Beruflich Dokumente
Kultur Dokumente
Fe [Ar] .........................................................................................................
2+
Fe [Ar] .........................................................................................................
(1)
2+
(ii) Draw the structure of the hexaaquairon(II) ion, [Fe(H2O)6] , clearly showing its
shape.
(1)
(iii) Give the equation for the complete reaction of hydroxide ions with a solution of
hexaaquairon(II) ions.
(1)
(iv) State what you would see if the product mixture in (iii) is left to stand in air.
...........................................................................................................................
...........................................................................................................................
(1)
2+ – ο
Fe + 2e Fe E = –0.44 V
(i) Define the term standard electrode potential with reference to this electrode.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
ο
(ii) Explain why the value of E suggests that the iron will react with an aqueous
2+
solution of an acid to give Fe ions and hydrogen gas.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
ο
(iii) State why E values cannot predict that a reaction will occur, only that it is
possible.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 10 marks)
Many medieval churches contain some very fine examples of stained glass coloured with
transition metal compounds. Blue and green colours result from adding cobalt or copper oxides
to molten glass. Copper oxide is added to colour the glass red, but it must be mixed with a
strong reducing agent to give this colour. The red colour is so strong that it can appear black,
and may need to be coated as a thin layer on top of colourless glass.
Like glass, many gemstones are based on silica and some on alumina. They are also coloured by
transition metal compounds. A solid matrix of either silica, SiO2, or alumina, Al2O3, has some
of the silicon or aluminium replaced by a small quantity of a transition metal. Replacing about
5% of the aluminium ions in alumina with chromium(III) gives ruby, important in laser
production. Replacement of aluminium ions by a mixture of iron(III) and titanium(III) gives
sapphire. The metal coming in must have the same charge and about the same radius as the
aluminium.
Based on ‘Colour, A Chemical Overview’ Chemistry Review volume 5, number 5, May 1996 written by Ken Kite
(a) The metals imparting colour to glass and gemstones mentioned in the passage are all
transition elements.
...........................................................................................................................
...........................................................................................................................
(1)
(ii) Explain the processes which lead to hydrated transition metal ions being coloured.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
...........................................................................................................................
(1)
(ii) The production of red copper oxide is involved in a test for a functional group in
organic chemistry. Name the reagent used in this test and the functional group it
detects.
Reagent .............................................................................................................
(c) Why would the addition of iron(II) oxide, FeO, or osmium(III) oxide, Os2O3, not replace
aluminium ions in alumina?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
(Total 20 marks)
3. Many modern day fabric softeners are manufactured with the liquid enclosed in a water soluble
capsule. The capsule is based on a polymer of ethenol.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
....................................................................................
(1)
(ii) Write the formula of the monomer which polymerises to form poly(vinyl acetate),
PVA (poly(ethenylethanoate)).
....................................................................................
(1)
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
Poly(ethene) ................................................................................................................
Fibre ............................................................................................................................
(1)
(Total 10 marks)
4. (a) (i) Write the equation for the reaction between cyclohexene, ,
and bromine.
(1)
(3)
(b) (i) Write the equation for the reaction between benzene, , and
bromine in the presence of a catalyst of anhydrous iron(III) bromide, FeBr3.
...........................................................................................................................
(1)
(4)
...........................................................................................................................
(1)
(i) the differences and similarities of the first steps involving the organic compounds
in both reactions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(d) State the number of peaks in the proton nmr spectrum of the product of the reaction
between cyclohexene and bromine.
.....................................................................................................................................
(1)
(Total 17 marks)
2+
5. A firm claims that their iron tablets contain 10 mg of Fe per tablet. A chemist wishes to check
this by titration using potassium manganate(VII) and dilute sulfuric acid.
2+ 3+ –
Fe (aq) Fe (aq) + e
– + – 2+
MnO4 (aq) + 8H (aq) + 5e Mn (aq) + 4H2O(l)
.....................................................................................................................................
.....................................................................................................................................
(1)
2+ –
(b) How many moles of Fe react with one mole of MnO4 ?
.....................................................................................................................................
(1)
(1)
–3
(ii) Use your answer to (i) to calculate the volume of 0.010 mol dm potassium
manganate(VII) solution that would be needed to react with one tablet.
(2)
(iii) Is this a suitable volume to verify the integrity of the firm’s claim? How would you
alter the experiment to obtain a more suitable volume?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
The “10 mg iron tablets” produced by a pharmaceutical company contain between 9 and
2+
11 mg of Fe .
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 8 marks)
6. Select, from A–D, the type of interaction which best describes the bonding between
A dative covalent
B London forces
C ion-dipole
D ionic
(1)
A dative covalent
B London forces
C ion-dipole
D ionic
(1)
(Total 2 marks)
C non-polar molecules
D linear molecules
Select from A–D, the similarity between each of the compounds below.
D
(1)
D
(1)
(Total 2 marks)
A Benzene, C6H6
B Glycine, NH2CH2COOH
C Propene, CH3CHCH2
D Propanone, CH3COCH3
D
(1)
D
(1)
D
(1)
D
(1)
(Total 4 marks)
9. When the colourless liquid chlorobenzene is shaken with bromine water, the chlorobenzene
becomes a yellow orange colour. What is the interpretation of this?
This is because
11. The rate equation for the reaction between aqueous sodium hydroxide and
2-chloro-2-methylpropane is
Rate = k[2-chloro-2-methylpropane]
A precipitation
B redox
C proton transfer
D complex formation
(Total 1 mark)
A polyester
C detergent
D protein
(Total 1 mark)
15. What class of organic compound has a characteristic smell and gives a solution in water with a
pH of about 10?
A arene
B amine
C aldehyde
D carboxylic acid
(Total 1 mark)
Compound Y could be
A propanoyl chloride
B propanoic acid
C propan-1-ol
D propanal
(Total 1 mark)
A Butan-1-ol
B Butan-2-ol
C 2-methylpropan-1-ol
D 2-methylpropan-2-ol
(Total 1 mark)
20. Which of the following is always proportional to Ecell for a chemical reaction?
A ∆ Hr
B ∆ Ssystem
C ∆ Ssurroundings
D ∆ Stotal
(Total 1 mark)
21. Which of the following ground state electron configurations corresponds to an element most
likely to form an oxide with catalytic properties?
2 2
A 1s 2s
2 2 6 2
B 1s 2s 2p 3s
2 2 6 2 2
C 1s 2s 2p 3s 3p
2 2 6 2 6 5 2
D 1s 2s 2p 3s 3p 3d 4s
(Total 1 mark)
(a) What are the oxidation numbers of carbon in methanol and methanoic acid?
MethanolMethanoic acid
A –1 +1
B –2 +2
C +1 –1
D +2 –2
(1)
2–
(b) How many moles of methanol react with one mole of dichromate(VI) ion, Cr2O7 ?
A 1
B ¾
C 1½
D 3
(1)
(Total 2 marks)
23. Which of the following will not act as a ligand in the formation of complexes?
A C6H5NH2
B CH3NH2
+
C NH4
D NH3
(Total 1 mark)
(i) Explain, in terms of kinetic factors, why the mixture is heated for a significant
amount of time.
