XCHA 2714

SECOND PUBLIC EXAMINATION

Honour School of Chemistry
CHEMISTRY PART IA
INORGANIC CHEMISTRY IA
TRINITY TERM 2008
Thursday, 5 June, 9.30 a.m. to 12.30 p.m.
Candidates should answer five questions.
Please start each question in a new booklet.
The numbers in square brackets indicate the approximate marks that the
examiners intend to assign to each part of the question.

The following abbreviations have been used:

Ph = C6H5

Me = CH3

acac =

py = C5H5N

en = H2NCH2CH2NH2

O
O

bipy =

phen =

EDTA4 = [(OOCCH2)2NCH2CH2N(CH2COO)2]4
1 equiv. = 1 molar equivalent
SALC = symmetry adapted linear combination
RMM = relative molecular mass

Do not turn over the page until you are told to do so.

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1.

Answer THREE of the following (a) (e), giving a full explanation in

each case:
[3 ! 20/3]

(a)

Deduce the number of carbonyl stretching bands observed in the infrared

spectrum of fac-Mo(PPh3)3(CO)3.

(b)

Depict the symmetry elements and hence identify the point group of ONE
of the following:
XeOF4

(c)

BrF3

Fe2+

Eu3+

Co(acac)3

Yb3+

Te2+

Which of the following have one or more unpaired electrons per formula
unit?
GaCl2(s) PdF2(s) NO(g)

(e)

[PtCl4]2

Give the ground state term symbol for THREE of the following gas-phase
ions:
Cr3+

(d)

B2H6

Ni(CO)4(l)

Li(s) Fe("#-C5H5)2(s)

Predict and sketch the appearance of the 31P NMR spectrum of both facRh(PPh3)3Cl3 and mer-Rh(PPh3)3Cl3.
[Consider only the following nuclear spins and abundances where
relevant: 31P: I = (100%); 103Rh: I = (100%). You may ignore
coupling to 1H.]

XCHA 2714

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2.

Answer ALL parts.

(a)

Account for the different coordination geometries of the metal in the

complex anions [NiCl4]2 and [Ni(CN)4]2.
[4]

(b)

Match the ligand-field splitting parameters (!/cm1) listed below to the

following species, giving reasons for your assignment.
2700

3300

8000

12986

[Co(en)3]3+ [CoF6]4 [Rh(en)3]3+

(c)

[CoI4]2

34600
[CoF6]3 [CoCl4]2 [6]

The following compounds adopt the spinel structure. In each case identify
the oxidation states of all the cations present and predict their
coordination geometries:
CoCr2O4

CoFe2O4

Give reasons for your assignments.

(d)

23200

ZnFe2O4
[5]

Compare and contrast the solid-state structures adopted by compounds

having the following empirical formulae:
(i)
(ii)

CrCl2 and MoCl2

CrO3 and WO3

What general principles and trends in d-block chemistry do these

examples illustrate?
[5]

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3.

Answer ALL parts (a) (d) which refer to the chemistry of selenium.

2A + 2B

D
Dilute
HCl

6AsF5, 80$C
Fe, Heat

Se8

Identify A and discuss its molecular and electronic structure. [4]

Identify B and explain why it is formed in the reaction.
[2]

Heating Se with metallic iron readily forms the solid C containing

41.40% Fe and 58.60% Se. Treatment of C with dilute aqueous HCl
gives off a toxic gas D containing 97.53% Se.
(i)
(ii)
(iii)

(c)

Treatment of Se with AsF5 in an inert solvent gives two products A and

B. The compound A contains a diamagnetic di-positive cation and is
composed of 45.55% Se, 21.59% As, 32.86% F. B is a compound of
arsenic and has a RMM of 131.9.
(i)
(ii)

(b)

O2, Pressure,
Heat

Cl2

(a)

F2, 0$C

Identify and suggest structures for C and D.

