Problems and Solutions to the Third

Phase Malaysian IChO Selection Camp

Prepared by
Yau Ching Koon

Version March 23, 2015

Copyright note: the author does not own the copyright to the problems, which
should belong to the following problem authors. However, all typesetting, minor
corrections and artworks accompanying the problems and all of the solutions do
belong to the author.
Problem authors:
Prof. Noorsaadah Abdul Rahman (carbonyl compounds)
Prof. Wan Jeffrey Basirun (electrochemistry)
Assoc. Prof. Lo Kong Mun (coordination compounds)
Dr. Azizah Mainal (thermodynamics)
Dr. Desmond Ang (reaction kinetics)
Dr. Noordini Mohamad Salleh (alcohols)

P ROBLEM 1. Nitrogen pentoxide, N2 O5 is an unstable and potentially dangerous

oxidizer. Upon decomposition, it produces nitrogen dioxide and oxygen:
2 N2 O5

4 NO2 + O2

Following is the proposed mechanism for the above reaction:

kf
N2 O5
NO3 + NO2

NO2 + NO3

kb
k2

NO + NO2 + O2
k3

NO3 + NO

2 NO2

Apply steady state approximation to determine the rate law.

[15 marks]

P ROBLEM 2. Dilatometry technique can be employed to study chemical kinetics of

reaction that shows change in effective volume. Example is the reaction between
ethylene oxide and perchloric acid. Followings are the data obtained from an
experiment conducted at constant temperature:
Reaction time (min)

Dilatometer reading

0
30
60
135
300

18.48
18.05
17.62
16.71
15.22
12.29

Assuming it is a first order reaction, determine the average rate constant.

[10 marks]
P ROBLEM 3. The rate law describing the decomposition of hydrogen iodide to
dihydrogen and diiodine is
rate = k [HI]2
3

If 0.01 mol of HI(g) is placed in a container with capacity of 1.0 L at 25 C, determine the time needed for the concentration of HI(g) in the container to decrease
by 10%. Given the rate constant of the decomposition is 2.4 1031 L mol1 s1 .
[5 marks]
P ROBLEM 4. Which of the following entities are state functions, and which are
not?
1. work
2. heat
3. temperature
4. enthalpy
5. internal energy
6. volume
[6 marks]
P ROBLEM 5. An electric motor produces a mechanical work of 30.0 kJ energy per
second. The motor also loses 4.5 kJ per second of heat to the surrounding. What
is the change in internal energy, U, of this motor?
[3 marks]
P ROBLEM 6. We are often concerned with the work done on or by a system as
it contracts or expands. The work done by this system depends on the volume
change and the external pressure.
1. What does the term free expansion mean?
2. What is the amount of work done in a closed system?
[2 marks]
P ROBLEM 7. Sketch a pV plot for an isochoric process. Write the appropriate
expression for the internal energy, U based on this process.
[4 marks]
4

P ROBLEM 8. Explain why the heat capacity for a gas at constant pressure, C p is
larger than the heat capacity at constant volume, CV .
[4 marks]
P ROBLEM 9. Given the thermochemical equation below, estimate the change in
the internal energy, f Um for the formation of ammonia, NH3 at 25 C.1
3
1
H2 (g) +
N2 (g)
2
2

NH3 (g)

f Hm = 46.1 kJ mol1

(R = 8.314 J mol1 K1 )

[5 marks]

P ROBLEM 10. Name two situations in which the change in internal energy, U is
equal to the change in enthalpy, H, i.e. U = H.
[4 marks]
P ROBLEM 11. Given the following heat of reaction:
H2 (g) + Cl2 (g)

2 HCl(g)

H = 184.6 kJ

Calculate the standard enthalpy of formation, f H for HCl.2

[3 marks]

P ROBLEM 12. What does it mean when the value of Gibbs free energy change, G
for a chemical reaction is
1. Positive?
2. Negative?
3. Zero?
[3 marks]
P ROBLEM 13. The latent heat of vaporization of water is 40.656 kJ mol1 , and its
melting point is 273.15 K at 1 atm pressure.
1 The

original question does not specify the amount of ammonia formed, hence any value for
f U is technically correct.
2 We shall assume that the given heat of reaction was determined at standard conditions. Oth are correct.
erwise any values of f H

1. Calculate the molar entropy change of vaporisation of water. (Note: the unit
for molar entropy change, Sm is J K1 mol1 .)
2. Would the change in entropy of the melting of ice be larger or smaller than
that of the entropy of vaporization of water? Explain.
[6 marks]
P ROBLEM 14. Provide a reasonable mechanism for the following reaction.
OH
H2 SO4 ,

P ROBLEM 15. Predict the products from each of the following reactions.

