(12)1, 18

When chlorine reacts with hot aqueous sodium hydroxide, the reaction below occurs.
Chlorine + sodium hydroxide water + sodium chloride + X
What is compound X?
A. Sodium chlorate (I)
B. Sodium chlorate (III)
C. Sodium chlorate (V)
D. Sodium chlorate (VII)
(12)1, 34
The number of moles of chlorine that react with 1mol of X is twice the number of moles of
chlorine that react with 1mol of Y.
Which of these pairs could be X and Y?
X Y
1 Mg(s) Na(s)
2 H
2
(g) KBr(aq)
3 Cold NaOH(aq) Hot NaOH(aq)

(12)1, 35
In which reactions does the oxidation state of chlorine change by one?
1. Electrolysis of brine (anode reaction)
2. Hydrogen + chlorine
3. Sodium chloride + concentrated sulfuric acid
(11)1, 15
HCl is stable to heat, but HI decomposes into its elements when heated.
What is responsible for this difference?
A. HI is a stronger reducing agent than HCl
B. HI is more volatile than HCl
C. The H-I bond is weaker than the H-Cl bond
D. The I-I bond is weaker than the Cl-Cl bond

(11)1, 36
1-bromopropane may be prepared by slowly adding concentrated sulfuric acid to a mixture of
propan-1-ol and sodium bromide, and keeping the reaction mixture cool.
CH
3
CH
2
CH
2
OH + HBr CH
3
CH
2
CH
2
Br + H
2
O
What could be a by-product of this reaction if the temperature is allowed to rise?
1. Br
2

2. SO
2

3. CH
3
CH(OH)CH
3

(11)2, 4
a) The elements of Group II, magnesium to barium, are metals while the elements of
Group VII, chlorine to iodine, are non-metals. [4]

i. State one physical property of the elements of Group II which shows them all
to be metals.
ii. State one trend in the physical properties of the elements of Group VII from
chlorine to iodine, and explain why this change occurs.

b) Among the elements of Group IV, those towards the top, carbon to germanium, have
very different properties from those at the bottom, tin and lead. [3]
For example, the melting points show a marked change after germanium.

element C Si Ge Sn Pb
Mp /C >3550 1410 937 232 327

Carbon, silicon and germanium each form a solid with the same type of structure.

i. What type of structure is present in solid carbon, silicon and germanium?
ii. Suggest why the melting points of these elements decrease from carbon to
germanium.

c) Carbon and silicon each form a tetrachloride. CCl
4
has no reaction with water; SiCl
4

reacts violently with water. [3]

i. Write a balanced equation for the reaction of SiCl
4
with water.
ii. Use the Data Booklet to obtain values for the C-Cl and Si-Cl bond energies.
iii. Suggest an explanation for the inertness of CCl
4
to water.

(11)3, 1
The halogens form many interhalogen compounds and ions, in which a halogen atom lower
down the group is surrounded by atoms of halogens higher in the group. Two such species
are the compound ClF
5
and the ion ICl
4
-
.
a) Calculate the oxidation number of iodine in ICl
4
-
. [1]

b) Draw dot-and-cross diagrams showing the electrons (outer shells only) in ClF
5
and
ICl
4
-
, and use the VSEPR (valence shell electron pair repulsion) theory to predict their
shapes. You may find both a written description and a 3-dimensional sketch useful in
your answer. [4]

c) N-chlorosuccinimide is used in some water purification tablets. It dissolves in water
to give a solution of chloric(I) acid, HClO, which kills waterborne bacteria.

N
O O
Cl
+
O H
2
N
O O
H
+
HClO


The amount of N-chlorosuccinimide in a tablet can be estimated by dissolving it in
water, and adding an excess of acidified KI(aq). The HClO is quantitatively reduced
to Cl
-
by I
-
ions, which are oxidised to I
2
. The I
2
is titrated with standard sodium
thiosulfate. The following reaction takes place during the titration. [4]

i. Construct a balanced equation for the reaction between HClO and acidified
KI(aq).

When one tablet was subjected to the above procedure, 6.0cm
3
of 0.0050moldm
-3

sodium thiosulfate were required to discharge the colour of I
2
.
ii. Calculate the mass of N-chlorosuccinimide in the tablet.


d) In 1881 the German chemist August Wilhelm von Hofmann discovered that treating
primary amides with aqueous alkaline bromine produced primary amines containing
one less carbon atom than the starting material. [4]

R-CONH
2
R-NH
2
Br
2
+ OH
-


The reaction is thought to proceed through the following stages.

R-CONH
2 R-CONHBr R-CON R-N=C=O R-NH
2
Br
2
I
-HBr
II III
OH
-
(aq)
IV
A
B

i. Construct a balanced equation for stage I.
ii. State the oxidation number of bromine in compound A.
iii. Deduce the number of electrons around the N atom in compound B.
iv. Suggest the other product of stage IV, and hence construct a balanced
equation for this stage.

e) The Hofmann reaction can be used as the last step in the following synthesis of
4-bromophenylamine from methylbenzene.
Suggest reagents and conditions for steps V to VIII, and the structures of compounds
C and D. [7]

CH
3
CH
3
Br
COCl
Br
NH
2
Br
C D
V VI VII VIII
Br
2
+ OH
-


(11)3, 5
a) State and explain how the acidities of water, phenol and ethanol compare with each other.
[4]
b) State the reagents and conditions needed to convert phenol into 4-nitrophenol. [1]
c) Suggest and explain how the acidity of 4-nitrophenol might compare with that of phenol.
[1]
d) Phenacetin was once used as an analgesic (pain killing) drug. It can be synthesised from
4-nitrophenol by the following route. [8]

OH
NO
2
OH
NH
2
J
K
I
O
-
NH
2
II
III
+ C
2
H
5
Br
OC
2
H
5
NH
2
OC
2
H
5
NHCOCH
3
IV

i. Suggest reagents and conditions for steps I, II and IV.
ii. What types of reaction are steps I, II, III and IV?
iii. Suggest why compound J is converted into K before step III is carried out?

e) Many antiseptic solutions contain chlorinated substituted phenols. These can be made by
the following reaction.

