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Inorganic Chemistry
Periodicity
1.
(a)
Melting Point
Electrical Conductivity
Ionic Radius
(Note: Ar does not form ion)
2.
(a)
(i)
(ii)
MgCl2 has the highest melting point as it has a giant ionic structure and a
large amount of energy is required to overcome the strong ionic bonds (or electrostatic
attraction) between Mg2+ and Cl ions. [1m]
Both AlCl3 and SiCl4 have low melting points as they have simple covalent structures and a small
amount of energy is required to overcome the weak van der Waals' forces between their
respective molecules. [1m]
AlCl3 has a higher melting point than SiCl4 as AlCl3 exists as dimers, Al2Cl6, in the solid state {due to
the formation of dative bonds}. Due to greater number of electrons in the Al2Cl6 molecule as
compared to that in the SiCl4 molecule, van der Waals' forces between the Al2Cl6 molecules are
stronger than those between the SiCl4 molecules. [1m]
(b)
(c)
ionic charge
charge density
ionic radius
Cation
ionic
radius /nm
Mg2+
0.065
30.8
7.0 or 6.5
Al3+
0.050
60.0
3.0
Fe3+
0.064
46.9
45
pH
[1m] for quoting ionic radius from the data booklet and stating the relationship
between charge density, ionic charge and ionic radius (or calculate charge density)
As the charge density of Fe3+ is between that of Mg 2+ and Al3+ , its degree (or extent) of
hydrolysis is greater than that of Mg 2+ but slightly less than that of Al3+. Hence, its pH is between
4 and 5. [1m]
Note: The higher the charge density of cation, the greater the degree of hydrolysis, the more
acidic is the resulting solution.
3.
(a)
Magnesium burns very vigorously in oxygen with a bright white light. A white solid residue of
MgO is obtained. [1m]
2 Mg(s) + O2(g) 2MgO(s) ()
Phosphorus burns vigorously in oxygen with a bright white light. A white solid residue of P4O10 is
obtained. [1m]
P4(s) + 5O2(g) P4O10(s)
()
Sulfur burns vigorously in oxygen with a blue flame. [1m]
(b)
()
3() [1m]
Al2O3 has a giant ionic structure with strong ionic bonds (or electrostatic attraction) between
Al3+ and O2 ions. It does not react with (or dissolve in) water due to the high magnitude of its
lattice energy. Hydration energy released through the formation of ion-dipole interaction is
insufficient to compensate for the energy required to break down the giant ionic lattice. [1m]
P4O10 and P4O6 have a simple molecular structure with strong covalent bonds between P and O
atoms in each molecule but weak van der Waals' forces between their respective molecules .
They react with water to give a strongly acidic solution of pH 2. [1m]
P4O10(s) + 6H2O(l) 4H3PO4(aq)
[1m]
P4O6(s) + 6H2O(l) 4H3PO3(aq)
(c)
Resulting solution of
Magnesium oxide
Aluminium oxide
remains
[1m] green
Phosphorus oxide
(d)
(i)
With NaOH(aq)
3.
4.
(d)
(a)
(ii)
With HCl(aq)
MgO(s) + 2HCl(aq) MgCl2 (aq) + H2O(l)
[1m]
[1m]
MgO, ionic and basic, is soluble in HCl(aq) but insoluble in water and NaOH(aq).
Al2O3, ionic and amphoteric, is soluble in both NaOH(aq) and HCl(aq) but insoluble in water.
SiO2, covalent and acidic, is only soluble in concentrated alkali. It is insoluble in water,
NaOH(aq) and HCl(aq).
All three oxides are insoluble in water ().
Step 1: Add excess HCl(aq) to a small portion of the white powder().
If the powder dissolves and reacts with the acid to give salt and
water, then it could be MgO or Al2O3 ().
-
Step 2: Add excess NaOH(aq) to another small portion of the white powder().
7 () [3m]
5-6 () [2m]
3-4 () [1m]
If the powder dissolves and reacts with the alkali to give salt and
water, then it could be Al2O3 ().
If the powder does not dissolve, it would be SiO2 or MgO() as
they are insoluble in aqueous alkali.