(1) BH3 THF

(2) NaOH, H2 O2

1.

conc. H2 SO4

2.

OH
3.
OH

(1) H2 SO4
(2) BH3 THF
(3) NaOH, H2 O2
6

P ROBLEM 16. Predict the organic product for each of the following reactions.
O
(1) CH3 MgBr, Et2 O

1.

(2) H3 O+

O
(1) CH3 CH2 Li, Et2 O

2.

(2) H3 O+

O
3.

(1) CH3 MgBr (excess), Et2 O

(2) H3 O+

P ROBLEM 17. Provide three methods that employ Grignard reagents to synthesize
the following compound.
OH

P ROBLEM 18. Provide the reagents needed to achieve each of the following transformations.
Br

OH
1.

2.

OH

Cl

Br

Br
OH

Cl

3.

Br

OH

4.

Br

OH
OH

H
H
5.

H
H

P ROBLEM 19. The reaction of CoCl2 with NH3 in the molar ratio of 1 : 4, 1 : 5
and 1 : 6 yielded four types of cobalt complexes with different colours: yellow
(max = 435 nm), purple (max = 495 nm), green (max = 700 nm) and violet
(max = 810 nm), respectively.
1. Draw the molecular structures of the four cobalt complexes.
8

2. Propose an experiment to differentiate these four types of cobalt complexes.

3. By using the ligand field splitting parameter, determine whether Cl or NH3
is a strong field ligand.

P ROBLEM 20. Draw the orbital energy level diagram for a d9 metal complex. Calculate its ligand field stabilization energy in unit of o . Draw the orbital energy
level diagram to show the effect of tetragonal distortion to the complex. Draw
also the orbital energy level diagram if the tetragonal distortion goes as far as
the total loss of the ligands along the z-axis and the formation of a square planar
complex.
P ROBLEM 21. Persulfate is a very strong oxidizing agent. If HCl is added into
a solution containing ammonium persulfate, explain (by calculations), whether
chlorine gas will be liberated or otherwise.
S2 O28 + 2 e
Cl2 + 2 e

2 SO24
2 Cl

E = 2.01 V vs. SHE

E = 1.36 V vs. SHE

P ROBLEM 22. Permanganate ion, MnO4 is also a very strong oxidizing agent,
but unlike persulfate, it needs acidic conditions to realize its full capacity as an
oxidizing agent.
Calculate at which pH, the permanganate ion will start oxidizing the chloride
ions in HCl into chlorine gas.




Assume, the MnO4 and Mn2+ are 1 mol dm3 and Cl2 pressure is 1 atm.
MnO4 + 8 H+ + 5 e

Mn2+ + 4 H2 O

E = 1.50 V vs. SHE

Solutions to Problems
Problem 1. The rate of this reaction can be measured by
rate =

1 d [ N2 O5 ]
1 d [NO2 ]
d [ O2 ]
=
=
2
dt
4 dt
dt

Consider three possible rate determining steps.

If kf is the rate determining step, then the rate of reaction is simply
rate = kf [N2 O5 ]
A plausible scenario of this case is illustrated by the graph below.

blue: N2 O5 , green: NO2 , black: O2 , yellow: NO3 , red: NO

10

If k3 is rate determining, then the faster k2 would have decomposed all of the
nitrogen trioxide and is inconsistent with the stoichiometry observed. Hence, k3
cannot be the rate determining step. A plausible scenario of this case is illustrated
by the graph below and take note of the rapid diminishing of the yellow line.

blue: N2 O5 , green: NO2 , black: O2 , yellow: NO3 , red: NO

If k2 is the rate determining step, we have
rate =

d [ O2 ]
= k2 [NO3 ] [NO2 ]
dt

Also, after some finite time, the kf and kb would have achieve equilibrium. We

11

may therefore write

kf [N2 O5 ] = kb [NO2 ] [NO3 ]
k
[NO2 ] [NO3 ]
K f =
kr
[ N2 O5 ]
Hence
rate = Kk2 [N2 O5 ] = kobs [N2 O5 ]
A plausible scenario of this case is illustrated by the graph below and take note of
different curvatures of the blue vs. green or black line.