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii) Suggest why butan-2-ol, which is only partially miscible with water, is much more
soluble in concentrated hydrochloric acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
(1)
(vi) How would you heat the mixture safely? Explain your choice of method.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
The mechanism for the reaction is either SN1 or SN2; these are given below
S N 1 C 2H C 3H C 2H C 3H
+ –
H 3 C C B r H 3 C C + : B r
H H
C 2H C 3H C 2H C 3H
+ –
H 3 C C + : O H H 3 C C O H
H H
– –
S N 2 H O : C 2H C 3H C 2H C 3H
H 3 C C B r H O C B r
H 3 C H
H
C 2H C 3H
–
H O C H + : B r
C 3H
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(c) The oxidation of butan-2-ol with hot potassium dichromate(VI) in acidic solution
produces butanone, CH3COCH2CH3.
...........................................................................................................................
(1)
(ii) The dichromate(VI) ion is reduced under these conditions to chromium(III) ions.
+ –
CH3CH(OH)CH2CH3 → CH3COCH2CH3 + 2H + 2e
Write the ionic half-equation for the reduction of dichromate(VI) ions, and hence
derive the overall equation for the oxidation of butan-2-ol.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
S p e c t r u m o f b u t a n - 2 - o l
1 0 0
T ra n s m itta n c e /%
5 0
0
4 0 0 0 3 0 0 0 2 0 0 0 1
– 1
W a v e n u m b e r/c m
S p e c t r u m o f t h e o r g a n i c p r o d u c t f r o m t h e o
1 0 0
T ra n s m itta n c e /%
5 0
0
4 0 0 0 3 0 0 0 2 0 0 0 1
– 1
W a v e n u m b e r/c m
–1 –1
Bond Wavenumber/cm Bond Wavenumber/cm
C—O (alcohols,
C—H (alkanes) 2850–3000 1000–1300
esters)
O—H (hydrogen-
C—H (alkenes) 3000–3100 3230–3550
bonded alcohols)
C=O (aldehydes, 1680–1750 O—H (hydrogen- 2500–3300
ketones, carboxylic bonded carboxylic
acids) acids)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(d) When potassium dichromate(VI) is dissolved in water, the following equilibrium is set up
2– 2– +
Cr2O7 (aq) + H2O(l) 2CrO4 (aq) + 2H (aq)
(i) If a solution of barium ions is then added to this solution, solid barium chromate,
BaCrO4, is precipitated; it is sparingly soluble in water, so the equilibrium given
below also exists in the solution
2+ 2–
Ba (aq) + CrO4 (aq) BaCrO4(s)
Explain what happens to the pH when the barium ions are added.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
2+ 2–
Pb (aq) + CrO4 (aq) → PbCrO4(s)
State how the pH of this solution differs from your answer in part (i).
...........................................................................................................................
...........................................................................................................................
(1)
(Total 20 marks)
A positive
B negative
26. The drug ibuprofen can be synthesised from benzene by the route shown below.
C 3H C 3H C 3H C 3H
H — C3 — H C —H C3 — H C —H C3 — H C —H C3 — C H
C 2H C 2H C 2H C 2H
C O / P d
S t Ae p S t Be p S t Ce p c a t a l y s t
C O H — C — H O — H C2 — C O H
C 3H C 3H C 3H
I b u p r o f e n
Catalyst .......................................................................................................................
(3)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
State the molecular formula of ibuprofen and show that these results are consistent with
it.
(4)
C 3H
H — C3 — C H
C 2H
I b u p r o f e n h a s t h e f o r m u l a
H — C2 — C O H
C 3H
C 2O H
O
— O — C
A s p i r i n h a s t h e f C o Hr m u l a
3
O H
P a r a c e t a m o l h a s t h e f o r m u l a
C 3H
H — N — C
O
(i) Explain, referring to the structure of each molecule, why infrared spectroscopy is
not a good technique to distinguish aspirin from ibuprofen.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
S p e c t r u m X
1 0 0
T ra n s m itta n c e (% )
5 0
0
4 0 0 0 2 0 0 30 0 0 0
W a v e n u– 1 m b e r / c m
S p e c t r u m Y
1 0 0
T ra n s m itta n c e (% )
5 0
0
4 0 0 0 2 0 0 30 0 0 0
W a v e n u– 1 m b e r / c m
S p e c t r u m Z
1 0 0
T ra n s m itta n c e (% )
5 0
0
4 0 0 0 2 0 0 30 0 0 0 1 0 0 0
– 1
W a v e n u m b e r / c m
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(iii) Ibuprofen and aspirin can be distinguished using their mass spectra.
...........................................................................................................................
Suggest the mass/charge ratio of one line which occurs in the mass spectrum of
aspirin but not ibuprofen, and the formula of the species which produces it.
...........................................................................................................................
...........................................................................................................................
(3)
(Total 14 marks)
–
C12 H 25 S 3 ON a +
(a) (i) Name the reagents and give the conditions where necessary for the
two steps needed to make
–
S 3 ON a + f r o m b e n z e n e .
Conditions .................................................................................................
Step 1 ................................................................................................................
(b) (i) What is the specific name given to the reaction when an alkyl group is
introduced into the benzene ring by electrophilic substitution?
...........................................................................................................................
(1)
(ii) Give the molecular formula of the reagent and of the catalyst needed to make
12 H 25 C f r o m b e n z e n e .
Reagent .............................................................................................................
Catalyst .............................................................................................................
(2)
(Total 8 marks)
28. Phenylethanoic acid occurs naturally in honey as its ethyl ester: it is the main cause of the
honey’s smell.
C 2H C O O H
The acid has the structure
C H 3 C H 2C l
s t e p 1 s t e p 2
C l2 , u v
s t e p 3
K C N
s t e p 4
C 2H C O O HC o m Ap o u n d
.....................................................................................................................................
.....................................................................................................................................
(2)
...........................................................................................................................
(1)
(ii) Suggest a mechanism for step 2. You should include the initiation step, the two
propagation steps and a termination step.
You may use Ph to represent the phenyl group, C6H5.
(4)
(3)
(Total 10 marks)
C 3H
C H
C 3H
+ 3 CC HH B3 r C H + H B r
c u m e n e
(i) Identify a suitable catalyst for the reaction between benzene and 2-bromopropane.
...........................................................................................................................
(1)
(4)
(b) If benzene and 1-bromopropane, CH3CH2CH2Br, are reacted under similar conditions to
those in part (a), the product is still cumene although 1-phenylpropane C6H5CH2CH2CH3
might have been the expected product.
C 3H
C H
C 3H
+ 3 CC HH 2 C H 2 B r + H B r
c u m e n e
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
+
(c) Phenol reacts with the benzenediazonium cation, C6H5N2 , in alkaline conditions to give
an azo dye.
(i) State the reagents needed to convert phenylamine into a solution containing
+
C6H5N2 ions.
...........................................................................................................................
(2)
(ii) Explain why the temperature of the reaction in (c)(i) needs to be kept between 0 °C
and 10 °C.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(2)
(d) (i) How would you show that propanone is a carbonyl compound and is a
ketone, not an aldehyde?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(3)
(Total 22 marks)
Cr: [Ar]…………………………….
Cu: [Ar]……………………………..
