33rd International Chemistry Olympiad ∗ Preparatory Problems

Worked Solutions to Problems

1. Water

A. Phase diagram

a. The three phases of water coexist in equilibrium at a unique temperature and

pressure (called the triple point):

Ttr = 273.16 K = 0.01 °C Ptr = 6.11 x 10−3 bar

b. If pressure decreases, boiling point decreases, but melting point increases

(slightly).

c. Beyond this point, there is no distinction between liquid and vapour phases of
water. Put alternatively, it is possible to have liquid to vapour transition by a
continuous path going around the critical point. (In contrast, solid-liquid
transition is discontinuous.)

d. T = 300K, P = 12.0 bar : liquid phase

T = 270K, P = 1.00 bar : solid phase

e. Below P = 6.11 x 10−3 bar, ice heated isobarically will sublimate to vapour.

f. If xl and xv are the mole fractions of water in liquid and vapour phases,

V = xl Vl + x v V v = x l Vl + (1 − xl ) V v
Vv − V
∴ xl = = 4.6 x 10−1
V v − Vl
Vl xl Vl
= = 0.140
V V
Vv
= 1 − 0.14 = 0.860
V

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

B. Clausius – Clapeyron equation

a. dP ∆H
=
dT T ∆V
∆H = molar enthalpy change in phase transition

∆V = molar change in volume in phase transition.

For ice-liquid water transition :

∆H > 0 ∆V < 0, since ice is less dense than water.

dP
∴ < 0
dT

Since ∆V is not large, the P-T curve for this transition is steep, with a
negative slope. Thus decrease of pressure increases the melting point
slightly.

For liquid water - vapour transition

ûH > 0 ûV< 0
dP
∴ > 0
dT

Decrease of pressure decreases the boiling point.

b. Clausius - Clapeyron equation for (solid) liquid - vapour transition is

dP P ∆Hvap
=
dT RT 2
This equation follows from the Clapeyron equation under the assumptions:

1. Vapour follows ideal gas law.

2. Molar volume of the condensed phase is negligible compared to molar

volume of vapour phase.

3. If further ∆Hvap is assumed to be constant (no variation with T), the eq.
is integrated to give

P2 ∆Hvap 1 1
ln =  − 
P1 R  T1 T2 

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Here P1 = 1.01 bar , T1 = 373.15 K

−1
T2 = 393.15 K ∆Hvap = 40.66 kJ mol
R = 8.31 J K−1 mol-1
∴ P2 = 2.01 bar

The estimate is based on assumptions 1, 2 and 3.

c. For ice - liquid water equilibrium, use Clapeyron equation

At T1 = 273.15 K, P1 = 1.01 bar

∆H
1. Assume that for a small change in T, is constant.
∆V
Integrating the Clapeyron equation above
∆H T 
P2 − P1 = ln  2 
∆V  T1 
T2 = 272.95 K, ûH(fusion) = 6008 Jmol −1

 1 1  −6 −1
∆V =  −  x 18.015 = − 1.63 x 10 m mol
3

 1.00 0.917 
P2 − P1 = 27.0 bar

P2 = 28.0 bar

The estimate is based on assumption 1.

C. Irreversible condensation

a. On the P-T plane, this equilibrium state is a solid phase (ice). Water in liquid
phase at this temperature and pressure is not an equilibrium state - it is a
supercooled state that does not lie on the given P-T plane.

b. Treating the metastable state as equilibrium state, we can go from the

supercooled liquid state to the solid state at the same temperature and
pressure by a sequence of 3 reversible steps.

1. Supercooled liquid at -12.0°C to liquid at 0°C

q1 = number of moles x Cp (liquid water) x change of temperature

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

28.5g
−1
x 76.1 J K −1 mol −1 x 12.0 K = 1445 J
18.015 g mol

2. liquid at 0°C to ice at 0°C

q2 = 28.5 g x (−333.5) J g−1 = − 9505 J

3. Ice at 0°C to ice at −12.0°C

q3 = number of moles x Cp (liquid water) x change of temp.

28.5
= −1
x 37.15 J K −1 mol −1 x (− 12.0 K )
18.015 g mol

= − 705.3 J

∴ q = q1 + q2 + q3 = − 8765 J

Since all the steps are at the constant pressure of 1.00 bar,
q = ∆H
But ∆H is independent of the path, i.e., it depends only on the end points.
Thus for the irreversible condensation of supercooled liquid to ice

q = ∆H = −8765 J

c. The actual irreversible path between the two end states of the system is
replaced by the sequence of three reversible steps, as above. For each
reversible step, ∆S can be calculated.

T2
Cp T2
∆S1 = n ∫T
T1
dT = n Cp ln
T1

28.5 g 273.15
∆S1 = −1
76.1 J K −1 mol −1 x ln
18.015 g mol 261.15

= 5.41 J K−1

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

∆H2 − 9505
∆S 2 = = = − 34.79 J K −1
T 273.15

28.5 g 261.15
∆S3 = −1
37.15 J K −1 mol −1 ln
18.015 g mol 273.15

= − 2.64 J K−1

∆S system = ∆S1 + ∆S 2 + ∆S 3 = − 32.02 J K −1

qsur 8765
∆S sur = = = 33.56 J K −1
Tsur 261.15

∆Suniv = ∆Ssystem + ∆Ssur = 1.54 J K −1

The entropy of the universe increases in the irreversible process, as expected

by the Second Law of Thermodynamics.