blue: N2 O5 , green: NO2 , black: O2 , yellow: NO3 , red: NO


12

Problem 2. For first order reactions, dilatometry utilizes the equation

ln

Vt V
= kt + const.
V0 V

Calculating the LHS term gives the following table.

t/min

ln [(Vt V ) / (V0 V )]

30
60
135
300

0.0720
0.1496
0.3368
0.7479

The gradient, using the regression mode on a calculator, gives the average rate
constant as
k = 2.499 103 min1 = 4.165 105 s1

13

Problem 3. A plausible elementary step of the reaction consistent with the rate
law is given by
2 HI

H 2 + I2

Therefore,
rate =

1 d [HI]
= k [HI]2
2 dt

where the integrated form reads

Z [HI]
t d [HI]

[HI]0 [HI]2
1
1

+
= 2kt
[HI]t [HI]0

= 2k

Z t
0

dt

Given that [HI]t = 0.9 [HI]0 and [HI]0 = 0.01/1 = 0.01 mol L1 , we have


1
1
1
t=

2 2.4 1031 0.9 0.01 0.01

= 2.31 1031 s

14

Problem 4.
1. w is not a state function
2. q is not a state function
3. T is a state function
4. H is a state function
5. U is a state function
6. V is a state function

15

Problem 5. The first law of thermodynamics gives

dU
dq dw
=
+
= 30 4.5 = 34.5 kJ s1
dt
dt
dt
The negative sign for both the work and heat indicates that the work and energy
produced are at the expense of the internal energy of the motor.


16

Problem 6.
1. Free expansion is the expansion of a matter into vacuum.
2. A closed system forbids the exchange of particles but allows the exchange
of energy. The exchange of energy obeys the first law of thermodynamics,
w = U q
It should worth noting that this work w includes p-V work, E-q (electrochemistry) work, -A (surface) work, etc.

17

Problem 7. The work done by a gas for an isochoric process is w = 0, the heat

p
or
V

absorbed or released is q = nCV,m T while the change in internal energy is

U = q + w = nCV,m T

18

Problem 8. Consider two separate gases, one heated at constant pressure and
one heated at constant volume. The gas heated at constant pressure stores part
of the heat absorbed into its internal energy and converts another part of the heat
into expansion-work. For the same amount of heat supplied, the gas heated at
constant volume does not need to (or rather by definition could not) expand,
and hence all the heat absorbed is stored as internal energy. Hence for the same
amount of heat supplied, the temperature rises more for the case where a gas is
heated at constant volume compared to heating at constant pressure. Thus, the
heat capacity of a gas at constant volume is smaller than that at constant pressure.


19

Problem 9. The enthalpy is

H = U + ( pV ) = U + pV + Vp
The definition for f Hm implies p = 0, while V for the formation is
V =

RT
[n (NH3 ) n (N2 ) n (H2 )]
p

assuming that H2 , N2 and NH3 all behaves ideally. Since for every mole of NH3
formed, half mole of N2 and three halves of H2 is consumed, we have
n (N2 ) =

1
n (NH3 ) ,
2

or
V =

n ( H2 ) =

RTn (NH3 )
,
p

3
n (NH3 )
2

Vm =

RT
p

Hence,
f Hm = f Um RT,
f Um = 46.1 103 + (8.314) (25 + 273.15) = 43.6 kJ mol1

20

Problem 10. Since dU = S dT p dV and dH = S dT + V dP, the condition

U = H implies that
p dV = V dp
or
d ( pV ) = 0
Either of these two equations can be satisfied in several ways. (1) An expansion
at which p = 0 or an expansion into vacuum. (2) A change in pressure at V = 0.
(3) Any process where d ( pV ) = 0 such as isothermal compression or expansion
for an ideal gas since d ( pV ) = nR dT = 0 implies dT = 0.


21

Problem 11. By definition, the standard enthalpy formation refers to the formation of one mole of a particular substance, here being HCl. Thus, for
1
1
H2 (g) +
Cl2 (g)
2
2

HCl(g)

the standard enthalpy of formation is

f Hm
=

184.6
= 92.3 kJ mol1
2

Due to the definition, the standard enthalpy of formation, f H and standard

are equivalent.
molar enthalpy of formation, f Hm


22

Problem 12.
1. The forward reaction is thermodynamically non-spontaneous.
2. The forward reaction is thermodynamically spontaneous.
3. The system is in equilibrium.
Note that Gibbs energy could, in general, describes a system and not limited to a
reaction only.


