A29547

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EXAMINATION BUT MUST NOT BE USED TO STORE
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COLLEGE OF ENGINEERING & PHYSICAL SCIENCES

SCHOOL OF CHEMISTRY
Year 2 Degree of MSci/BSc with Honours
Chemistry
Chemistry with Industrial Experience
Chemistry with Analytical Science
Chemistry with Bioorganic Chemistry
Chemistry with Business Management
Chemistry with Pharmacology
Chemistry with a Modern Language
Chemistry with Study Abroad
BSc / MSci NatSc Degree
CHM2C2-A/B / 03 25025 & 03 21407
Chemistry of the Elements II: s-, d- & p-Block & X-ray Diffraction
Summer Examinations 2015
Time Allowed: 2 Hours
Four questions should be attempted.
EACH QUESTION MUST BE ANSWERED IN A SEPARATE BOOK AND THE
NUMBER CLEARLY STATED ON THE FRONT OF THE BOOK. All these books
should be assembled with a completed grid (obtainable from an invigilator) and securely
fastened together.
(This examination counts towards your final degree assessment.

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1.

(a)

Across the second row of the periodic table (from Li to Ne), there is a general
increase in the first ionization energy.
(i) Write an equation to define the first ionization energy of Lithium and
briefly explain the general increase in ionization energy across period 2.
(ii) Briefly explain why B and O are exceptions to this trend (i.e. why the
ionization energy of B is less than Be and the ionization energy of O is less
than N).
(4 marks)

(b)

PbO2 is oxidizing and can be readily reduced to the more stable PbO.. In
contrast, GeO is a reducing agent. Explain these observations.
(6 marks)

(c)

The group 15 elements P, As, Sb and Bi all form pentafluorides e.g. PF5. Two
of the fluorides are covalent molecular species and two are polymeric solids.
State which compounds form which type of structure and explain your
reasoning.
(5 marks)

(d)

Compare and contrast the structure of clays and zeolites. Briefly explain how
zeolites are used in laundry detergents.
(5 marks)

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2.

(a)

Draw the molecular structure of diborane (B2H6) and use molecular orbital
theory to fully explain the structure.
(4 marks)

(b)

Boron and aluminium both form trichlorides.

(i) Draw structures for these two compounds and explain why only the
aluminium trichloride forms a dimer.
(3 marks)
(ii) Boron trichloride reacts readily with Lewis bases such as ammonia (NH3).
Using a diagram, explain how this reaction occurs and give the structure of
the product. Would you expect the enthalpy of reaction of BCl3 with
ammonia to be larger or smaller than the enthalpy of reaction of BF3 with
ammonia? Explain your answer.
(4 marks)

(c)

When metal salts are dissolved in water, the cation and anion are hydrated to
form aqua species.
(i) Write an equation for the hydrolysis of the aqueous species [Al(H2O)6]3+.
(2 marks)
(ii) Given the ionic radii below, would you expect [Ga(H2O)6]3+ to be more or
less acidic than [Al(H2O)6]3+? Fully explain your answer.
Cation

Ionic radius (pm)

3+

53.5

Ga3+

62.0

Al

(4 marks)
(iii) Experimentally, the values of pKa for hydrolysis of [Al(H2O)6]3+ and
[Ga(H2O)6]3+ are 4.95 and 2.60, respectively. Comment on these values.
(3 marks)
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3.
Equations Useful in X-ray Diffraction

2d hkl sin hkl

1
d hkl

h2 k 2 l 2
(in the cubic crystal system)
a2

Ahkl f j cos 2 hx j ky j lz j
j 1

Bhkl f j sin 2 hx j ky j lz j
m

j 1

(a)

At room temperature a crystalline sample is known to be cubic, body-centred

with a unit cell parameter of 8.426 . A student measures the diffraction
patterns produced by this sample at different temperatures using a
diffractometer with an X-ray source of wavelength 1.7902 .
(i) Predict the first three peak positions in the X-ray powder diffraction pattern
produced by this sample at room temperature.
(5 marks)
(ii) The sample is heated to 500C and a second diffraction pattern is
measured. Assuming that the sample has not undergone a phase change
predict the main difference between this and the pattern measured at room
temperature, explaining your reasoning.
(2 marks)
(iii) The sample is further heated to 800C and a third X-ray diffraction pattern
is measured. In this case there are several differences in the pattern
compared to those measured at room temperature and 500C including the
splitting of the (400) peak into two peaks. Suggest an explanation for this
splitting in terms of crystal systems and, based on this explanation give the
Miller indices of the two new peaks.
(5 marks)

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QUESTION 3 CONTINUES

(b)

Elemental cobalt adopts a cubic face-centred structure with one Co atom

position at (0, 0, 0) and the remaining three generated by the face-centring. By
calculating the structure factor F110 explain why the (110) peak is
systematically absent in the powder diffraction pattern of cobalt.
(8 marks)

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4.

