9

The name of chromium is derived from the Greek word chr ma, which means colour, because
many of its compounds are colored.
(a)

When chromium metal is dissolved in dilute sulfuric acid, it produces a blue solution
containing Cr2+(aq). The blue solution slowly turns green even in the absence of air.
This mixture is then filtered to separate the green solution and the unreacted metal. The
green filtrate, V, is divided into two portions, each of 10.0 cm3.
To one portion of solution V, adding sodium hydroxide solution produces a grey green
precipitate, W. In excess sodium hydroxide, a dark green solution, X, is formed. The dark
green solution turns into a yellow solution, Y, upon warming with hydrogen peroxide
solution.
(i) By quoting and using relevant Eo values from the Data Booklet, explain why the blue
solution turns green.
(ii) Suggest the formula of the complex ion present in solution V.
(iii) Explain why solution V is green in colour.
(iv) Identify W and X and suggest balanced equations for the formation of W from V, and
for the formation of X from W.
(v) What type of reaction occurs when X is converted into Y?

[9]
(b)

The other portion of solution V is reacted exactly with 11.0 cm3 of 0.030 mol dm 3 sodium
carbonate, producing the same greygreen precipitate, W. No carbon dioxide is given off
during the reaction.
(i) Given that the pH of solution V is 3.0, calculate the concentration of the ion you have
suggested in (a)(ii).
[Ka of the ion suggested in (a)(ii) = 9.8 10 5 mol dm 3]
(ii) Using your answer to (b)(i) and the information given above, calculate the number of
moles of sodium carbonate that would react with one mole of the ion in solution V.
(iii) Hence, determine the ionic equation for the above reaction between sodium
carbonate and solution V.
[4]

AJC JC2 PRELIM 2013

9647/03/H2

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-4-

Nickel is a typical transition element in the d-block of the Periodic Table. It is commonly used as a
catalyst and as an alloying ingredient.
(a)

Explain why nickel is regarded as a transition element.

[1]

(b)

In an experiment to study the reaction between nickel and the metal ion, M2+(aq), an
electrochemical cell was set up using the Ni2+/Ni and M2+/M half-cells at 298 K.
During the experiment, the concentration of Ni2+ ions in the Ni2+/Ni half-cell was kept at
1.0 mol dm3 but the concentration of M2+ ions in the M2+/M half-cell was changed. The
e.m.f. of the cell was measured with each change of solution in the M2+/M half-cell, and the
results obtained are tabulated below.
[M2+] / mol dm3

101

102

103

104

105

106

e.m.f. / V

0.091

0.061

0.032

0.002

0.028

0.057

1.0

2.0

3.0

4.0

5.0

6.0

lg

[M2+]

(i)

Plot a graph of e.m.f. against lg [M2+].

(ii)

With the aid of the graph plotted and relevant data from the Data Booklet, determine
the standard electrode potential of the M2+/M half-cell.

(iii)

The above electrochemical cell is dead when the overall cell reaction reaches
equilibrium. With the aid of the graph plotted, calculate the equilibrium constant, K c , for
the cell reaction shown below at 298 K.
Ni(s) + M2+(aq) Ni2+(aq) + M(s)

(iv)

(c)

Using your answer from (ii) and relevant data from the Data Booklet, predict what
might be observed when a rod of metal M is dipped into an aqueous copper(II)
nitrate(V) solution.
[8]

Nickel forms many hydrated salts such as NiCl 2 .6H 2 O and NiSO 4 .7H 2 O. When some
NiCl 2 .6H 2 O is dissolved in water, a green solution containing [Ni(H 2 O) 6 ]2+ ions forms.
Addition of excess aqueous ammonia to this green solution results in a blue solution
containing [Ni(NH 3 ) 6 ]2+ ions.
(i)

State and explain whether the HOH bond angle in H 2 O in an isolated gaseous H 2 O
molecule is larger or smaller than that in the [Ni(H 2 O) 6 ]2+ ion.