(1)
State how these electronic configurations differ from others in the first transition
series and explain why this difference arises.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
3+
(b) Chromium can form the ion [Cr(H2O)6] in aqueous solution.
(i) Draw the structure of this ion so as to clearly show its shape.
(1)
(ii) How are the bonds between the water ligands and the metal ion formed?
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
(2)
(iv) State what you would see as dilute sodium hydroxide is gradually added to a
3+
solution of [Cr(H2O)6] until it is in excess.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(v) What property of chromium(III) hydroxide is shown by the reaction in part (iv)?
...........................................................................................................................
(1)
3
25.0 cm of this solution was added to an excess of potassium iodide solution.
2– – + 3+
Cr2O7 + 6I + 14H → 2Cr + 3I2 + 7H2O
–3
The iodine liberated was titrated with 0.100 mol dm sodium thiosulphate
solution.
2– – 2–
I2 + 2S2O3 → 2I + S4O6
Calculate the amount (moles) of iodine liberated and hence the percentage, by
mass, of chromium in the alloy.
(5)
(ii) In titrations involving iodine, starch is usually added near the end-point to make
the colour change clearer, although in many cases it is not really necessary.
...........................................................................................................................
...........................................................................................................................
(1)
(Total 16 marks)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(b) Explain why a reference electrode is needed whenever a standard electrode potential is
measured.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
+ – ο
O2 + 2H + 2e H2O2 E = + 0.68 V
+ – ο
H2O2 + 2H + 2e 2H2O E = + 1.77 V
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(iii) Explain why your answer to (ii) does not necessarily show that hydrogen peroxide
will disproportionate under standard conditions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 9 marks)
B e n z e r n e e a gW e n t A 2 m o l e s X o f r Be a g e n t
C 6 H 6 C 6 H 6 S O c 3a t a l y s t Y C 8H 10 SO 3
O H
re ag e n t Z C 2 l ( g )
B C
C 8 H 1 0 S O 3 C 8 H 1 0 O
H 3C C 3H
C l
D e t t o l
Study this reaction scheme carefully before answering any of the questions below.
(1)
...........................................................................................................................
(1)
(iii) State the type of reaction and the mechanism for the conversion of benzene into A.
...........................................................................................................................
(1)
...........................................................................................................................
(1)
(b) (i) Suggest the structural formula of B. You may find it helpful to study
the formula for Dettol, as well as your answer to (a)(i), when answering this
question.
(1)
(iii) What gaseous inorganic compound will also be produced during the formation of
B?
...........................................................................................................................
(1)
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 10 marks)
C O O H
H — C — H
N H 2
(i) Draw the full structural formula of the zwitterion of glycine, showing all bonds.
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b) Suggest the formula of the organic product formed when glycine reacts, under suitable
conditions, with
+
(i) hydrogen ions, H
(1)
–
(ii) hydroxide ions, OH
(1)
(1)
(1)
(c) Glutamic acid is also an amino acid. The formula of glutamic acid is shown below.
H 2N — C — CO O H
C H 2
C H 2
CO O H
Glutamic acid exists as two optical isomers whereas glycine does not.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
O O O O
— C 2 ( C4 H ) C N H 2 ( 6C H ) N H C 2 ( 4C H ) C N H
Give the formulae of TWO monomers which could react together, under suitable
conditions, to form nylon-6,6.
(2)
(Total 13 marks)
C 3H
B r
R e a 3c tB i 2 o r n / F e B 3 r
C 3H C 3H C H O
R e a 2c t i o n R e a 4c t i o n
M 2n O
N O T o l u e n e B e n z a l d e
2
F u m i n g
R e a 1c t i o n R e a 5c t i o n
H 2 S O 4
C o m p o u n d A C 2O H
B e n z o i c a c i d
...........................................................................................................................
(1)
(1)
...........................................................................................................................
...........................................................................................................................
(2)
...........................................................................................................................
(1)
Reaction Type
...........................................................................................................................
Mechanism
...........................................................................................................................
(2)
(ii) Suggest why Reactions 1, 2 and 3 all take place under milder conditions than
similar reactions involving benzene.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
.....................................................................................................................................
(1)
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 12 marks)
35. Vanillin, the main ingredient of vanilla essence, is one of the commonest flavouring ingredients
found in foods. Synthetic vanillin, which is identical to natural vanillin, can be manufactured
from methoxybenzene. One synthetic route is shown below:
S 3O H O H
O C3 H O C3 H O C3 H O C H 3
C H O
m e t h o x y b e n z e n e 2 - m e t h o x y b e n z e
s u l p h o n i c a c i d
...........................................................................................................................
(1)
(ii) Name the type of reaction which occurs and its mechanism.
...........................................................................................................................
(2)
...........................................................................................................................
...........................................................................................................................
(1)
(ii) The impure vanillin may contain soluble and insoluble impurities. Describe how
each of these is removed during recrystallisation.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii) How would you check the purity of the vanillin after recrystallisation, other than by
using an infrared spectrometer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
I n f r a r e d S p e c t r u m o f 2 - M e t h o x y p h e n o
1 0 0
8 0
T ra n s m itta n c e
/ % 6 0
4 0
2 0
3 0 0 0 2 0 0 0
–1
W avenum ber/cm
I n f r a r e d S p e c t r u m o f P r o d u c t
1 0 0
8 0
T ra n s m itta n c e
/ %
6 0
4 0
3 0 0 0 2 0 0 0
–1
W avenum ber/cm
–1
Wavenumber / cm
C C Stretching Vibrations Arene 1600 – 1450
C—H Stretching Vibrations Arene 3030
O—H Stretching Vibrations Alcohols and phenols 3750 – 3200
C O Stretching Vibrations Aldehydes 1740 – 1720
Ketones 1700 – 1680
Carboxylic acids 1725 – 1680
Esters 1750 – 1735
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 10 marks)
Cu : [Ar] ......................................................................................................................
+
Cu : [Ar] ......................................................................................................................
(1)
+
(b) (i) Explain why Cu ions are colourless.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
ο
E /V
2+ – +
Cu (aq) + e Cu (aq) + 0.15
+ –
Cu (aq) + e Cu(s) + 0.52
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
+
(iii) Explain why your answer to (ii) does not rule out the existence of Cu (aq) under
standard conditions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(2)
Suggest a formula for F, given that all the hydrogen is present in hydroxide ions.
...........................................................................................................................
(2)
(iii) When excess concentrated ammonia is added to F, a deep blue solution is formed.
Give the formula of the ion responsible for this colour.
...........................................................................................................................
(1)
...........................................................................................................................
(1)
(d) Copper metal can be used as a catalyst. When propan-1-ol vapour is passed over heated
copper, the following reaction occurs:
CH3CH2CH2OH → CH3CH2CHO + H2
(i) Outline how, by the use of 2,4-dinitrophenylhydrazine and suitable tables of data,
you could show that the product is propanal.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
(1)
(iv) Suggest why the oxidation of the alcohol by passing it over heated copper does not
lead to further oxidation of the aldehyde.
...........................................................................................................................
...........................................................................................................................
(1)
(v) There are a few places on the surface of the metal where catalysis can occur.
These are called ‘active sites’.