[4]
Explain why D is less stable to decomposition than the analogous
sulfur compound.
[2]
Comment on the observation that the pKa of D is 3.9 while that of
the sulfur analogue is 6.9.
[2]

The reaction between Se and F2 at 0 $C gives E (RMM=155) which has a

dipole moment.
Identify E and predict its 77Se NMR spectrum in solution at 50 $C. [2]

[Nuclear spins (and abundances where relevant): 19F: I = (100%);

77
Se: I = (7.6%)]
Question continues

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(d)

Heating Se under O2 pressure gives a white solid G containing 71.17%

Se. G readily dissolves in water to give an oxy-acid with pK1 = 2.5.
(i)
(ii)

[2]
Identify G and account for the pK1 value of the oxy-acid.
Comment on the fact that the analogous reaction between sulfur
and oxygen, although extremely slow, gives a product with a
different stoichiometry.
[2]

[Relative atomic masses: Se = 79.0, As = 74.9, Fe = 55.8, Cl = 35.5, F = 19.0,

O = 16.0, H = 1.0]

XCHA 2714

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4.

Answer ALL parts.

(a)

Using caesium chloride as an example, explain the meaning of the terms

given in (i) (iii) as used in the description of a crystalline material. [6]
(i)
(ii)
(iii)

(b)

lattice
basis
structure

The first seven lines in the X-ray powder diffraction pattern of a cubic
metal oxide, recorded using Cu K! radiation with a wavelength of
1.5418 , occur at scattering angles (2"/degrees) of
34.970 40.600 58.766

70.246 73.871 87.876

98.250

Identify the lattice type, index the lines and determine the unit cell
parameter.
[8]
(c)

The crystal structure of calcium fluoride can be described in terms of a

face-centred cubic lattice with a basis consisting of a calcium ion at
(0, 0, 0) and fluoride ions at (, , ) and (, , ). How many CaF2
formula units are there in the unit cell?
[1]

(d)

Show that in the X-ray diffraction pattern of calcium fluoride only the
calcium ions contribute to the observed lines having Miller indices that
satisfy the condition h+k+l = 2n + 1.
[5]
[You may take the structure factor of the hkl reflection from a
centrosymmetric structure to be Fhkl = % f i cos2#(hxi + kyi +lzi) ].
i

XCHA 2714

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[3 ! 20/3]

5.

Answer THREE of parts (a) (d).

(a)

Comment on the stepwise stability constants (Kn) in aqueous solution for

complexes of Co2+, Ni2+ and Cu2+ with the ligand H2NCH2CH2NH2:

(b)

log K1

log K2

log K3

Co2+

5.89

4.83

3.10

Ni2+

7.52

6.28

4.26

Cu2+

10.55

9.05

1.00

With reference to the diketone (I) and diamine (II) shown below,
discuss the factors controlling the formation of macrocyclic ligands
using metal ion templates.

H3 C

CH3

N
O

H2N

O
(II)

(I)

(c)

Discuss the potential for isomerism in the following species:

[Ru(bipy)3]2+

(d)

NH2

[Co(en)2Cl2]+

Pt(NH3)2Cl2

Comment on the stepwise stability constants (listed below) of Fe2+ with

bipy and of Cd2+ with Br in aqueous solution:
log K1

log K2

log K3

log K4

Fe2+/bipy

4.20

3.70

9.30

&

Cd2+/Br

1.56

0.54

0.06

0.37

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6.

Answer ALL parts (a) (d).

(a)

Draw Lewis structures for the following molecules:

N2O4

O3
(b)

N2F4

[3]

A molecular orbital energy level diagram for CO2 is shown below.

Inclusion of the oxygen 2s orbitals in bonding has minor effects on the
energies of the molecular orbitals.
3'u
3' g

2(u

2p

2s
1(g

2 ! 2p

1(u
2'u
2'g
1'u
1'g

2 oxygens

carbon
O

(i)

2 ! 2s

Sketch the combination of atomic orbitals for the 2!g, 2!u, 1"u
and 1"g molecular orbitals and discuss the nature of the bonding
in each.
[6]
Question continues

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(c)

(ii)

Calculate the bond order of each XeF bond in the linear

molecule XeF2. It has been suggested that the Xe 5dz2 orbital
might be involved in bonding in XeF2. Discuss which of the
molecular orbitals in the diagram above might be involved and
how Xe 5dz2 participation might alter their energies.
[3]