(b)
NaCl is ionic and hence it dissolves readily in water. Due to low charge density of Na+,
no hydrolysis occurs and the resulting solution is neutral (pH 7). [1m]
Hydration: NaCl(s) + aq Na+(aq) + Cl (aq)
PCl5 is covalent and it hydrolyses in water to form a strongly acidic solution of pH 1 due to
formation of strong acids, H3PO4(aq) and HCl(aq). [1m]
Hydrolysis: PCl5(l) + 4H2O(l) H3PO4(aq) + 5HCl(aq)
5.
(a)
Dative bond
Cl
Cl
Dative bond
(b)
Al Cl
Cl Al Cl
Cl
(c)
When Na2O is added to a solution of litmus, the solution turns from purple to blue because a
strongly alkaline solution is formed. [1m]
Na2O(s) + H2O(l) 2NaOH(aq)
(d)
(i)
Mg
2+
[1m]
(ii)
[1m]
2.0
= 0.0198 mol
3(24.3) + 2(14.0) Or
[1m]
[1m]
[1m]
2.0
3(24.3) + 2(14.0)
[1m]
Multiple-Choice Questions
6.
Answer: B
MgCl2 dissolves in water to give Mg2+(aq) and Cl(aq). Due to low charge density of Mg2+, no hydrolysis
or only slight hydrolysis occur. Hence, no acidic HCl is produced when small amount of water is added.
Al2Cl6, PCl5 and SiCl4 undergo vigorous hydrolysis. Hence, when small amount of water is added, white
fumes of HCl is seen.
7.
Answer: C
8.
Answer: D
Option
Group
Chloride
Structure
State @ r.t.p
A
II
MgCl2
Giant Ionic
Solid
B
III
AlCl3
Simple Molecular
Solid
C
IV
SiCl4
Simple Molecular
liquid
D
V
PCl3
PCl5
Simple Molecular
liquid
Solid
R has a liquid chloride with low boiling point of 76oC, thus it should have a simple covalent structure.
Not Option A and B.
R fumes in air, PCl3(l) fumes easily in air.
Amount of AgNO3 used = Amount of free Cl ions = (0.30 x 100/1000)=0.0300 mol
RClx 3Cl identity of the chloride is PCl3
9.
Answer: B
To be most effective in precipitating the finely divided negatively charged solid particles
cation chosen must have the highest charge density
D: () SiCl4 is a simple covalent molecule which
hydrolyses in water to give SiO 2 and HCl, but SiO2 has
Mg2+
Al3+
Fe3+
Radius
(From Data
Booklet)
Charge
density
0.050
0.064
30.8
60.0
(highest)
46.9
ionic charge
ionic radius
10
0.065
11
Working from A, Na is B, Mg is C, Si is D.
Answer: B
Answer: C
Group II
1.
(a)
2Ca(s) + O2(g)
2CaO(s)
2Ba(s) + O2(g)
2BaO(s)
2.
(a) (i)
2M(s) + O2(g)
O
R
2MO(s)
where M is Ca and Ba
q q
LE is an indication of strength of ionic bond
r r
3.
(a)
CaCO3(s)
(b)
Ca2+ has a smaller ionic radius and thus a higher charge density than Ba2+. [1m]
The smaller Ca2+ polarises the large CO32 anion to a greater
making CaCO3 less thermally stable and so decomposes at a lower temperature. [1m]
(c)
4.
(a)
CaO(s) + CO2(g)
Lime (CaO), being basic, is used in agriculture to reduce the acidity of soil and so renders it suitable
for cultivation. [1m]
3 () : [2m]
1-2 () : [1m]
(b)
BaO(s) + H2O(l)
Ba(OH)2(aq)
[1m] balanced equation (s.s. not required)
Ba(OH)2(aq) + H2SO4(aq)
BaSO4(s) + 2H2O(l)
[1m] balanced equation (s.s. not
(c)
required)
The solid remaining after magnesium nitrate is heated is MgO(s). [1m]
The white solid, MgO, dissolves sparingly in water to give a weakly alkaline solution of Mg(OH) 2
with MgO(s) and Mg(OH)2(s) suspension. [1m]
(a)
(b)
% by mass
Amount
element
Mg
72
72
2.96
24.3
100 72 28
28
2.00
14.0
Mole ratio
(c)
Mg3N2(s) + 6H2O(l) 3Mg(OH)2(s) + 2NH3(g) [1m] balanced equation (s.s. not required)
Mg(OH)2 is the white suspension. [1m]
OR
Mg3N2(s) + 3H2O(l) 3MgO(s) + 2NH3(g) [1m] balanced equation (s.s. not required)
MgO is the white suspension. [1m]
Multiple-Choice Questions
6.