Suggest why this leads to the rate of reaction being independent of the gas pressure
unless this pressure is extremely low.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 20 marks)
In the volumetric analysis of the composition of brass, the first step is to react a weighed sample
of the alloy with nitric acid. This gives a greenish-blue solution.
(a) The following standard electrode potentials are needed for this question:
ο
E /V
2+ –
Zn + 2e Zn – 0.76
2+ –
Cu + 2e Cu + 0.34
– + –
NO3 + 2H + e NO2 + H2O + 0.81
ο
(i) Use the half equations given above and the values of E to calculate the standard
electrode potential for the reaction between zinc and nitric acid and derive the
equation.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii) Suggest why zinc does not produce hydrogen with nitric acid.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
Name the light blue complex ion and draw its structure so as to show its shape.
Name .................................................................................................................
Structure:
(2)
(iv) If concentrated hydrochloric acid is added to a portion of the light blue solution it
turns green.
State the type of reaction that occurs and give an equation for the reaction.
...........................................................................................................................
...........................................................................................................................
(2)
(b) The light blue solution from (a)(iii) is then neutralised, and reacted with an excess of
potassium iodide solution.
2+ –
2Cu (aq) + 4I (aq) → 2CuI(s) + I2(aq)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(ii) Explain why, in practice, the reaction in (i) does occur and iodine is liberated.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii) When the precipitate formed in the reaction in (i) is filtered off and then dissolved
in concentrated aqueous ammonia, a colourless solution is produced.
...........................................................................................................................
(1)
(iv) If the colourless solution from (iii) is left to stand in air for some time, it turns blue.
State why this is so, naming the reactant responsible for the change.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
3
Excess potassium iodide solution was added to 25.0 cm portions of this solution, and the
–3
liberated iodine titrated with 0.100 mol dm sodium thiosulphate solution. The mean titre
3
was 16.55 cm .
2+ –
2Cu (aq) + 4I (aq) → 2CuI(s) + I2(aq)
2− − 2–
2S2O3 (aq) + I2(aq) → 2I (aq) + S4O6 (aq)
(i) State which indicator you would use for the titration and the colour change seen at
the end point.
...........................................................................................................................
...........................................................................................................................
(2)
(ii) Explain why the indicator is not added until the reaction is nearly complete.
...........................................................................................................................
...........................................................................................................................
(1)
(5)
(Total 22 marks)
(a) (i) Use the data to explain why dilute hydrochloric acid is not used to
acidify solutions of potassium manganate(VII).
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(ii) Explain why titrations involving potassium manganate(VII) solution do not require
the addition of an indicator.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
Explain, in terms of the half equations listed above, why the ratio of
manganate(VII) ions to iron(ii) ions is 1 : 5 in this reaction.
(1)
Some tablets, of total mass 6.00 g, were dissolved in distilled water and made up to
3 3
200 cm in a volumetric flask. 25.0 cm portions of this solution were titrated
–3
against a 0.0200 mol dm solution of acidified potassium manganate(VII). The
3
mean titre was 20.10 cm .
(5)
(c) An important application of redox reactions is in car batteries. The electrolyte is aqueous
sulphuric acid and the standard electrode potentials involved are shown below.
ο
E /V
2+ –
Pb (aq) + 2e Pb(s) –0.13
+ – 2+
PbO2(s) + 4H (aq) + 2e Pb (aq) + 2H2O(l) +1.46
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
(1)
(Total 11 marks)
3
39. Air is drawn through 10.0 cm of an aqueous solution of vanadium(II) chloride of concentration
–3
0.100 mol dm . The colour of the solution slowly changes as oxidation takes place.
(i) Draw a diagram of suitable apparatus for carrying out the air-oxidation of the
vanadium(II) chloride solution.
(1)
(ii) Complete the half equation for acidified manganate(VII) ions acting as an oxidising
agent.
– + – 2+
MnO4 (aq) + ..............H (aq) + 5e (aq) → Mn (aq) + ..............H2O(1)
(1)
(4)
(iv) Suggest ONE reason why acidified potassium manganate(VII) is a useful oxidising agent
in redox titrations.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 7 marks)
– – –
Step 1 IO3 (aq) + 3HSO3(aq) → I (aq) + 3HSO4 (aq)
– – +
Step 2 IO3 (aq) + 5I (aq) + 6H (aq) → 3I2(aq) + 3H2O(l)
(a) (i) Describe a test you could carry out to confirm the presence of iodide
ions in a solution. Indicate the result of the test.
Test ...................................................................................................................
...........................................................................................................................
Result ................................................................................................................
...........................................................................................................................
(2)
(ii) Identify the TWO elements in Step 1 which show a change of oxidation number
during the reaction.
–
(iii) The equation for Step 1 shows that 1 mole of iodate ions, IO3 , reacts with 3 moles
of hydrogensulphite ions, HSO3. Show that your answers to (ii) agree with this
ratio.
(1)
3
(i) What piece of apparatus would you use to measure out the 10.0 cm portion?
...........................................................................................................................
(1)
(ii) Suggest a suitable indicator to show the end-point of this titration. State the colour
change you would see.
Indicator .................................................................................................................
(iii) Calculate the number of moles of sodium thiosulphate used in the titration.
(1)
(1)
–3
(v) Calculate the concentration, in mol dm , of the iodine solution.
(1)
(Total 12 marks)
41. Paracetamol can be manufactured from phenol using the reaction sequence below.
O H O H O H O H
S t e p 1 S t e p 2 S t e p 3
N 2O N 2H N H C 3 O C H
A B C P a r a c e t a m o l
.....................................................................................................................................
.....................................................................................................................................
(2)
.....................................................................................................................................
(1)
...........................................................................................................................
(1)
(ii) Suggest a test and its results for the amino group in compound C.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(d) (i) Write a balanced equation for the reaction occurring when
paracetamol is boiled with an aqueous solution of sodium hydroxide.
(2)
...........................................................................................................................
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(4)
...........................................................................................................................
...........................................................................................................................
(1)
(f) Suggest which bond gives rise to the broadest absorption in the infrared spectrum of
paracetamol.
State the range of wavenumbers for this absorption.
...........................................................................................................................
...........................................................................................................................
(2)
...........................................................................................................................
(1)
(ii) Suggest the formulae of the ions responsible for the peaks at mass / charge ratios
43 and 93.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(h) Suggest ONE advantage of using paracetamol, rather than aspirin, as a pain reliever.
.....................................................................................................................................
.....................................................................................................................................
(1)
(Total 20 marks)
Ni
3d 4s
[ Ar ]
2+
Ni
3d 4s
[ Ar ]
(2)
.....................................................................................................................................
.....................................................................................................................................
(1)
e x c e s s
p a l e g N r He e ( a n q 3 )
S t e p 2 :
p r e c i p i t a t eb l u e s Xo l u t i o n
2+
(i) What types of bond are present in the [Ni(H2O)6] ion?
...........................................................................................................................
...........................................................................................................................
(2)
(ii) Write an equation for the formation of the pale green precipitate.
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
(2)
2+
(d) Explain why the hexaaquanickel(II) ion, [Ni(H2O)6] , is coloured.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 14 marks)
43. (a) (i) Describe the appearance of the organic product obtained when an
aqueous solution of bromine is added to aqueous phenol.