(ii)

Explain briefly why the two nickel(II) ion-containing solutions have different colours.
[4]

2
Answer any four questions.
1.

(a)

State and explain in terms of electronic structure, two characteristic

chemical properties of transition metals or their compounds.
[4]

(b)

Transition element complexes such as those of iron are common

reagents in colourful demonstrations of redox reactions. In one particular
demonstration, the following observations were made.
When aqueous iron(III) sulfate was added to aqueous sodium iodide, the
reaction mixture turned brown. The brown colour is discharged upon
addition of aqueous sodium hexacyanoferrate(II), Na4Fe(CN)6.
On the other hand, when aqueous sodium hexacyanoferrate(III),
Na3Fe(CN)6, was added to a fresh sample of the aqueous sodium iodide,
the colour of the reaction mixture remained unchanged.
(i)

Explain the above observations using relevant data from the Data
Booklet.

(ii)

Comment on the relative stability of the different oxidation states

of iron in the presence of different ligands.
[5]

(c)

Haemoglobin (Hb) is composed of 4 polypeptide chains: two alpha chains

and two beta chains of polypeptides. Each chain contains one haem
group, each of which contains one iron ion. The iron is the site of oxygen
binding; each iron can bind one O2 molecule thus each haemoglobin
molecule is capable of binding a total of four O2 molecules.
The ironoxygen interaction is very weak; the two can easily be
separated without damaging the haem unit or the oxygen molecule. The
binding of an oxygen molecule to the iron in a haem unit is therefore
completely reversible.
(i)

Explain how O2 molecule binds to the Fe of the haem group.

3
1.

(c)

(ii)

Each Hb molecule has a complex quaternary structure. Briefly

describe what this means.

(iii)

A haemoglobin molecule in which the iron has separated from the

oxygen molecule is called deoxyhaemoglobin. Blood containing
red-blood cells filled with O2 is brighter red. Suggest an
explanation for the observation of this colour.

(iv)

Haemoglobin is susceptible to denaturation. Explain the term

denaturation as applied to proteins and state two types of R group
interactions that can be disrupted when heat is applied to proteins.
[7]

(d)

Iron(II) ethanedioate, FeC2O4, reacts with manganate(VII), MnO4,

forming Fe3+ and carbon dioxide. In an experiment, 0.144g of FeC2O4
reacted with 20.0 cm3 of 0.150 mol dm-3 of MnO4.
(i)

Write an ion-electron equation for the oxidation of FeC2O4 to Fe3+

and carbon dioxide.

(ii)

Determine the oxidation number of manganese in the product

formed after the reduction of manganate(VII).
[4]
[Total: 20]

[Turn over

17
7

For
Examiners
Use

This question is about some reactions of copper compounds

step I

(a)

step II

Complete the electronic configuration in s, p, d, f notation for Cu atom, where

[Ar]: 1s2 2s2 2p6 3s2 3p6
Cu: [Ar]

(b)

(i)

[1]

Identify ion P.
Ion P:

(ii)

Copper forms an octahedral complex with fluorine with the formula CuF64 .
Suggest why ion P is formed instead of CuCl64 .
Explanation:
...............
...............
............... [2]

(c)

Describe the observations in step I and II and write balanced equations for the
two reactions.
Observations in step I:
Equation:

Observations in step II:

...

Equation:

Jurong Junior College

[3]

9647/02/PRELIM/2013

[Turn over

18
7

(d)

For
Examiners
Use

Ethylenediamine, H2NCH2CH2NH2, (abbreviated as en) is a bidentate ligand.

When a dilute aqueous solution containing ethylenediamine is added to ion R, a
purple solution of ion S is formed. The following shows the stability constant,
Kstab, for the formation of three possible copper complexes with the en ligand
from [Cu(H2O)6]2+.

(i)

From the Kstab values shown above, what is the likely formula of ion S?
Ion S:

(ii)

Draw a diagram to illustrate the structure of ion S.

You should show the following clearly in your diagram.
how the ligands are bonded to the copper ion.
the shape around copper in the ion.

(iii)

Explain why H2NNH2 cannot act as a bidentate ligand.

................
................

(e)

[4]

Water, ammonia and ethylenediamine are common ligands used in transition

metal chemistry. From the reactions given in the scheme on Page 18, arrange
these three ligands in order of increasing ligand strength. Explain your answer.
................
................
................
................

[2]

[Total: 12]

Jurong Junior College

9647/02/PRELIM/2013

3
Explain whether the enthalpy change of dimerisation is endothermic or exothermic.
Hence, predict the colour change of the reaction mixture when the temperature is
increased.
[2]
[Total: 20]
2

Transition elements, such as cobalt, copper and chromium, have different properties that
can distinguish themselves from the main group element such as magnesium. With their
unique properties, transition elements are capable of having variable oxidation states and
forming coloured complexes.
(a)

What do you understand by the term transition element?