A: ()
B:
()
C : ()
D : ()
Ability to form M2+ from M increases down the group (reducing power increases down Group II).
Hence, reactivity of Group II metal increases down the group.
Down the group, as charge of M2+ ions remain the same, ionic radii increases, thus charge density of
ions decreases, strength of ion-dipole interaction between ions and water molecules decreases,
magnitude of Hhyd of the ions decreases down the group.
The thermal stability of the carbonates of the Group II elements increases down the group.
Oxides of Group II elements, except BeO, react with water to form their ionic hydroxides, which give
alkaline solutions with pH > 7. The hydroxides become increasingly soluble in nature, therefore
pH of the alkaline solutions increases down the group.
Answer : (B)
7.
A : ()
Group II compounds are ionic and will only conduct electricity in the aqueous and molten state.
B:
Oxides of Group II elements, except BeO, react with water to form their hydroxides, which give alkaline
()
solutions.
C:
All Group II metals from Ca & below Ca can react readily or vigorously with cold water to give H2(g) and
()
D : ()
Reactivity of Group II metals increases down the group. Ra is therefore the most reactive element in
Group II.
Answer : (D)
8.
CaCO3 decomposes at a lower temperature indicates that it is thermally less stable than CaSO4.
Since metal cation in both compounds is the same (i.e. Ca 2+), the difference in thermal stability of the Grp
II cpds is attributed by the difference in the polarisability of anion.
The higher the polarisability of the anion, the easier it is to decompose their compounds.
Since CaCO3 decomposes at a lower temperature, CO32 ions are predicted to be more easily polarised
than SO42 ions.
Answer : (C)
9.
(1):
()
(2):
()
(3):
()
Answer : (A)
10.
oxygen
water
H is MO(s)
water
X is M
OH 2 (aq)
J is M OH 2 (aq)
evaporate to dryness
heat residue
evaporate to dryness
K is MO(s)
heat residue
Y is MO(s)
dissolve in
Z is M NO3 2 (aq)
nitric acid
Answer : (A)
Group VII
1.
N93/P1/Q7
(a)
(i)
X aq Ag aq AgX s
Cl : White precipitate (AgCl) (), which is soluble in both dilute and concentrated
NH3(aq) to give a colourless solution of Ag(NH 3)2+ ().
Br : Cream precipitate (AgBr) (), which is sparingly soluble in dilute NH3(aq) but soluble in
concentrated NH3(aq) to give a colourless solution of Ag(NH 3)2+ ().
I : Yellow precipitate (Ag I) (), which is insoluble in both dilute and concentrated NH3(aq)()
NaX s H2SO 4 l
(ii)
2HX g H2SO 4 l
8HI g H2SO 4 l
HX g
X 2 g
4I2 g
NaHSO 4 s
SO2 g
H2S g
2H2O l
4H2O l
where
l, Br
[1]X=C
each
forand I.
where X= correct
Br and I.
balanced eqn
When NH3(aq) is added, Ag+ forms a stable complex, Ag(NH 3)2+, resulting in a decrease of [Ag +
(aq)] causing the equilibrium position of (1) to shift right. Thus the solubility of all silver halides
increases when NH3(aq) is added. [1]
Since Ksp(AgCl) > Ksp(AgBr) > Ksp(Ag I), the solubility of silver halides in NH 3(aq) decreases.
[1]
Explanation for (a)(ii)
Concentrated sulfuric acid is an oxidising agent, and it may be reduced depending on the
reducing power of X. Since the reducing power of halides decreases in the order:
,
-
I > Br > Cl
HI can reduce conc. H2SO4 (O.S. of S =6 ) to mainly H2S (O.S. of S = 2) and itself
[1]oxidised
to I2.
HBr can reduce conc. H2SO4 (O.S. of S = 6 ) to SO2 (O.S. of S = 4 ) and itself oxidised to Br2.
2.