...........................................................................................................................
(1)
(2)
(1)
(iv) Suggest, in terms of the bonding in ethanoyl chloride, why the reaction in (a)(iii)
proceeds without the need for heat or a catalyst.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(b) Phenylamine, C6H5NH2, is formed by the reduction of nitrobenzene, C6H5NO2. Give the
reagents which are used.
.....................................................................................................................................
.....................................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
(2)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(1)
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(5)
(Total 17 marks)
(i) Write the empirical formula of A and use the combustion data to show that the
empirical formula is correct.
(3)
(ii) A reacts with an excess of bromine water to form B, C6H10Br2. Suggest structural
formulae of A and B.
(2)
State appropriate conditions, and write the balanced equation, for this reaction.
(4)
(2)
(Total 11 marks)
45. This question is about the arene, naphthalene. The structure of naphthalene can be shown as
.....................................................................................................................................
(1)
– 1
+ 2 H ∆H = – 1 2 0 k J
(i) Calculate the enthalpy change of the hydrogenation reaction shown below.
+ 2 5 H
–1
ΔH = ...................... kJ mol
(1)
(ii) Experimental work shows that ΔH for the hydrogenation of naphthalene is actually
–1
–333 kJ mol . What does this suggest about the stability and structure of
naphthalene?
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(iii) Would you expect naphthalene to decolorise bromine solution? Justify your
answer.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(i) Suggest the reagent and catalyst you would need to make
C H 3( 2 C H )
from naphthalene.
Reagent ..............................................................................
Catalyst ..............................................................................
(2)
...........................................................................................................................
(2)
(Total 9 marks)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(b) When a metal is placed in a solution of its ions, the electrical potential set up between the
metal and the solution cannot be measured without using a reference electrode. Explain
why this is so.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
ο
E /V
2+
Zn (aq) + 2e Zn(s) –0.76
2+ –
Fe (aq) + 2e Fe(s) –0.44
2+ –
Sn (aq) + 2e Sn(s) –0.14
– –
O2(g) + 2H2O(1) + 4e 4OH (aq) +0.40
(i) Write an overall equation for the first stage in the rusting of iron.
...........................................................................................................................
...........................................................................................................................
(2)
ο
(ii) Calculate E for the reaction in (i) and show that it is feasible.
...........................................................................................................................
...........................................................................................................................
(2)
ο
(iii) Use the E values above to explain why zinc is used in preference to tin for
preventing corrosion of steel car bodies.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(3)
(Total 10 marks)
(a) Write the ionic equation to show the disproportionation of the chlorate(I) ion. Use
oxidation numbers to explain the meaning of the term disproportionation in this reaction.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
–
(b) Domestic bleaches are dilute solutions of sodium chlorate(I). The amount of ClO ions in
a sample can be found by reacting it with excess acidified potassium iodide solution.
– – + –
ClO + 2I + 2H → I2 + Cl + H2O
The iodine produced is then titrated with standard sodium thiosulphate solution.
3 3
• 10.0 cm of a domestic bleach was pipetted into a 250 cm volumetric flask and made
up to the mark with distilled water.
3
• A 25.0 cm portion of the solution was added to excess acidified potassium iodide
solution in a conical flask.
–3
• This mixture was titrated with 0.100 mol dm sodium thiosulphate solution, using
starch indicator added near the end point.
3
• The mean titre was 12.50 cm .
(i) Give the colour change you would see at the end point.
...........................................................................................................................
...........................................................................................................................
(1)
2– 2– –
2S2O3 + I2 → S4O6 + 2I
3
Calculate the amount (moles) of chlorate(I) ions in 1.00 dm of the original bleach.
(5)
3
(iii) Use the equation below to calculate the mass of chlorine available from 1.00 dm
of the original bleach. Give your answer to 3 significant figures.
– – +
ClO + Cl + 2H → Cl2 + H2O
(1)
2– 2– + –
S2O3 + 4Cl2 + 5H2O → 2SO4 + 10H + 8Cl
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(d) Starch-iodide paper can be used to test for chlorine. It contains starch and potassium
iodide.
Explain the reactions taking place when a piece of damp starch-iodide paper is put in a
gas jar of chlorine. State what you would see.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 14 marks)
...........................................................................................................................
...........................................................................................................................
(1)
(ii) Which of the elements, from scandium to zinc inclusive, are in the d-block but are
not transition elements?
...........................................................................................................................
(1)
2+ 2+
(b) (i) Complete the electronic configurations of the Fe and Mn ions
below.
2+
Fe [Ar] ..............................................................................................................
2+
Mn [Ar] .............................................................................................................
(1)
2+ 3+ 2+
(ii) Suggest why Fe ions are readily oxidised to Fe ions, but Mn ions are not
3+
readily oxidised to Mn ions.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(2)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(e) Ammonium vanadate(V), NH4VO3, reacts with dilute sulphuric acid to form a solution
+
containing yellow VO2 ions.
(i) Write an ionic equation for the reaction of the anion in NH4VO3 with dilute
sulphuric acid.
...........................................................................................................................
(1)
...........................................................................................................................
...........................................................................................................................
(1)
+
(iii) Addition of zinc to the solution containing VO2 ions causes the colour to change
from yellow to green then to blue, followed by green again and finally violet.
State the formulae of the ions responsible for each of these colours.
H 2 ∆H = – 1 2
–
0
1
k J m o l
2 H
2 ∆H = – 2 4
–
0
1
k J m o l
3 H2 ∆H = – 2 0
–
8
1
k J m o l
Explain, in terms of the bonding in benzene, why the enthalpy change of hydrogenation
–1
of benzene is not –360 kJ mol .
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(4)
(c) Benzene, C6H6, reacts with bromoethane, CH3CH2Br, in the presence of a catalyst, to
form ethylbenzene, C6H5CH2CH3, and hydrogen bromide.
...........................................................................................................................
(1)
(4)
...........................................................................................................................
(1)
(Total 13 marks)
50. This question is about the element chromium and its compounds.
(a) (i) State the full electronic configuration of a chromium atom in the
ground state, using the s,p,d notation.
(1)
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
2+
(b) Compounds containing the chromium(II) ion, Cr , are unstable in aqueous solution
because they are readily oxidised by oxygen in the air.
State the appropriate electrode potentials and half-cells, and use them to explain why this
oxidation takes place.
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(3)
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)
...............................................................................................................................
(1)
(iii) Deduce the number of hydrogen peaks in the NMR spectrum of the complex from
the structural formula Cr2(CH3CO2)4(H2O)2. Justify your answer.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)
You should state the bond associated with each absorption and give the
corresponding absorption value in wavenumbers.
................................................................................................................................
................................................................................................................................
................................................................................................................................
................................................................................................................................
(2)
(2)
(ii) State the colour change you would expect to see if exhaled air containing an
excessive amount of ethanol reacted with the breathalyser chemicals.
................................................................................................................................
(1)
................................................................................................................................
................................................................................................................................
(1)
(Total 17 marks)
51. The reaction sequence below shows a method that could be used to convert benzene into
benzoic acid.
(a) (i) Name the reagent and catalyst that could be used to convert benzene
into A in Step 1.
Equation
Explanation ............................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)
(b) (i) B has several isomers. Draw the structural formula of ONE of these
isomers, and give its systematic name.
