Name :
33rd IChO 
Student code :
Problem 5
11 Points
Halogen Chemistry
Halogens in their reactions among themselves and with a variety of other elements
give rise to a large number of compounds with diverse structure, bonding and
chemical behaviour. Metal halides, halogen derivatives and interhalogens represent
major types of halogen compounds.
(A)
Photography
A “black and white” photographic film contains a coating of silver bromide on a
support such as cellulose acetate.
5.1
Write the photochemical reaction that occurs when light falls on AgBr(s)
coated on a film.
h
2 AgBr (s) 
 2 Ag (s)  Br /2Br 
2
0.5 mark
5.2
During the developing process, unexposed AgBr is washed away by
complexation of Ag(I) by sodium thiosulphate solution. Write down this
chemical equation.
AgBr (s)  2 Na 2S 2O3  Na 3 [ Ag (S 2O3 )2 ]  NaBr
1 mark
5.3
These washings are often disposed of as waste. However, metallic silver can
be recovered from them by adding cyanide, followed by zinc. Write down the
reactions involved.
[ Ag (S 2 O 3 ) 2 ]3  2 CN  [ Ag (CN) 2 ]   2 S 2 O 32
2 [ Ag (CN) 2 ]   Zn  [ Zn (CN) 4 ] 2  2 Ag 
(0.5)
(1)
1.5 marks
Official version
Page 19 of 39
33rd IChO 
(B)
Problem 5
Student code :
Shapes, spectra and reactivity
The most reactive halogen, fluorine, reacts with other halogens, Cl2, Br2, and I2
under controlled conditions giving a tetraatomic, hexaatomic and an octaatomic
molecule, respectively.
5.4
Write the formulae and 3 dimensional structures of these interhalogen
molecules on the basis of VSEPR theory. Show the disposition of the lone
pairs on the central atom, where appropriate.
Formula
Structure
F
ClF3
:
:
(0.5)
Cl
(1)
F
F
F
BrF5
(0.5)
F
F
F
Br
F
(0.5)
..
F
F
IF7
(0.5)
I
F
F
(0.5)
F
F
F
3.5 marks
A mixture of iodine vapour and chlorine gas when fed into a mass spectrometer
gave two sets (A and B) of mass spectral peaks corresponding to molecular ions of
two chemical species at m/z :
A:
(162,164)
B:
(464, 466, 468, 470, 472, 474, 476)
Official version
Page 20 of 39
33rd IChO 
5.5
Problem 5
Student code :
Identify the molecular species corresponding to m/z = 162, 164, 466 and 476.
Draw the structure of the heaviest species (m/z = 476) indicating clearly the
lone pairs on I atom(s). Show the isotopic composition of each species.
Mass
Species
162
I35Cl
(0.5)
164
I37Cl
(0.5)
466
I235Cl537Cl
(0.5)
476
I237Cl6
(0.5)
Cl
..
Cl
..
Cl
I
I
Cl
..
Cl
Cl
..
(1)
3 marks
In aqueous medium chlorine gas oxidises sodium thiosulphate to an ion
containing the highest oxidation state of sulphur.
5.6
Write down the chemical equation for this reaction.
4 Cl2  S2O32  5 H2O  8 Cl  2 SO24  10 H
1 mark
5.7
Write down the Lewis dot structure of the thiosulphate ion. Circle the sulphur
atom that has the lower oxidation state.
2: O:
..
:S
..
S
..
:
O
..
:O:
1 mark
5.8
Chlorine dioxide reacts with sodium hydroxide as shown below. Identify the
products X and Y (both containing chlorine) and balance the equation.
( 2 ) ClO 2  ( 2 ) NaOH  ( NaClO 2 )  ( NaClO 3 )  H2 O
X
Official version
Y
2 marks
Page 21 of 39
33rd IChO 
5.9
Problem 5
Student code :
Reaction of chlorine an alkali is used for manufacturing bleach. Write the
chemical reaction for its formation.
Cl2  Ca(OH) 2  Ca(Cl)(OCl)  H2 O
or
Cl2  CaO  Ca(Cl)(OCl)
or
2OH   Cl2  Cl  OCl   H2 O
1 mark
5.10
The oxidation state(s) of chlorine in bleach is (are):
–1
and
+1
1 mark
(C)
Alkali metal halides and X–ray crystallography
X–ray crystallography reveals many aspects of the structure of metal halides. The
radius ratio (r+/r) is a useful parameter to rationalize their structure and stability.
A table of radius ratio (r+/r) for some alkali halides is given below. The variation of
the electrostatic component of lattice energy of alkali halides with radius ratio (r  kept
constant) is shown schematically for NaCl–type and CsCl–type crystal structures.
Energy
Li+
Na+
K+
Rb+
Cs+
Cl
0.33
0.52
0.74
0.82
0.93
Br
0.31
0.49
0.68
0.76
0.87
I
0.28
0.44
0.62
0.69
0.78
CsCl type
NaCl type
1.0
5.11
r+/r
For a given anion, the graph for NaCl–type structure levels off at low r+/r
values because of
(a)
cation–cation contact along the face diagonal.
(b)
anion–anion contact along the face diagonal.
(c)
cation–anion contact along the cell edge.
[Mark X in the correct box.]
Official version
1 mark
Page 22 of 39
33rd IChO 
5.12
Problem 5
Student code :
Which among the halides LiBr, NaBr and RbBr is likely to undergo phase
transition from NaCl–type to CsCl–type structure with change of temperature
and /or pressure?
RbBr
5.13
0.5 mark
Show by calculation the radius ratio (r+/r) at which the energy of CsCl–type
structure levels off.
In CsCl–type structure,
Cell edge, a = 2r–
(0.5)
3a  2 (r  r )
Body diagonal,
(0.5)
r
 3  1  0.732
r
(0.5)
1.5 marks
5.14
Using Cu K X–rays ( λ = 154 pm), diffraction by a KCl crystal (fcc structure)
is observed at an angle () of 14.2 . Given that (i) diffraction takes place from
the planes with h2 + k2 + l2 = 4, (ii) in a cubic crystal dhkl = a/ (h2 + k2 + l2)1/2,
where 'd' is the distance between adjacent hkl planes and 'a' is the lattice
parameter, and (iii) reflections in an fcc structure can occur only from planes
with 'all odd' or 'all even' hkl (Miller) indices, calculate the lattice parameter 'a'
for KCl.
λ  2d sin 
λ
d 200 
 314 pm
2 sin 
d 200 
a
(h  k  l )
2
a  628 pm
2
2 1/ 2

(0.5)
(0.5)
a
(2  0  0 )
2
2
2 1/ 2

a
2
(0.5)
(0.5)
2 marks
Official version
Page 23 of 39
33rd IChO 
5.15
Problem 5
Student code :
Indicate in the table given below the required information for the 2nd and 3rd
nearest neighbours of a K+ ion in the KCl lattice.
2nd nearest neighbours
sign of
the
charge
+
number
12
3rd nearest neighbours
distance
(pm)
number
444
8
sign of
the
charge

distance
(pm)
544
3 marks
5.16
Determine the lowest value of diffraction angle  possible for the KCl
structure.
Lowest  value is for the plane with hkl = (111)
d 
a
12  12  12
sin 111 

628
3
 363 pm
λ
154 pm

 0.212
2d111 2  363 pm
 111  12.2 
(0.5)
(0.5)
(0.5)
(0.5)
2 marks
Official version
Page 24 of 39