(a)
S 4 O62 aq 2e
I2 2e
2S 2O 32 aq
E 0.09 V
2I
E 0.54 V
Must show
calculation of Eocell with
working + sign + unit.
E cell
= +0.54 +0.09 = +0.45 V > 0 energetically feasible
[1]
Observation : Black solid iodine dissolves in aqueous potassium iodide to give a brown
solution.[1] Upon addition of thiosulfate, the brown solution decolourises. [1]
[I2 dissolves to give brown solution due to the formation of the stable
I3 complex ion :
I2 s I aq I3 aq .]
(b)
Fe3 aq e
Fe 2 aq
I 2 2e
2I
E 0.77 V
Must show
E cell
= +0.77 +0.54 = +0.23 V > 0 energetically feasible
[1]
(c)
Fe3 aq e
Cl2 2e
Fe 2 aq
2Cl
E 0.77Must
V show
E cell
= +1.36 +0.77 = +0.59 V >0 energetically feasible
[1]
Chlorine undergoes disproportionation reaction with cold NaOH(aq) at room temperature to form
ClO and Cl . [1]
Cl2 g 2OH aq Cl aq C lO aq H2O l
OR
Overall eqn :
OR
(i)
Cl2 g + H2 g
2HCl g
[1]
(ii)
H2 g X 2 g
H
2HXX =
g Cl, Br, I
(iii)
Cl2 2e
2Cl
E 1.36 V
I2 2e 2I
E 0.54 V
Since E(Cl2/Cl) is more positive than E(I2/I), chlorine is a stronger oxidising agent than iodine.
S 4 O26 2e 2S 2O32
E 0.09 V
4SO2 4H 6e
SO24 4H 2e
3.
(iii)
Ecell
E O Cl2 /Cl E O S 4O62 /S 2O32
1.36 0.09
S 4O62 2H2O
E 0.51 V
SO2 4H2O
E 0.17 V
energetically feasible
+1.27 V > 0
()
Thus, Cl2 is able to oxidise S2O32 to S4O62.
(+2)
(+2.5)
Ecell
E O Cl2 /Cl E O SO2 /S 4 O62
1.36 0.51
energetically feasible
+0.85 V > 0
()
Thus, Cl2 is able to oxidise S4O62 to SO2.
(+2.5)
(+4)
Ecell
E O Cl2 /Cl E O SO24 /SO2
3 () : [1]
02() : [0]
each (), calculation of Eocell must
+1.19 V > 0 energetically feasibleFor
be shown
+ working + sign+ unit
()
Thus, Cl2 is able to oxidise SO2 to SO42.
(+4) (+6)
Based on the above Eocell calculations, Cl2 is able to oxidise S2O32 to SO42 .
Reaction between I2 and S2O32 .
1.36 0.17
Ecell
E O I2 /I E O S4O62 /S2O32
0.54 0.09
energetically feasible
+0.45 V > 0
()
Thus, Cl2 is able to oxidise S2O32 to S4O62.
(+2)
(+2.5)
Ecell
E O I2 /I E O SO2 /S 4O26
0.54 0.51
no oxidation occurs
()
+0.03 V > 0
2 () : [1]
1 () : [0]
For each (), calculation of Eocell must
be shown + working + sign + unit
Based on the above Eocell calculation, I2 is only able to oxidise S 2O32 to S4O62 (O.N of S
increases from +2 to +2.5)
[Note: Although Eocell for oxidation of S4O62 to SO2 by I2 is +0.03 V, the question has stated that I2 can
Examiner's report: Candidates were keen to add up all the sulfur E values, together with the Evalue for
Cl2/Cl , and show that this was a more viable overall reaction than with I2. The logic of this addition is highly
erroneous. Looking at the steps individually, it is clear that each halogen can oxidise thiosulfate to tetrathionate.
The key step in the overall process is the further oxidation of tetrathionate to SO 2. With I2, the E O cell for
this step is only +0.03V (so no oxidation occurs), whereas with C l2 it is +0.85V. Once that is oxidised, the further
oxidation of SO2 to sulfate by Cl2 is much easier (E O cell = +1.19V).