Structural formula
Name ......................................................................................................................
(2)
(ii) Name the reagent and catalyst you would use to try to make your isomer from A.
................................................................................................................................
(2)
.......................................................................................................................................
(1)
(e) Suggest TWO reactions in which you would observe the same results when carried out
with either compound C or benzoic acid. Describe what you would see in each of the two
reactions.
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(4)
(Total 19 marks)
52. (a) Benzene, C6H6, reacts with ethanoyl chloride, CH3COCl, to give a compound of
(i) Identify another substance that must be present for this reaction to occur and state
the function of this substance in this reaction.
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(2)
(4)
(b) Phenol, C6H5OH, reacts differently from benzene with ethanoyl chloride. State the type
of reaction that would occur between phenol and ethanoyl chloride and give the structure
of the organic product.
(2)
(2)
(ii) A polymer can be formed by reacting one of these isomers with the di-acyl
chloride, ClCOCH2COCl.
(2)
N N O H
can be obtained from phenylamine and phenol in two steps. Identify the intermediate
formed and give the reagents and conditions for each step.
…………..…………...……………….………………….…………………………..
…………..…………...……………….………………….…………………………..
…………..…………...……………….………………….…………………………..
…………..…………...……………….………………….…………………………..
…………..…………...……………….………………….…………………………..
…………..…………...……………….………………….…………………………..
(4)
(Total 16 marks)
2
1s ...............................................................................................................................
(1)
2+
(ii) a Zn ion:
2
1s ...............................................................................................................................
(1)
............................................................................................................................................
............................................................................................................................................
............................................................................................................................................
(2)
2+
(c) Draw a 3-dimensional representation of the [Zn(H2O)6] ion, including the bond angles.
(4)
(d) (i) State what you would see when ammonia solution is added to an
aqueous solution of zinc(II) ions, first in a small amount and then to excess.
.....................................................................................................................................
.....................................................................................................................................
(2)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
2+
(e) (i) Explain why [Zn(H2O)6] ions have no colour.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
.....................................................................................................................................
(1)
(Total 16 marks)
54. (a) (i) Define the term standard electrode potential, making clear the
meaning of standard in this context.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(1)
(b) The following data will be required in this part of the question.
ο
E /V
– + – 2+
MnO4 + 8H + 5e Mn + 4H2O +1.52
+ –
O2 + 2H + 2e H2O2 +0.68
+ –
H2O2 + 2H + 2e 2H2O +1.77
(i) Derive the equation for the reaction between hydrogen peroxide and
ο
manganate(VII) ions in acidic solution and use E values to show that the reaction
is feasible.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 12 marks)
55. (a) Give the structural formula of the organic product when phenol is reacted with:
(1)
(1)
(1)
(i) State the reagents and conditions needed to make benzenediazonium chloride from
phenylamine.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)
(2)
............................................................................................................................
(1)
(Total 9 marks)
If a solution contains both iron(II) and iron(III) ions, the concentration of each ion can be
found by:
• titrating samples of the original solution with standard potassium manganate(VII) solution
• reacting samples of the original solution with zinc and dilute sulphuric acid and then titrating
with the same potassium manganate(VII) solution.
ο
E /V
2+ –
Zn + 2e Zn – 0.76
2+ –
Fe + 2e Fe – 0.44
3+ – 2+
Fe +e Fe + 0.77
– + – 2+
MnO4 + 8H + 5e Mn + 4H2O + 1.51
ο
(a) (i) Use suitable E values to show that both iron(II) and iron(III) ions in
solution should react with zinc to give iron metal.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
3+ 2+ 2+
2Fe + Zn → 2Fe + Zn
.....................................................................................................................................
.....................................................................................................................................
(1)
(b) (i) Derive the ionic equation for the reaction between iron(II) ions and
–
manganate(VII), MnO4 , ions.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(ii) State what you would see as iron(II) ions in solution are titrated with potassium
manganate(VII). How would you detect the endpoint of the titration?
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
Another portion of the same volume of the same solution was reacted with zinc, and then
3
titrated with the same potassium manganate(VII) solution; 25.30 cm was required.
What mass of zinc had reacted?
(5)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
–3 2+
(ii) Suggest with reasons which of 0.1 mol dm aqueous solutions of [Fe(H2O)6] and
3+
[Fe(H2O)6] would be the more acidic.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(Total 20 marks)
Fe [Ar].....................................................................................................
2+
Fe [Ar].....................................................................................................
(2)
(1)
(iii) Give the equation for the complete reaction of sodium hydroxide solution with a
solution of hexaaquairon(II) ions.
............................................................................................................................
(1)
(iv) State what you would see if the product mixture in (iii) is left to stand in air.
............................................................................................................................
............................................................................................................................
(1)
(v) Give the equation for a reaction in which iron metal is used as a catalyst.
............................................................................................................................
(1)
2+ – ο
Fe + 2e Fe E = –0.44 V
(i) Define the term standard electrode potential with reference to this electrode.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)
ο
(ii) Explain, with the aid of an equation, why the value of E suggests that iron will
2+
react with an aqueous solution of an acid to give Fe ions and hydrogen gas.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)
ο
(iii) State why E values cannot predict that a reaction will occur, only that it is
possible.
............................................................................................................................
............................................................................................................................
(1)
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(Total 15 marks)
58. Alanine, 2-aminopropanoic acid, is the simplest chiral amino acid found in nature and is
optically active.
H O
H 2 NC C
C 3H O H
.....................................................................................................................................
.....................................................................................................................................
(1)
.....................................................................................................................................
.....................................................................................................................................
(2)
(iii) If alanine is made from propanoic acid the product mixture does not show optical
activity. Explain why this is so.
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
hydrochloric acid
sodium hydroxide
(2)
Draw the structure that is actually present in the solid, and explain why the melting
temperature is so high.
............................................................................................................................................
...........................................................................................................................................
............................................................................................................................................
(2)
(d) Polyamides are made from a diacid dichloride and a diamine; they are condensation
polymers.
.....................................................................................................................................
.....................................................................................................................................
(1)
(2)
(iii) Draw sufficient of the polymer chain that would result from the reaction of the
compounds in (ii) to make the structure of the polymer clear.
(2)
(2)
(Total 16 marks)
59. This question is about the reactions of benzene and some related compounds.
Reagent ..................................................................................................................
Conditions...............................................................................................................
(2)
...............................................................................
(1)
(b) (i) Give the structural formula of the organic compound A formed in
Reaction 2.
(1)
Type .......................................................................................................................
Mechanism ............................................................................................................
(2)
(iii) Phenol, C6H5OH, will react with bromine in a similar way to benzene, but no
catalyst is needed. Explain why phenol will react readily with bromine without a
catalyst.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)
...............................................................................................................................
(1)
(ii) Explain how aluminium chloride acts as a catalyst in Reaction 3. You may find it
helpful to use an equation in your answer.
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(2)
(d) (i) What condition is needed for chlorine to react with benzene in
Reaction 4?
...............................................................................................................................
(1)
...............................................................................................................................
(1)
(Total 13 marks)
–1
60. (a) The enthalpy of hydrogenation of cyclohexene is –120 kJ mol .