23

Problem 13.
1. 40.656 kJ of energy is required to convert one mole of water to its vapour.
Hence the molar entropy of vaporisation of water is
Sm =

40.656
q
=
= 108.95 J mol1 K1
T
373.15

2. The entropy of fusion of ice is expected to be smaller than the entropy of

vaporisation of water. During fusion, the heat are absorbed to break the
hydrogen bond network partially, giving some translational motion to the
water molecules. However, during vaporisation, the heat are absorbed to
break all the hydrogen bonds between the molecules and hence is larger in
magnitude compared to the heat absorbed during fusion.

24

Problem 14.

25

Problem 15.

(1) BH3 THF

(2) NaOH, H2 O2

1.

OH

conc. H2 SO4

2.

OH
3.
OH

(1) H2 SO4
(2) BH3 THF
(3) NaOH, H2 O2

OH

26

Problem 16.
O

OH
(1) CH3 MgBr, Et2 O

1.

(2) H3 O+

OH

O
(1) CH3 CH2 Li, Et2 O

2.

(2) H3 O+

O
3.

OH
O

(1) CH3 MgBr (excess), Et2 O

(2) H3 O+

27

Problem 17.
O

OH
(1) MeMgBr, THF
(2) H3 O+

OH
(1) nPrMgBr, THF
(2) H3 O+

OH
O

(1) PhMgBr, THF

(2) H3 O+

28

Problem 18.
Br

OH
PBr3

1.

O
SOCl2

2.

O
OH

Cl

Br

Br
OH

Cl
PCl5

3.

Br

OH

2 eqv. PBr3

4.

Br

OH
OH

H
H
5.

conc. H2 SO4

H
H

29

For part (5.), the combination (1) TsCl, pyridine (2) DBU can also be used (answer
due to Chan Jer Yong). DBU = 1,8-diazabicyclo[5.4.0]undec-7-ene.


30

Problem 19.
1. The structure of the four complexes of cobalt are shown below, (I)(IV). (I)
and (II) are 1 : 4 adduct, (III) is a 1 : 5 adduct and (IV) is a 1 : 6 adduct.
Cl

Cl

H3 N

NH3

H3 N

Co

Co

H3 N

NH3

H3 N

H3 N

NH3

Cl
NH3

Cl
I

NH3

II

Cl

Co

NH3

Cl

NH3

H3 N

H3 N

NH3

NH3

NH3

NH3

Co

2+

2 Cl

NH3

III

IV

2. The solution may be best described in James E. Huheey, Ellen A. Keiter and
Richard L. Keiter (1993), Inorganic Chemistry: Principles of structure and reactivity 4th edn., HarperCollins College Publisher, New York, USA, pp. 387
389. These pages are reproduced here.

31

32

33

34

3. Nothing can be inferred because all four compounds belong to four separate
symmetry point group, viz. D4h for (I), C2v for (II), C4h for (III) and Oh for
(IV). The separation between the highest fully-filled d-orbital and lowest
empty or partially-filled d-orbital, is dependent on the point group.

35

Problem 20. The orbital energy level diagram for a d9 complex is shown below.
Also shown are the energy levels due to tetragonal distortion and that of square
planar.

x y

t 2g
xy
z

Do
eg

tetragonal
distortion

xz, yz

square planar

The ligand field stabilization energy is





2
3
3
E = 6 o + 3
o = o
5
5
5

36

Problem 21. The e.m.f. for the reaction

S2 O28 + 2 Cl
is

2 SO24 + Cl2

E = 2.01 1.36 = 0.65 V

Since E > 0 V, the forward reaction is spontaneous at 298 K and 105 Pa. Chloride
ions will be oxidized by persulfate ions to form chlorine gas.


37

Problem 22. The e.m.f. for the reaction

2 MnO4 + 16 H+ + 10 Cl
is

2 Mn2+ + 8 H2 O + 5 Cl2

E = 1.50 1.36 = 0.14 V

Under non-standard conditions, the e.m.f. of the reaction is given by Nernst equation


2+ 2 f (Cl )5
a
Mn
RT
2
ln
E = E

2
16
10

nF
a MnO
a (H+ ) a (Cl )
4

For the forward reaction to proceed spontaneously, E > 0 or (although not given,
we shall assume that a (Cl ) = 1 for simplicity)
1
RT
< E
ln
16
+
nF
a (H )
0.14 10 96485
16 ln { a (H+ )} <
= 54.49
8.3145 298.15
54.49 lg e
pH lg { a (H+ )} <
= 1.48
16

38