SO24 4H 2e
2S 2O32
E 0.09 V
S 4O62 2H2O
E 0.51 V
SO 2 4H2O
E 0.17 V
Cl2 2e
2Cl
E 0.77 V
E 1.36 V
Ecell
1.36 0.77 0.59 V >0
energetically feasible
I2 2e
2I
Ecell
0.54 0.77 0.23 V <0
0.77 V
E 0.54 V
2S 2O32
E 0.09 V
S 4O 26 2H2O
E 0.51 V
2I
Ecell
0.54 0.60 0.06 V <0
0.60 V
E 0.54 V
4.
(a)
The thermal stability of hydrogen halides decreases down Group VII. [1]
This is because the atomic radius of X increases, and thus, the HX bond becomes
longer and weaker. Hence HX bond is more readily ionized .[1]
Or
Thus, HX bond energy decreases and the HX bond becomes weaker. [1]
Hence HX bond is more readily ionized .
4.
(b)
Cl2 2e
2Cl
E O 1.36 V
Br2 2e
2Br
E O 1.09 V
Ecell
1.36 1.09
= +0.27 V > 0 (energetically feasible)
[1]
(i)
Element
Ag
Br
Mass/g
45.8
33.9
20.3
33.9
0.424
79.9
20.3
1.27
16
Amount/mol
45.8
[1]
for correct workings
0.424
108
Ratio
(ii)
(iii)
AgBrO3 BrO3
and
AgCl C l
BrO 3 : C l
Since
[1]
= 5.00 10 3 : 3.00 10 2 1: 6
Multiple-Choice Questions
1.
J95/P4/Q15
Answer : B
A ()
Down the group, atomic size of halogen atom increases. Thus, XX bond length increases.
B ()
Down the group, the number of electrons per molecule increases. Hence the strength of van der
Waals force between X2 molecules increases.
C ()
Down the group, the number of electrons per molecule increases. More energy is required to
overcome the increasing strength of van der Waals forces between X2 molecules. Thus, b.p. of
X2 increases.
Down the group, atomic size of halogen atom increases. The HX bond becomes longer and
weaker. Hence, HX bond energy decreases down the group.
D ()
2.
N00/P3/Q15
Answer : D
Cl2 undergoes disproportionation reaction with HOT NaOH(aq):
Cl2 g 6OH aq
5Cl aq
Cl O3 aq
H2 O l
Recall:
Cl2 2e
2Cl
I 2 2e 2I
3.
Answer : A
E O 1.36 V
E O 0.54 V
Since E( I2/I ) is more negative
than E(Cl2/Cl ), I will be more
readily oxidised to I2.
Equations : X s H2SO 4 l
HX g
HSO 4 s , X
Cl, I
2HI g H2SO 4 l
I 2 g SO 2 g 2H2O l
8HI g H2SO 4 l
4I 2 g
H2S g
4H2O l
N03/P1/Q17
Answer : B
X is able to reduce both Y2 and Z2 and thus X is a stronger reducing agent than Y and Z.
Z is able to reduce Y2 and thus Z is a stronger reducing agent than Y.
Y is not able to reduce both X and Z and thus Y is the weakest reducing agent.
reducing power of halides decreases in the order : X > Z > Y .
5.
Answer : B
For electrolysis of brine (concentrated NaCl(aq)),
Species present are Na+, Cl and H2O
Since Cl2 is found in compartment P and OH is found in compartment S, sodium chlorate(I) can be
produced by mixing contents of P and S.
Cl2 g 2OH aq
cold Cl aq ClO aq H2O l
6.
N11/P1/Q15
Answer: C
A ()
7.
B ()
A correct statement, but it does not explain why HI decomposes more easily. Ease of
decomposition depends on the strength of the HX bond.
An incorrect statement. HCl is more volatile than HI due to HCls lower boiling point resulting from
weaker van der Waals forces between HCl molecules. This is because HCl has lesser number of
electrons per molecule than HI.
C ()
2HX g
D ()
X 2 g
H2 g
N98/P3/Q36
Answer : A
1 () The electronegativity decreases on descending the group.
2 () The number of electrons in the X 2 molecule increases down the group. More energy is required to
overcome the increasing strength of van der Waals forces between the halogen molecules and
hence the volatility of halogens decreases on descending the group.
3 () Their reactivity as oxidising agents decreases on descending down the group as E o (X2/X) values
become less positive down the group.
Practice Paper 7
8.
J04/P1/Q36
Answer : C
1 () Hydrogen iodide is colourless.