+ 2 H
+ 22 H
.....................................................................................................................................
(1)
+ 32 H
.....................................................................................................................................
(1)
–1
(iii) The enthalpy of hydrogenation of benzene is –208 kJ mol . Explain in terms of the
structure and bonding in benzene why this value is different from your answer to
(a)(ii).
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(3)
(b) Benzene, C6H6, reacts with bromine to form bromobenzene, C6H5Br, and hydrogen
bromide.
(i) Give the formula of the catalyst that is needed for the reaction.
.....................................................................................................................................
(1)
(4)
(iii) State the type of mechanism that is commonly found with reactions of benzene and
its derivatives.
.....................................................................................................................................
(1)
(Total 11 marks)
(1)
(b) Three of the reactions in the diagram are electrophilic substitution reactions.
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
......................................................................................................................................
(2)
(1)
(d) Give the molecular formulae of two of the products, A and B, formed when
methoxybenzene reacts with bromine in an inert solvent.
(2)
(e) (i) Suggest the name for the organic product, C, formed when
methoxybenzene reacts with concentrated sulphuric acid.
............................................................................................................................
(1)
(ii) Suggest ONE use for the class of chemicals to which C belongs.
............................................................................................................................
(1)
D ........................................................................................................................
E ........................................................................................................................
(2)
...........................................................................................................................
...........................................................................................................................
(2)
...........................................................................................................................
(1)
(ii) Suggest why methoxybenzene rather than benzene is used in schools and colleges.
...........................................................................................................................
(1)
(Total 14 marks)
2+
(ii) a Ni ion.
2
1s ..............................................................................................................................
(1)
(3)
(c) If ammonia solution is added slowly to an aqueous solution containing nickel(II) ions, a
pale green precipitate initially forms. This dissolves to give a blue solution in excess
ammonia.
.....................................................................................................................................
(1)
(ii) State the type of reaction occurring when ammonia solution is added as in (i) and
explain the formation of the precipitate.
.....................................................................................................................................
.....................................................................................................................................
(2)
.....................................................................................................................................
.....................................................................................................................................
.....................................................................................................................................
(2)
(Total 10 marks)
......................................................................................................................
......................................................................................................................
(2)
(ii) Write the mechanism for the reaction, including the formation of the species that
attacks the benzene molecule.
(4)
......................................................................................................................
(1)
(b) Further reaction produces trinitrobenzene. Draw the structural formulae of the three
isomeric trinitrobenzenes.
(c) Give the reagents and conditions required for the conversion of nitrobenzene into
phenylamine, C6H5NH2.
...............................................................................................................................
...............................................................................................................................
(2)
(d) (i) Draw the structural formula of the organic product of the reaction
between phenylamine and ethanoyl chloride, CH3COCl.
(1)
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(6)
(Total 19 marks)
(i) Cr:
3d 4s
[A r]
(1)
3+
(ii) Cr :
3d 4s
[A r]
(1)
excess conc
NH 3 (aq) NH 3 (aq)
→ →
3+
[Cr(H2O)6] (aq) Step 1 green precipitate Step 2 solution X
3+
(i) Name the two types of bond present in the [Cr(H2O)6] ion.
......................................................................................................................
......................................................................................................................
(2)
......................................................................................................................
(1)
......................................................................................................................
(1)
......................................................................................................................
(1)
......................................................................................................................
(1)
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(Total 11 marks)
(a) Hydrated nickel(II) salts are green in colour. Give the electron configuration of a
nickel(II) ion and hence state why the ion is coloured.
.......................................................................................................................................
.......................................................................................................................................
.......................................................................................................................................
(2)
(b) (i) Which is the only nickel compound, in Table 5.3 in the Book of Data,
in which the nickel atom does not have an oxidation number of +2?
............................................................................................................................
(1)
............................................................................................................................
(1)
(i) Write the equation, including state symbols, for the displacement of one water
molecule by an ammonia molecule.
(1)
(ii) Would you expect ΔSsystem for this reaction to be positive, negative or close to
zero? Justify your answer.
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(2)
(d) The complexes formed when ammonia solution is added to nickel(II) chloride solution
have the formula [Ni(H2O)x(NH3)6–x]Cl2. An experiment was carried out to determine the
value of x in one of them.
A sample of 5.000 g of this complex was dissolved in water and reacted with excess
silver nitrate. 6.133 g of silver chloride was produced.
(i) Write the ionic equation, including state symbols, for the formation of silver
chloride.
(1)
Each mole of the complex contains two moles of chloride ions. Calculate the
number of moles of the complex present in the 5.000 g sample.
(3)
(iii) Use your answer in (ii) to calculate the value of x and hence the formula of this
complex ion.
(1)
(2)
(Total 14 marks)
66. Benzene, C6H6, reacts with ethanoyl chloride, CH3COCl, by an electrophilic substitution
reaction in the presence of aluminium chloride as a catalyst.
(a) Identify the electrophile involved in this reaction and write an equation to show its
formation.
................................................................................................................................
................................................................................................................................
(2)
(b) Draw the mechanism for the electrophilic substitution of benzene by ethanoyl chloride.
(3)
O H
C 6H 5 C C O O H
C H 3
(5)
(Total 10 marks)
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(5)
......................................................................................................................
(1)
–
the reduction of the manganate(VII) ion, MnO4 , in acidic solution.
......................................................................................................................
(1)
(ii) Combine the two half equations above to produce the ionic equation for the
oxidation of iron(II) ions by manganate(VII) ions in acidic solution.
......................................................................................................................
(1)
(3)
Half equation E /V
3+ – –0.04
Fe (aq) + 3e Fe(s)
2+ – –0.44
Fe (aq) + 2e Fe(s)
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
...............................................................................................................................
(3)
(Total 14 marks)
………………...……………….……………………………………………………..
………………...……………….……………………………………………………..
(1)
A n a q u e o u s s o lu tio n o f
c h ro m iu m (II I) c h lo rid e
N a O H (a q ) Z n (s ) + H C l(a q )
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
………………...……………….………………….…………………………..
(2)
………………...……………….………………….…………………………..
(1)
(c) Evaporating cold aqueous chromium(III) chloride produces violet crystals. However
when hot aqueous chromium(III) chloride crystallises, green crystals result.
Both types of crystal have the same composition by mass: 19.5% chromium, 40.0%
chlorine and 40.5% water.
(i) Show that the empirical formula of these two salts is Cr(H2O)6Cl3.
(2)
(ii) The addition of excess aqueous silver nitrate to aqueous solutions of either of these
two salts produces a precipitate of silver chloride, AgCl.
+ –
Ag (aq) + Cl (aq) → AgCl(s)
Under these conditions all the chloride from the violet salt is precipitated but only
two-thirds of the chloride from the green salt.
(2)
(Total 8 mark)
69. (a) Pure copper is needed for electrical applications. The purity of a sample of copper
can be found by reacting it with concentrated nitric acid, neutralising the resulting
solution and treating it with excess potassium iodide. Iodine is liberated and this can be
titrated with standard sodium thiosulphate solution. The reactions are:
2+ –
2Cu (aq) + 4I (aq) → 2CuI(s) + I2(aq)
3
A copper foil electrode from an electric cell weighs 1.74 g. It was made into 250 cm of a
3
solution of copper(II) ions. To 25.0 cm of this solution excess iodide ions were added,
–3
and the mixture titrated with 0.100 mol dm sodium thiosulphate solution. On average
3
26.8 cm was required. Calculate the percentage purity of the copper foil.
