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CHEM10101 Examination Paper January 2011

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CHEM10101 Examination Paper January 2011

CHEM10101 Introductory Chemistry (Jan 2011)
Outline Answers

Section A
1. (B) not allowed because l must be < n.

2. (B)

3. (C) Use VSEPR: Xe has 8 valence electrons, 1 each from F, 1 for negative charge: total
14, so 7 electron pairs arranged on pentagonal bipyramid. The two lone pairs keep as far
apart as possible. Hence, pentagonal planar with lone pairs in axial positions.

4. (D) from configuration [He]2s
2
2p
3
, one electron in each 2p orbital (Hund rule). Spin
quartet and orbital singlet.

5. (B) Only (ii) and (iii) are true.

6. (C) Only (iii) and (iv) are true.

7. (D) The reaction profile has a local energy minimum associated with an intermediate.

8. (D) Propan-2-ol is formed by the reduction of propanoic acid with lithium aluminium
hydride.

9. (C)

10. (B)

11. (A)

12. (D)

CHEM10101 Examination Paper January 2011

Section B
13. (a)

(i) Two valence electrons on Be, one for each H. Total 4 valence electrons, 2 pairs, hence
linear.
(ii) Group orbitals for two H atoms



Should derive scheme that looks something like:

In phase
Out-of-phase
Overlaps with Be 2s, 2p
2H(in-phase) with 2s
2H(out-of-phase)
with 2p
z
CHEM10101 Examination Paper January 2011



(iii) Overall bond order = 2 (two Be-H single bonds)
(iv) Additional electron in degenerate non-bonding pair. This would be unstable with
respect to distortion (bending). CH
2
would be bent.

13. (b)
[NH
2

] Five valence electrons on N, one each for H, one for charge. Total 8 valence
electrons; 4 pairs. Tetrahedral with respect to electron pairs, bent with respect to atoms.

[ClF
3
] Seven valence electrons on Cl, one each for F. Total 10 valence electrons; 5 pairs.
Trigonal bipyramidal with respect to electron pairs. Lone pairs in equatorial positions, hence
T-shaped with respect to atoms.

[SbF
5
] Five valence electrons on Sb, one each for F. Total 10 valence electrons; 5 pairs.
Trigonal bipyramidal with respect to electron pairs and atoms.
Out-of-phase
in-phase
Be 2H
nb(2p
x,y
)
!(2s)
!(2p
z
)
!*(2s)
!*(2p
z
)
CHEM10101 Examination Paper January 2011

14. (a)

(i) n = principal quantum number; R
H
= Rydberg constant; Z = atomic number.

(ii) Ionisation energy for H is energy required to take electron from n = 1 to ". In other
words, it is R
H
. 2nd ionisation energy for He corresponds to He
+
# He
2+
+ e

, and He
+
is a
one-electron (hydrogenic) ion. Hence, I
2
(He) = 2
2
. R
H
= 4.388 x 10
5
cm
1
.

(iii) Longest wavelength corresponds to the lowest energy, hence n = 1 # 2,3,4
1/$ = Z
2
R
H
[1/n
1
2
1/n
2
2
] (with R
H
in cm
1
) with n
1
= 1

n = 1 # 2 1/$ = 3.291 x 10
5
cm
1
$ = 3.039 x 10
6
cm (3039 nm)
n = 1 # 3 1/$ = 3.900 x 10
5
cm
1
$ = 2.564 x 10
6
cm (2564 nm)
n = 1 # 4 1/$ = 4.114 x 10
5
cm
1
$ = 2.431 x 10
6
cm (2431 nm)

(iv) For H (and other one-electron ions) the energy only depends on the principal quantum
number, n, hence all transitions between two states of given n are at the same energy. For
multi-electron atoms, like He, the energies depend on both n and the orbital quantum number,
l. Hence, 2s and 2p (etc.) at different energies and there will be many more transitions in the
absorption/emission spectra.

(b)
(i) K: [Ar]4s
1

Cr: [Ar]4s
2
3d
1

(ii) K: S = 1/2, orbital singlet (L = 1) #
2
S
Cr: S = %, orbital pentet (L = 2) #
2
D

CHEM10101 Examination Paper January 2011

Section C
15.