[1]

(b)

When air is bubbled through an aqueous solution containing CoCl2, NH4Cl and NH3,
and the resulting solution evaporated, crystals of a salt X can be isolated. X has the
following composition by mass:
Co, 25.2 %; N, 24.0 %; H, 5.1 %; Cl, 45.7 %
On adding an excess of aqueous silver nitrate to an aqueous solution containing
0.01 mol of X, 1.43 g of silver chloride is precipitated.
Determine the formula of the octahedral cation in X. Hence, calculate the oxidation
number of the cobalt atom in X.
[4]

(c)

Haemocyanin is a copper containing oxygen transport molecule in horseshoe crabs.

Both oxygenated and deoxygenated forms of haemocyanin contain copper ions.
Haemocyanin is colourless when deoxygenated and blue when it is exposed to
oxygen.
Suggest the oxidation states of copper in the oxygenated and deoxygenated forms
of haemocyanin. Hence explain the difference in colour observed.
[3]

(d)

Reagents containing transition elements are commonly used in organic synthesis. A

common reagent used is potassium dichromate(VI).
In the organic synthesis below, observations are made when an optically active
organic halogen derivative A, C5H11ClO is reacted with several reagents to yield the
final organic product E, C10H16O4.
Compound A, C5H11ClO is an organic halogen derivative that fumes with thionyl
chloride in pyridine. When A reacts with aqueous sodium hydroxide, it yields
equimolar of B and C with the same molecular formulae, C5H12O2.
When B and C are separated, each compound is found to rotate planepolarised
light in opposite directions with equal magnitude. C is then heated under reflux with
acidified potassium dichromate(VI) to yield D which produces effervescence with
sodium carbonate. When D is further refluxed in the presence of concentrated
sulfuric acid, a neutral organic product E, C10H16O4 is obtained.
(i)

DHS 2013

Suggest, with explanations, the structures for compounds A, B, C, D and E.

9647/03

[Turn Over

4
(ii)

Describe the mechanism of the reaction of A with aqueous sodium hydroxide

to produce B and C. Indicate clearly in your mechanism how equimolar of B
and C is obtained.
[12]
[Total: 20]

(a)

A lowcost lithiumcopper air fuel cell consisting of a copper electrode immersed in

an aqueous alkaline electrolyte and a lithium electrode immersed in an organic
electrolyte has recently been developed. Mixing of the two electrolyte solutions is
prevented by using a solid electrolyte separator where only lithium ions can pass
through the separator.
air

Cu metal
electrode

Li metal
electrode

Aqueous alkaline
electrolyte
Organic
electrolyte
Solid electrolyte
separator

The copper electrode is oxidised by oxygen in the air to copper(I) oxide. During
discharge, copper(I) oxide will be reduced to copper solid at the electrode. Similarly,
during discharge, lithium will be oxidised to give lithium ions and pass through the
separator into the aqueous alkaline electrolyte.

(b)

(i)

State the direction of the flow of electron during discharge in the lithiumcopper
air fuel cell.

(ii)

Write ionic halfequations for the reaction that occur at each electrode during
discharging.

(iii)

It is discovered that the voltage of this fuel cell is +2.30 V. Using relevant data
from the Data Booklet, predict the electrode potential for the cathode reaction.
State an assumption that you have made.

(iv)

Explain why lithium ions are allowed to pass through the separator.

(v)

Two different electrolytes are used in this lithiumcopper air fuel cell. Suggest a
reason why an aqueous alkaline electrolyte cannot be used solely in this fuel
cell.
[8]

The copper(I) oxide is reddishbrown in colour. When concentrated hydrochloric acid

is added to it and the mixture warmed, it is observed that the precipitate dissolved to
give a colourless solution. The copper complex ion formed is linear in shape.
Suggest an identity for the copper complex ion and an equation for the reaction.
[2]

DHS 2013

9647/03

[Turn Over

5
(c)

An experiment is conducted to determine the formula of complex ion formed between

copper(II) and ammonia.
100 cm3 of 0.100 mol dm3 of copper(II) sulfate is mixed with 100 cm3 of aqueous
ammonia. The resulting solution, which contains an excess of ammonia, is then
shaken with trichloromethane and allowed to stand for equilibrium to be established.
25.0 cm3 of trichloromethane layer is found to neutralise 26.00 cm3 of
0.025 mol dm3 hydrochloric acid while 25.0 cm3 of aqueous layer required
21.00 cm3 of 1.00 mol dm3 hydrochloric acid for neutralisation.
The equilibrium constant of ammonia between the aqueous layer and the
trichloromethane layer is 25.0.
NH3 (aq)
K=

NH3 (CHCl3)

[ammonia] aqueous
[ammonia] CHCl3

Calculate the following:

(d)

(i)

the concentration of ammonia in the trichloromethane layer.