(a)

(i) Explain why the d-d transitions in the electronic spectra of transition metal
complexes are less intense than charge transfer transitions.
(ii) Give the dn configuration for each of the three complexes [MnO4],
[Mn(H2O)6]2+ and [Mn(H2O)6]3+ and arrange the three complexes in order
of increasing intensity of their electronic transitions, explaining your
reasoning.
(4 marks)

(b)

The bond between a transition metal and a carbon atom is weak, so transition
metal alkyl complexes are unstable.
Criticise and correct this statement. Include as part of your argument reference
to the following compounds: - [Ti(CH3)4] (1) decomposes at 40 C;
[Ti(CH3)4(Me2PCH2CH2PMe2)] (2) stable for several hours at room
temperature; [Ti(CH2CMe3)4] (3) decomposes at its melting point above
100 C.

(5 marks)

QUESTION 4 CONTINUED OVER THE PAGE

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QUESTION 4 CONTINUES
(c)

Explain all the following observations: The infrared spectrum of HMn(CO)5 shows prominent peaks at 2016, 2008,
1984 and 1783 cm1. Its 1H NMR spectrum has just one peak, with a value of
7.85 ppm.
The infrared spectrum of DMn(CO)5 again shows prominent peaks at 2016,
2008 and 1984 cm1, but the 1783 cm1 peak disappears and is replaced by one
at 1287 cm1. No peak is seen in its 1H NMR spectrum.
(5 marks)

(d)

Bond lengths are shown for the Fe-C and Fe-P distances in the two compounds
[Fe(CO)5] and [Fe(CO)3(PPh3)2].

C-O stretching vibrations are observed in the infrared spectrum of [Fe(CO)5] at

2025 and 2000 cm-1, and in the infrared spectrum of [Fe(CO)3(PPh3)2] at 1944,
1866 and 1881 cm-1
Identify and explain the trends in both Fe-C distance and C-O stretching
frequency, on replacing CO ligands by PPh3. Include in your answer a diagram
showing how a transition metal binds to a CO ligand.
(6 marks)
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5.

(a)

Stability constants KML have been measured for the formation of complexes of
copper(II) with four neutral tetradentate ligands, shown below

(i) Explain what is meant by the terms hard acid and soft acid.
(ii) Use the data above to show whether copper(II) is behaving as a soft acid or
a hard acid in these compounds, explaining clearly the reasons for your
conclusions.
(iii) State which other important principle of coordination chemistry is
illustrated by these data. Explain your reasoning.
(5 marks)
QUESTION 5 CONTINUED OVER THE PAGE
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QUESTION 5 CONTINUES

(b)

Vanadium forms both a neutral hexacarbonyl, [V(CO)6], and the anion

[V(CO)6].
(i) Explain why [V(CO)6] is less stable than [V(CO)6].
(ii) In their infrared spectra, a CO stretching vibration is observed at
1976 cm1 for [V(CO)6], and 1860 cm1 for [V(CO)6]. Explain this
difference.
(5 marks)

(c)

Reduction of the complex [FeCl2{P(OMe)3}3] with Na/Hg gives

[Fe{P(OMe)3}5]; the corresponding reduction of [FeCl2(PMe3)2] with Na/Hg
gives [Fe(PMe3)4].
(i) Give the oxidation states and dn electron configurations of iron in
[FeCl2{P(OMe)3}3] and [Fe{P(OMe)3}5]
(2 marks)
(ii) Explain whether the compounds [Fe{P(OMe)3}5] and [Fe(PMe3)4] obey the
18-electron rule.
(2 marks)
(iii) Suggest why Fe(0) forms a four-coordinate complex [Fe(PMe3)4] with
trimethylphosphine but a five-coordinate complex [Fe{P(OMe)3}5] with
trimethyl-phosphite.
(1 mark)

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QUESTION 5 CONTINUES

(iv) In toluene solution, [Fe(PMe3)4] is partly present in the form below:

Explain how and why this molecule is formed. Suggest how it might be
detected in solution.
(3 marks)
(v) Why does Ni(0) form a four-coordinate complex [Ni{P(OMe)3}4] whereas
Fe(0) forms a five-coordinate complex [Fe{P(OMe)3}5] with the same
ligand?
(2 marks)
[Tolman cone angles for the phosphine ligands are as follows:
P(OMe)3 = 107; PMe3 = 118].

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6.

(a)

The Latimer Diagram for chromium in acidic solution is given below:

VI

Cr2O72

0.55

Cr5+

IV
1.34

Cr4+

III
2.10

Cr3+

II
0.424

Cr2+

0
0.90

Cr

(i) Using these data, construct a Frost diagram for Cr in acidic solution
(6 marks)
(ii) Identify from the Frost diagram (explain your answers fully):
The most stable oxidation state for Cr in acidic conditions,
Any species liable to disproportionate or comproportionate (include in your
answer a balanced equation for each of these processes).
(6 marks)

(b)

CoF2 adopts a rutile structure, whereas Co(OH)2 and CoI2 both adopt a CdI2
structure. Describe the key features of these two structure-types and account for
the above observations.
(6 marks)

(c)

Explain why V4+ ions in aqueous solution have a distorted octahedral

coordination with one very short bond
(2 marks)

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