
(2)
(Total 7 marks)

20. Rusting of iron is commercially very important, both to those who lose articles to rust and those
who manufacture their replacements.
(a) Show how rusting occurs at a wet iron or steel surface, making clear its electrochemical
nature.
(6)
(b) Explain why rusting is usually faster in marine or industrial environments.
(2)
(Total 8 marks)


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