(ii)

the concentration of free ammonia in the aqueous layer, using the given
equilibrium constant.

(iii)

the total concentration of ammonia (free and complexed) in the aqueous layer.

(iv)

the value of n in the formula of the complex ion [Cu(NH3)n]2+, stating one
assumption made in the calculation.
[8]

Sodium 2aminobenzoate is a bidentate ligand that can form a complex with

Cu2+(aq). Different volumes of 0.05 mol dm3 Cu2+(aq) and 0.025 mol dm3 sodium
2aminobenzoate are mixed to form a few mixtures.

These mixtures show light absorbancy as shown in the graph below. The
absorbance is proportional to the concentration of the complex.
Absorbance

0
10
DHS 2013

3.33
6.67

5
5

6.67
3.33
9647/03

10
0

Volume/ cm3
Cu (aq)
Sodium 2aminobenzoate
2+

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6
Determine the mole ratio of the copper ion to the 2aminobenzoate ligand in the
octahedral complex formed, with the maximum light absorbance, and draw its
structure.
[2]
[Total: 20]
4

A tooth is made up of two parts: the crown and the root. Dental crown is the visible part of
the teeth which is made of enamel and dentine.
Enamel

Crown

Dentine

Root

The enamel is made of hydroxyapatite, Ca5(PO4)3OH. In the mouth, mineral substances

such as calcium ions and phosphate ions that are present in saliva contribute to the
formation and decomposition of the hydroxyapatite. These two processes occur
simultaneously until an equilibrium is reached. The formation process is called
mineralisation of the enamel, whereas the decomposition process is called
demineralisation.
Ca5(PO4)3OH(s)

5Ca2+(aq) + 3PO43(aq) + OH(aq)

Presence of dental plaque is a major cause for demineralisation of tooth. The pH of dental
plaque can be significantly reduced by presence of acetic and lactic acids. If it goes below
the critical pH for a long period of time, demineralisation process can occur and dental
cavities will appear.
(a)

Explain how an acidic medium can affect the demineralisation of teeth.

[2]

(b)

It is known that fluoride ions ensure a better protection for teeth. One of the proposed
mechanisms to explain this phenomenon suggests that fluoride ions can substitute
the hydroxide ions of hydroxyapatite during the mineralisation process to form
fluoropaptite, Ca5(PO4)3F, which has a lower solubility.
(Ksp value of fluoroapatite = 1.0 x 1060)
(i)

Write the balanced equation for the reaction describing the demineralisation of
fluoroapatite in water. Hence write a Ksp expression of fluoroapatite.

(ii)

Calculate the solubility of fluoroapatite in water and hence the concentration of

phosphate ions.

(iii)

In the presence of a weak acid, HF, the concentration of fluoride ions from
demineralisation of fluoroapatite is less than expected. Explain why this is so.
[7]

DHS 2013

9647/03

[Turn Over

15
6

Chromium is a typical transition element and it forms many stable coloured complexes
that are capable of exhibiting various types of isomerism.
(a)

Chromium(III) chloride with the general formula CrCl3 6H2O can exist as hydrated
isomers which differs in the number of water molecules attached as ligands to the
metal ion.
(i)

One of the hydrated isomers is [CrCl2(H2O)4]Cl 2H2O. Explain why an aqueous

solution of this isomer is green.
..
..
..
..
..
..
..
..

(ii)

Suggest the formulae of two other possible hydrated isomers of chromium(III)

chloride.
..
.