2 () Heat energy from the hot rod is sufficient to provide the activation energy required for an
I 2 s
H2 g
One of the products, I2, will condense to a solid once it touches the cool walls of the glass jar.
9.
N01/P3/Q36
Answer : A
Since the chemistry of CN is similar to Cl :
1 () AgCN (like AgCl) is insoluble in water but soluble in aqueous ammonia.
2 () HCN (like HCl) dissolves in water, ionises, and forms an acidic solution.
3 () NaCN (like NaCl) reacts with concentrated sulfuric acid to produce HCN gas (like HCl is formed
with NaCl).
10.
Answer : D
1 () Chlorine undergoes disproportionation with hot potassium hydroxide to give chlorate(V).
3Cl2 g 6KOH aq
2 ()
Cl
O
3 ()
hot
5KCl aq
KClO3 aq
3H2O l
Transition Metals
(a)
A transition element is a d-block element that forms one or more stable ions with
incompletely filled d orbitals.
A ligand is an anion or neutral molecule which has at least one lone pair of electrons
to form dative covalent/ co-ordinate bonds.
A complex ion is composed of a central metal atom or ion surrounded by ligands
attached via dative covalent/ co-ordinate bonds.
(b)
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Page20
1.
Practice Paper 7
:CO
(c) :O2
1.
Fe2+
Fe2+
N
+ CO
Diagram
N
not
required
Polypeptide chain
in your
+ O2
N
Polypeptide chain
When a patient suffering from CO poisoning breathes in pure O2, the high
concentration of O2 causes the equilibrium position to shift such that O2 displaces
the CO (i.e. to the left of the above equilibrium). Hence haemoglobin regains its ability to
transport O2.
2.
(a)
(i)
[1m]
2+
[1m]
Using E =
[1m]
[Fe(H2O)6]3+ + 6CN
Kstab =
2.
(b)
[Fe(CN)6 3 ]
[1m]
[Fe(H 2O)6 3+ ] [CN ]6
*(ii)
A large Kstab value indicates that the position of the above equilibrium
lies to the right [1m] and shows that the complex ion is more readily/
easily formed. [1m]
(i.e. a large Kstab value shows that the complex ion is more stable and
therefore, more readily formed.)
*(iii)
1:
[1m]
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[1m]
Page20
(b)
Practice Paper 7
(a)
6() [3m]
4 5 ()
[2m]
2 3 ()
[1m]
(i)
(ii)
[Fe(H2O)6]3+(aq) +
yellow
[1m]
Colour of solution changes from
yellow to blood-red.
SCN is a stronger ligand than H2O. It displaces H2O ligand to form a stronger
dative covalent/ co-ordinate bond with Fe3+ and hence a more stable blood-red
[1m] 2+(aq) complex.
[Fe(H2O)5(SCN)]
E /V
3+
2+
Fe + e
Fe
+0.77
Fe2+ + 2e
Fe
0.44
Zn2+ + 2e
Zn
0.76
2Fe3+(aq) + Zn(s) 2Fe2+(aq) + Zn2+(aq)
E cell = +0.77 (0.76) = +1.53 V > 0 (energetically feasible) [1m]
Colour of solution changes from yellow (Fe3+(aq)) to pale green as Zn reduces
Fe3+(aq) to pale green Fe2+(aq), itself oxidised[1m]
to colourless Zn2+(aq).
Note: If excess Zn is used, Fe2+(aq) can be further reduced to Fe(s) and colour of
solution changes from pale green to colourless (due to Zn2+(aq)).
4. (i)
(a)
The reaction between I and S2O82 ions has high activation energy because
both iodide ions and peroxodisulfate, S2O82 ions are negatively charged. As a
result, the reaction is very slow and needs to be catalysed. [1m]
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Page20
Practice Paper 7
Iron is able to vary its oxidation state (+2/+3) (or can exist as Fe 2+ and Fe3+)
because the 3d and 4s orbitals have similar energies. [1m]
Calcium exists only as Ca2+ (or has only +2 oxidation state) by losing a fixed
number of electrons from their outermost shell since removal of the next
electron from an inner quantum shell requires too much ionisation
energy. [1m]
Fe2+ is a homogeneous catalyst that provides an alternative reaction path with
[1m]
lower activation energy.