(i)

Show that the lowest energy unoccupied molecular orbital

(LUMO) of CO2 is the 2"u orbital.
[1]

(ii)

The molecule NO2 has a bent structure. A linear structure for

NO2 would have one electron in the 2"u orbital. Assess the
effect of bending the linear molecule in the xz plane on the
overlap and thus energy of the px and py components of the 2"u
molecular orbital shown below. Hence rationalise why the bent
structure of NO2 is at a lower energy than the linear structure. [5]
[Detailed analysis of any changes in orbital mixing on bending is
not required.]
x
z
px component

(d)

py component

Use your answer to (c) to explain why ozone (O3) has a bent structure and
calculate the bond order of each OO bond.
[2]

XCHA 2714

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7.

Answer part (a) and TWO of parts (b) (d).

(a)

Discuss the trend shown below for the 3rd ionisation energy of the
lanthanide elements (Ln) and the implications in the occurrence of the +2,
+3 and +4 oxidation states for these elements.
[6]
The iodides LnI3 and sulfides Ln2S3 of the lanthanide elements are
insulators. Explain the observation that heating these compounds with the
lanthanide metal gives conducting solids with, for example, La, Ce and
Nd but the products for Eu and Yb are insulators.
[4]

3rd Ionisation energy / kJ.mol

-1

2600

2400

2200

2000

1800

1600

Gd 11
Tb 12
Dy 13
Ho 14
Er 15
Tm 16
Yb 17
Lu 18
3 Ce
4 Pr
5 Nd
6 Pm
7 Sm
8 Eu
9 10
2 La
Number of valence electrons

(b)

Identify the compounds A, B and C in the reaction sequence below and

comment on the structure and properties of B and C in light of the data
provided.
[5]
UO2 + HF

ClF3

H2O

A and C have formula weights of 314 and 308, respectively.

B has a boiling point of 56 C.
The infrared spectrum of C shows a strong band at ~950 cm1 which is
shifted if 18OH2 is used in the reaction with B. This band also persists
when C is dissolved in strong acid or alkali.
[Relative atomic masses: U = 238, O = 16, F = 19]
Question continues

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(c)

Comment on the similarities and differences in the solid-state structures

of the following compounds.
[5]
LuCl3

LaCl3

UCl3

AlCl3

ReCl3

Ionic radii (in pm) for octahedral coordination are provided below for
comparison purposes although the ions in the compounds above do not
necessarily have 6-fold coordination:
La3+ 106;
(d)

Lu3+ 86;

U3+ 103;

Al3+ 54;

Re3+ 68

Discuss the observation that, in water, the lanthanide ions Ln3+ readily
form complexes with ligands such as EDTA4 and acac but not with NH3
and en (H2NCH2CH2NH2). Account for the thermodynamic data given
below for the formation of lanthanide complexes Ln(EDTA) at 298 K.
[5]
Ln

)G

/ kJ mol*1

)H / kJ mol*1

)S / J mol*1 K*1

La3+

$86.7

$12.2

249.8

Nd3+

$91.6

$13.2

262.1

Gd3+

$96.0

$10.6

286.6

Lu3+

$109.2

$10.5

331.0

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8.
(a)

Answer BOTH parts (a) and (b).

Identify and draw the structure of the organometallic product for
THREE of the following reactions (i) (v). Give the valence electron
count of BOTH the organometallic reactants and products.
[3 ! 4]
(i)

Mo(CO)6 + excess PPh3

(ii)

Cr(CO)6 + PhLi

(iii)

Mn(CO)5Me + PPh3

Fe

(iv)

(v)
Ti

(b)

+ CH3COCl

Cl
Cl

AlCl3

+ 2 MeLi

Comment on the following two sets of data.

(i)

(ii)

[2 ! 4]

CO stretching vibrations (in cm1)

CO

2143

[V(CO)6]

1858

Cr(CO)6

1984

[Mn(CO)6]+

2094

C=C bond lengths (in pm)

C2H4

133.0

Pt(PPh3)2("2-C2H4)

143.0

K[PtCl3("2-C2H4)]

137.5
End of paper

XCHA 2714

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