(iii) When aqueous ammonia is added gradually to a solution containing

[Cr(H2O)6]3+, a grey-green precipitate is formed. When aqueous ammonia is
added in excess, the precipitate dissolves to give a purple solution. Explain the
observations with the aid of relevant equations, including state symbols.
..
..
..
..
..
..
..
[8]

9647/02/CJC JC2 Preliminary Exam 2013

16
(b)

Certain octahedral transition metal complexes are able to exhibit both geometric
(cis-trans) and optical isomerism.
Cis-trans isomers are isomers which differ in the arrangement of two ligands.
Cis- isomers are isomers where the two ligands are 90 apart from one another in
relation to the central metal ion, whereas trans-isomers are isomers where the two
ligands are 180 apart in the complex.
(i)

Select a suitable hydrated isomer of chromium(III) chloride which contains a

complex ion capable of exhibiting cis-trans isomerism. Draw the structures of
the two isomers and label clearly which is the cis- and trans- isomers.

9647/02/CJC JC2 Preliminary Exam 2013

17
(ii)

Another chromium-containing complex, [CrCl(NH3)(en)2]2+, exists as three

isomers. [en: ethylenediamine, H2NCH2CH2NH2]
Isomer A rotates plane-polarised light to the right.
Isomer B rotates plane-polarised light to the left.
Isomer C has no effect on the plane-polarised light.
Draw the structures of isomers A to C.
You may use

NH2

NH2

to represent ethylenediamine.

[5]
[Total: 13]

9647/02/CJC JC2 Preliminary Exam 2013

11

(b)

Starting with oxalic acid as the only organic reagent, propose a synthetic scheme to obtain
the following compound.

Your answer should include reagents and conditions used, as well as any intermediate
compound.
[2]
(c)

(i)

Oxalate ions, C2O42, are toxic to the human body. If sufficient amounts are ingested
and released into the bloodstream, the high concentration of oxalate ions would
cause the precipitation of calcium oxalate in the urine, which can accumulate into
painful kidney stones.
Assuming that the body excretes an average of 250 mg of calcium ions per litre of
urine, what is the minimum concentration of oxalate ions needed to precipitate
calcium oxalate in the urine?
Numerical value of solubility product of calcium oxalate, CaC2O4: 2.7 x 109

(ii)

(d)

A student added an excess amount of calcium oxalate in water to obtain a saturated

solution at equilibrium.
I

Write an equation to show why the saturated solution has a pH above 7 at

25 oC.

II

Predict and explain what happens when excess dilute HCl is added to the
saturated solution.
[5]

The oxalate ion, C2O42, forms a complex with platinum in oxaliplatin, a drug used in cancer
treatment.

(i)

Explain why oxaliplatin is considered a complex.

(ii)

State the oxidation number and coordination number of platinum in oxaliplatin.

(iii)

Explain why a complex can be formed between platinum and oxalate ion, unlike
calcium in (c) which forms a precipitate.
[4]
[Total: 20]

Hwa Chong Institution 2013

9647 / 03 / C2 Prelim 2013

A pink complex salt A has the molecular formula CoN5H17OCl3 (Mr = 268.4).
1.00 g of A is dissolved in water and the solution is titrated with 0.500 mol dm3 silver
nitrate solution. It is found that 22.40 cm3 of silver nitrate is required for complete
reaction.
When the pink solid A is heated, water vapour was evolved to give a purple solid B.
A and B have the same coordination number.
i

Calculate the number of moles of free chloride ions per mole of A.

ii

Draw the structure of the complex ion in A

iii

Suggest the formula of the complex ion in B.

.........

Account for the difference in the colour of A and B.

.........
.........
.........
[5]

wa Ch n

nstit ti n 2013

02 C2 Prelim 2013

Aqueous hydrogen peroxide is fairly stable, but when a mixture of a cobalt(II) salt and
tartaric acid is added to aqueous hydrogen peroxide, the initially pink solution slowly
turns into a green Co(III) species.

tartaric acid
After a while, oxygen gas is vigorously evolved and the solution turns back to pink again.
Both tartaric acid and the cobalt(II) salt are recovered from the solution at the end.
i

Explain the reactions that occurred in the observations that are in italics.
.........
.........
.........
.........

ii

State the role of the cobalt(II) salt and give two pieces of evidence to support your
answer.
Role of the cobalt(II) salt:
Evidence 1:
.........
.........
Evidence 2:
.........
.........

iii

Write an equation for the overall reaction.

.........

With the aid of relevant data in the Data Booklet, show that Co3+ is not stable in
aqueous solution and hence comment on the role of tartaric acid.
.........
.........
.........
.........
.........
[9]

wa Ch n

nstit ti n 2013

02 C2 Prelim 2013