(a) Describe and explain the structural features that provide stabilising effects within the
species 1, 2, 3 and 4 shown below.

1 4
N O
C
CH
3
CH
3
H
2
O
3
H C O
O
O


1 methyls; hyperconjugation; diagram (3 marks)
2 resonance; delocalisation; resonance form diagram (3 marks)
3 resonance; resonance form diagram (2 marks)
4 resonance ; arrows (2 marks)
Marks for well-worded explanations, clear correct diagrams

(b) Provide a detailed analysis of the reaction shown below. Your analysis should include:
(i) full mechanisms (electron movement arrows) for each step;
(ii) diagrams showing the 3-D structure of the reacting centres at each step of the reaction;
(iii) an explanation of the observed selectivity.

5
HCl
ether
CH
3
6
only product
CH
3
Cl

Stepwise addition mechanism (4 marks)
Geometric structure of intermediate cation (3 marks)
Explanation of regioselectivity (3 marks)
Marks for well-worded explanations, clear correct diagrams
CHEM10101 Examination Paper January 2011

16.
(a) Arrange the following compounds in order of increasing acidity, giving explanations
for your choice:

ClCH
2
CO
2
H PhOH CH
3
CO
2
H EtOH

Correct order is EtOH < PhOH < CH
3
CO
2
H < ClCH
2
CO
2
H (most acidic)
Acidity is related to the stability of the anion of the conjugate base, which depends on the
effectiveness of delocalisation of negative charge. Canonical forms for the delocalised
anions should be given, as well as inductive electron withdrawal by the Cl atom.

(b) Give the products for the following reaction, and a mechanism that accounts for the
formation of each product:

Ph NH
2
+
Br


The secondary amine hydrobromide should be given, formed by S
N
2 substitution. Products of
further substitution (tertiary amine, quaternary ammonium salt) may be given here, or
mentioned below.

Comment on the suitability of this type of reaction for the preparation of secondary amines.

There may be problems with further substitution to give the tertiary amine and quaternary
ammonium salt.

(c) Give two different combinations of Grignard reagent (organomagnesium halide) and
aldehyde which could be used to prepare the alcohol 1. Draw a mechanism for the reaction
using one combination.

Ph
OH
1

Phenylmagnesium bromide and butanal OR benzaldehyde and butylmagnesium bromide.
Standard mechanism: Nucleophilic addition of Grignard to carbonyl, followed by
protonation on work-up.

CHEM10101 Examination Paper January 2011

Section D

17. (a) (i) Harmonic potential well (parabola), equally spaced vibrational levels, something
like:

(ii) &V = +1 so spectrum should have one absorbance peak, at 2986 cm
1
( = E/hc).

17. (b) (i) Something like:

(ii) Bond has a finite dissociation energy, therefore weakens as its vibrational energy
increases.

(iii) Separation between energy levels (therefore vibrational transitions) become closer, so
more complex spectrum seen, although requires population of V =1 (and higher) energy
levels. Formally "forbidden" transitions ('V (1) can also appear.
CHEM10101 Examination Paper January 2011

18. (a)
Either in words (amount of heat required to raise the temperature of one mole of a substance
by 1 K) or mathematically:


T
q
dT
dq
C
!
!
" =

Should recognise that amount can also be defined in terms of mass = specific heat cap.
(Bonus mark if mention that the derivative is actually a partial one, i.e. C
V
and C
p
exist)

(b)
Equipartition of energy, each degree of freedom contributes 0.5RT to system. For noble
gas, total energy is 1.5 RT (translation only), hence heat capacity (constant volume) is 1.5R )
observed value.

(c)
(i) N
2
: translation contribution seen () 1.5R), but rotational modes contributes another 0.5R
each, hence observed C
V
of approximately 2.5R. Note this value implies vibrational modes do
not contribute: only accessed at higher temperatures. Students should recognise that each of
the above types of motion involves significantly - orders of magnitude - larger energy
changes.

(ii) Bond strength affects vibrational energy (the latter is lower if the former is lower), so a
weaker bond would mean that the molecule could be vibrationally excited at lower
temperatures, and thus the vibrational contribution to the heat capacity would be seen within
the above temp range.

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