3+ eqn &
[1m]
with
Step (1): S2O82(aq) + 2Fe2+(aq) 2SO42(aq)
+ 2Fe
(aq)
E
calculations
cell
(b)
I2
+
3+
Fe +
2e
e
2I
Fe2+
+0.54 V
+0.77 V
E cell = 0.77 0.54 = +0.23 V > 0 (energetically feasible) [1m] with working & units
2Fe3+(aq) + 2I(aq) 2Fe2+(aq) + I2(aq) [1m] state symbols not required
Brown solution formed is I2(aq)
In the presence of CN, Fe3+ exists as Fe(CN)63.
I2
+ 2e
2I
Fe(CN)63 + e
Fe(CN)64
+0.54 V
+0.36 V
5.
(a)
(i)
[1m]
Hence the 6 ligands in P are 2 Cl and 4 H2O
ligands.
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E cell = 0.36 0.54 = 0.18 V < 0 (not energetically feasible) [1m] with working & units
Fe(CN)63 is unable to oxidise iodide ions to iodine. Hence no brown solution was
formed.
Practice Paper 7
[1m]
Hence the 6 ligands in Q are 6 H2O ligands.
Structural formula of cation in solution Q is Cr(H2O)63+
(ii)
:Cl
H2O:
:OH2
Cr
H2O:
: OH2
[1m]
:Cl
(b)
(i)
Cr in the +6 oxidation state has high charge density and very strong
polarising power. It causes the surrounding water molecules to be polarised,
resulting in the formation of CrO42 [1m]
(ii)
2CrO42(aq) + 2H+(aq)
6.
(a)
Cu(I): 1s22s22p63s23p63d10
(b)
Cu(II): 1s22s22p63s23p63d9
Cu(I) complexes are not coloured because electron transition between 3d orbitals is
not possible since all 3d orbitals are completely filled/ no unfilled or partially filled
3d orbitals. [1m]
Cu(II) complexes are coloured because Cu2+ has a partially filled 3d-orbital. Thus
electron transition between 3d orbitals is possible. [1m]
Cu2+ + e
Cu+
+0.15 V
Cu+ + e
Cu
+0.52 V
E cell = 0.52 0.15 = +0.37 V > 0 (energetically feasible) [1m] with working & units
*(c)
(i)
B is Cu(OH)2 [1m]
NH3 acts as a base. It provides the OH ions to form Cu(OH)2
[1m]
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Practice Paper 7
(ii)
C is [Cu(NH3)4(H2O)2]2+
[1m]
equation
In this reaction, the stronger NH3 ligands replace the weaker water ligands to
form stronger dative covalent/ co-ordinate bonds with Cu2+ and hence a more
stable [Cu(NH3)4(H2O)2]2+ complex. [1m].
D: [CuCl2] [1m]
*(d)
Multiple-Choice Questions
1.
Ans: C
Net charge on complex = resultant of charges on metal ion and on ligands (CN).
Therefore, iron has 2+ charge in the complex [Fe(CN)6]4.
Since the electronic configuration of Fe atom is [Ar]3d64s2,
electronic configuration of Fe2+ is [Ar]3d64s0 (remove 4s e first).
2.
Ans: C
Ligands are anions or neutral molecules with at least one lone pair of electrons.
Therefore the NH4+ cation will not be a ligand.
Ans: B
In forming the TE ions, 4s electrons removed first, followed by paired 3d electrons.
Atom
Cr
[Ar]
Fe
[Ar]
Mn
[Ar]
Ni
[Ar]
Ion
Cr3+
[Ar]
3+
[Ar]
Fe
3d
4s
3d
4s
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3.
Practice Paper 7
4.
Mn3+
[Ar]
Ni2+
[Ar]
Ans: B
A is incorrect because Al also forms covalent bonds with Cl in AlCl3.
C is incorrect because Pb/ Sn (in Group IV) also have more than one O.S. (+2 and +4).
D is incorrect because Ca has [Ar]4s 2 configuration and all metal atoms in Period 5 onwards
have a completely filled 4s orbital.
5.
Ans: C
Cr3+
Cr(OH)3
(grey green ppt)
excess
NaOH
Cr(OH)63
(dark green cpx)
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6.
NaOH