(6)
+
–
C6H5N 2 Cl → C6H5Cl + N2
The catalytic effect of transition metals or their ions is often attributed to their having
several stable oxidation states. Explain why such states are possible in transition metals
and why they are important in catalysis.
(4)
(ii) Explain why the temperature needs to be carefully controlled in the reaction in part
(i).
(2)
(iii) Write the equation for the reaction of benzenediazonium chloride with phenol
using structural formulae. Give the conditions under which benzenediazonium
chloride reacts with phenol and state what you would see.
(5)
(d) Phenylamine is prepared from benzene. Give the reagents and conditions needed for each
of the steps in the conversion of benzene to phenylamine.
(6)
(Total 25 marks)
sodium carbonate
Brady’s reagent
(2,4-dinitrophenylhydrazine)
potassium dichromate(VI) +
sulphuric acid
(6)
(b) Both X and Y can take part in reactions in which esters are formed.
(i) Complete the structural formula of the ester which forms when X reacts with
methanol.
(1)
(1)
(2)
(iv) When X forms an ester with methanol, a catalyst is needed for the reaction to
proceed at a reasonable speed when heated gently.
...........................................................................................................................
(1)
(v) Explain why ethanoyl chloride is reactive enough to form an ester with Y at a
reasonable speed without a catalyst and without heating.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(2)
(c) The benzene ring in Y reacts readily with bromine in a substitution reaction.
(i) Name the type of reagent which attacks a benzene ring in substitution reactions.
...........................................................................................................................
(1)
.............................................................................................................................
(1)
(iii) Suggest a structural formula for an organic product of the reaction of bromine with
Y.
(1)
(iv) Y reacts with bromine more readily than benzene does. Suggest a reason for this.
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
...........................................................................................................................
(1)
(Total 17 marks)
3+
71. (a) Complete the electronic structure of a scandium atom, a chromium atom and a Cr
ion.
3d 4s
Sc [A r]
Cr [A r]
C r 3+ [A r]
(3)
....................................................................................................................................
....................................................................................................................................
....................................................................................................................................
(2)
3+ 3+
(c) Cr exists in aqueous solution as the green ion [Cr(H2O)6] .
3+
(i) Complete the ‘electrons in boxes’ diagram for the complex ion [Cr(H2O)6] .
Distinguish clearly the chromium electrons from those of the ligand.
3d 4s 4p
[A r]
(2)
3+
(ii) Draw the [Cr(H2O)6] ion so as to clearly show its shape.
(1)
3+
(iii) Explain the origin of the colour in [Cr(H2O)6] .
............................................................................................................................
............................................................................................................................
............................................................................................................................
............................................................................................................................
(3)
............................................................................................................................
............................................................................................................................
(2)
............................................................................................................................
............................................................................................................................
(1)
(Total 14 marks)
72. Adrenalin is a hormone which raises blood pressure, increases the depth of breathing and delays
fatigue in muscles, thus allowing people to show great strength under stress.
Benzedrine is a pharmaceutical which stimulates the central nervous system in a similar manner
to adrenalin.
H O H
C H 2 C H (C H 3) N H 2 H O C H (O H ) CH 2 N C H 3
B e n z e d rin e A d re n a lin
(a) (i) On the structure for benzedrine mark with a (*) any asymmetric
carbon atom that causes chirality.
(1)
..........................................................................................................................
..........................................................................................................................
..........................................................................................................................
(2)
(1)
(1)
(iii) excess ethanoyl chloride in the presence of the catalyst anhydrous aluminium
chloride.
(2)
(d) It is possible to eliminate a molecule of water from adrenalin which for the purpose of
this question may be represented as R–CH(OH)–CH2–NH–CH3. Draw the structural
formulae of the two stereoisomers produced.
(2)
(e) The mass spectra of both benzedrine and adrenalin have a peak at a mass/charge ratio of
44. Draw the structure of the species which give these peaks.
(i) in benzedrine;
(1)
(ii) in adrenalin.
(1)
(Total 11 marks)
3d 4s
M n [A r]
M n 2+
[A r]
(2)
......................................................................................................................
(1)
Equation .......................................................................................................
(iii) The precipitate produced slowly darkens on exposure to air. Suggest a reason for
this and state two characteristic properties of transition elements that are being
shown by manganese.
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(4)
– 2– + 2+ 2–
2MnO4 + 5SO3 + 6H → 2Mn + 5SO4 + 3H2O
Sodium sulphite, Na2SO3, is slowly oxidised in air to sodium sulphate, Na2SO4, and
hence it is very difficult to keep it pure.
1.75 g of an impure sample of sodium sulphite was dissolved in water and made up to
3 3 3
250 cm with distilled water. 25.0 cm of this solution required 22.8 cm of 0.0216 mol
–3
dm potassium manganate(VII) solution for complete oxidation.
(i) Calculate the change in oxidation number of sulphur in the reaction of sulphite ions
with manganate(VII) ions.
(1)
(ii) Calculate the amount (in moles) of manganate(VII) ions used in the titration.
(1)
3
(iii) Calculate the amount (in moles) of sodium sulphite present in 25.0 cm of the
solution.
(1)
(2)
(1)
(Total 16 marks)
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
Substance –1
∆ Hc /kJ mol
C6H6(l) –3273
H2(g) –286
C(s) –394
(3)
(c) If the standard enthalpy of formation is calculated from average bond enthalpy data
assuming that benzene has three C==C and three C––C bonds, its value is found to be
–1
+215 kJ mol .
Explain, with reference to the structure and stability of benzene, why this value differs
from that calculated in (b). Use an enthalpy level diagram to illustrate your answer.
................................................................................................................................
................................................................................................................................
................................................................................................................................
(4)
(i) The reaction is first order with respect to benzene and first order with respect to
bromine. Write the rate equation for the reaction.
......................................................................................................................
(1)
+ +
(ii) The mechanism of this reaction involves an attack by Br followed by loss of H .
S te p 1 . H
B r +
+ B r
S te p 2 . H B r
+ Br +
+H
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(Total 14 marks)
1
– – +2.87
2 F2 + e F
1
– – +1.36
2 Cl2 + e Cl
1
– – +1.07
2 Br2 + e Br
1
– – +0.54
2 I2 + e I
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)
(ii) State which element or ion in the table above is the strongest oxidising agent.
......................................................................................................................
(1)
(b) The standard electrode potentials for chromium(III) changing to chromium(II) and for
chromium(VI) changing to chromium(III) are given below.
3+ – 2+
Cr +e Cr E = –0.41V
1 7
2– + – 3+
2 Cr2 O7 + 7H + 3e Cr + 2 H2O E = +1.33V
......................................................................................................................
(1)
(ii) On the basis of the data provided, list those halogens which will oxidise
chromium(II) to chromium(III) but not to chromium(VI).
......................................................................................................................
(1)
......................................................................................................................
......................................................................................................................
......................................................................................................................
......................................................................................................................
(2)