OH
C H
3
CH
3
OH
C H
3
CH
3
Cl
Cl

Suggest reagents and conditions necessary for this reaction. [1]

(10)2, 2
1-Bromobutane may be made by reacting together butan-1-ol, sodium bromide and
concentrated sulfuric acid in the presence of water, as described below.
Data about these four compounds and 1-bromobutane are given in the table.
Compound
Boiling point
/C
Density
/gcm
-3

M
r

Solubility in
water
1-bromobutane 102 1.35 137 Insoluble
Butan-1-ol 118 0.81 74 Moderate
Sodium bromide 1390 3.20 103 Soluble
Concentrated
sulfuric acid
330 1.84 98 Soluble
Water 100 1.00 18 -

Preparation of impure 1-bromobutane

1. Place 35g of powdered sodium bromide, 30cm
3
of water and 25cm
3
of butan-1-ol in a
250cm
3
two-necked flask. In one neck is placed a tap funnel and in the other neck is
placed a reflux condenser.
2. Place 25cm
3
of concentrated sulfuric acid in the tap funnel and then add the acid drop
by drop to the reagents in the flask. Keep the contents well shaken and cool
occasionally in an ice-water bath.
3. When all of the acid has been added, gently boil the mixture for about 45 minutes,
shaking the flask gently from time to time.
4. Rearrange the apparatus for distillation. Distil off the impure 1-bromobutane (about
30cm
3
).

a) The overall reaction may be considered to take place in two stages, the first between
inorganic reagents only and the second involving the organic reagent.
Write an equation for each of these stages. [2]

b) By using the amounts given above, one of the reagents, butan-1-ol or sodium bromide,
will be present in an excess in this preparation.
Use the data above to determine, by calculation, which reagent is in an excess. [3]

c) When the concentrated sulfuric acid is added to the reaction mixture (step 2), cooling
is necessary. Two by-products, one inorganic and one organic, may be produced if the
temperature is not controlled carefully. [5]
i. Suggest the main cause of heat being produced at this stage.
ii. What by-products may be formed? In each case, identify the by-product and
write an equation showing its formation.


d) The reaction mixture is heated for 45 minutes (step 3).
Why is this process necessary for the preparation of many covalent organic
compounds? Explain your answer. [2]

e) When the mixture is distilled (step 4), the main product is 1-bromobutane. Two other
compounds are also present as impurities in the distillate.
Use the data earlier to suggest the identities of these two compounds and a reason for
their presence. [2]

The preparation of organic compounds usually produces a mixture of the required compound
and other impurities. Obtaining the required compound in a pure state involves the
application of chemical knowledge and principles.
The purification of crude 1-bromobutane is described below. These data are repeated earlier.
Compound
Boiling point
/C
Density
/gcm
-3

M
r

Solubility in
water
1-bromobutane 102 1.35 137 Insoluble
Butan-1-ol 118 0.81 74 Moderate
Sodium bromide 1390 3.20 103 Soluble
Concentrated
sulfuric acid
330 1.84 98 Soluble
Water 100 1.00 18 -

Purification of impure 1-bromobutane

5. Shake the distillate with water in a separating funnel and separate the aqueous layer
from the 1-bromobutane. Reject the aqueous layer.
6. Return the 1-bromobutane to the funnel, add about half its volume of concentrated
hydrochloric acid, and shake. Separate and discard the layer of acid.
7. Shake the 1-bromobutane cautiously with dilute aqueous sodium carbonate in the
separating funnel, releasing the pressure at intervals.
8. Transfer the 1-bromobutane into a conical flask and add some granular anhydrous
calcium chloride. Swirl the mixture until the liquid is clear.
9. Filter the 1-bromobutane into a clean, dry round-bottom flask and distil it. Collect the
fraction by boiling over a suitable range.

f) After distillation from the reaction mixture, the impure 1-bromobutane is shaken with
water (step 5) and the two layers are allowed to separate.
Will the 1-bromobutane be the upper or lower layer? Explain your answer. [1]


g) After separating the 1-bromobutane from the water there will still be a very small
amount of one of the original reactants present as an impurity. To remove this, the 1-
bromobutane is shaken (step 6) with concentrated hydrochloric acid a strong acid. A
reaction occurs with the impurity present in the 1-bromobutane, making it more
soluble in water. [3]
i. Suggest with which of the original reactants the concentrated hydrochloric
acid reacts.
ii. By using structural formulae, construct an equation for this reaction.
iii. Suggest why the product in (ii) is more soluble in water than the original
reactant.

h) What impurity will be removed when the 1-bromobutane is then treated with dilute
aqueous sodium carbonate (step 7)?
Write an equation for this reaction. [2]

i) Suggest what is removed when the impure 1-bromobutane is treated with anhydrous
calcium chloride (step 8). [1]

j) The final step in the process of purification is distillation of the pure product (step 9).
Suggest a suitable range of temperature for the collection of the required fraction. [1]