2. van der Waals gases

a. For a van der Waals gas

PV bP na n2 a b
ý = = 1+ − + 2
nR T RT VRT V RT

The ratio of the magnitudes of the second and third terms on the right side is :

b b
PV ≈ RT, taking PV = nRT up to zeroth order.
na a
The ratio of the magnitudes of the fourth and third terms on the right side is :
nb bP
≈
V RT
i. From the ratios above, it follows that at sufficiently high temperature for
any given pressure, the second term dominates the third and fourth
terms. Therefore,
bP
ý ≅ 1+ > 1
RT

For small P, Z nearly equals unity.

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

ii. At lower temperatures, the third term can be greater (in magnitude)
than the second term. It may be greater (in magnitude) than the fourth
term also, provided P is not too large. Since the third term has a
negative sign, this implies that Z can be less than unity.

iii. For a = 0

bP
ý = 1+
RT
which shows that Z increases linearly with P.

b. Helium has negligible value of a. Graph (1) corresponds to He and (2)

corresponds to N2.

c. Above T > Tc, only one phase (the gaseous phase) exists, that is the cubic
equation in V has only one real root. Thus isotherm (2) corresponds to T < Tc .

d. At T = Tc , the three roots coincide at V = Vc This is an inflexion point.

dP d2P
= = 0
dV V dV 2 V
c c

The first condition gives

RTc 2na
= (1)
(Vc − nb) 2
Vc
3

The second condition gives

RTc 3na
= (2)
(Vc − n b) 3
Vc
4

These equations give

8a
Vc = 3 n b and Tc =
27b R
For He, Tc = 5.2 K

For N2, TC = 128K

Since, Tc (N2) is greater than Tc (He), N2 is liquefied more readily than He.

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 33rd International Chemistry Olympiad ∗ Preparatory Problems
V2
e.
W = ∫ P dV
V1

V2

RT a 
= ∫ − 2  dV
V 
V −b V 
1

 V −b  1 1
= RT ln  2  + a  − 
 V1 − b   V2 V1 
= 56.7 L bar mol − 1

3. Rates and reaction mechanisms

a. Mechanism 1 :

1 d [H I]
= k1 [I] 2 [H2 ]
2 dt
Since the first step is fast, there is a pre - equilibriu m :
[I] 2
K =
[I2 ]
d[HI]
∴ = 2 k1 K [I2 ] [H2 ] = k [H2 ] [I2 ]
dt

Mechanism 2 :

1 d [HI]
= k 2 [I2 ]d [H2 ]
2 dt
[I ]
K' = 2 d
[I2 ]
d [HI]
∴ = 2 k2 K' [I2 ] [H2 ] = k [H2 ] [I2 ]
dt

Both mechanisms are consistent with the observed rate law.

− Ea
b. i. k = Ae RT

1 1 k
E a  −  = R ln 2
 T1 T2  k1
With the given numerical values,

E a = 170 kJ mol − 1

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

ii. The activation energy is greater than the bond dissociation energy of
I2. Hence the second step is rate determining in both the mechanisms.

c. The activation energy Ea’ for the reverse reaction is

E'a = Ea − û8

= 170 + 8.2 = 178.2 kJ mol − 1

d. i.
d [I2 ]
= k 3 [IAr] [I]
dt
[IAr][Ar]
K' ' =
[I][Ar]2
d [I2 ]
∴ = K ' ' k 3 [I]2 [Ar]
dt
= k [I]2 [Ar]

ii. A possible reason why this is negative is that Ea 3 is positive and less in
magnitude than ∆H°, while ∆Ho is negative.

k = k 3K ' '
− û*
°
−
E a3
= A 3e RT
e RT

we know û G ° = û þ° − T û S°
û6 ° (Ea3 + û þ° )
−
∴ k = A3 e R
e RT

The activation energy for the overall reaction is E a3 + û þ°

4. Enzyme catalysis

a. i. The differential rate equations for the Michaelis-Menten mechanism are

d [ES]
= k1 [E] [S] - k1' [ES] − k 2 [ES] (1)
dt
d[P]
= k 2 [ES] (2)
dt

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

In the steady-state approximation, d[ES]

= 0 (3)
dt
Eq. (1) then gives [ES] = k1 [E] [S] (4)
k1' + k 2
Now [E] = [E] + [ES] (5)
0

where [E]0 is the total enzyme concentration. Eqs. (4) and (5) gives

[E]0 [S]
[ES] = (6)
K m + [S]
k 1' +k 2
where K = is the Michaelis-Menten constant.
m k1

d[P] k 2 [E]0 [S]

From eq. (2), = (7)
dt K m + [S]

Since the backward rate is ignored, our analysis applies to the initial rate of
formation of P and not close to equilibrium. Further, since the enzyme
concentration is generally much smaller than the substrate concentration, [S]
is nearly equal to [S]0 in the initial stage of the reaction.

Thus, according to the Michaelis-Menten mechanism, the initial rate versus

substrate concentration is described by eq. (7), where [S] is replaced by [S]0.

For [S] << Km,

k2
Initial rate = [E]o [S] (8)
Km
i.e., initial rate varies linearly with [S].

For [S] >> Km,

Initial rate = k2 [E]0 (9)

i.e., for large substrate concentration, initial rate approaches a constant

value k2 [E]0.

Thus the indicated features of the graph are consistent with Michaelis-Menten
mechanism.

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

ii. The asymptotic value of initial rate is k2 [E]0

From the graph,

k2 [E]0 = 3.0 x 10-6 M s−1

With [E]0 = 1.5 x 10−9 M

we get k2 = 2.0 x 103 s−1

iii. From eq. (7), for [S] = Km, the initial rate is half the asymptotic value.
From the graph, therefore,

Km = 5.0 x 10−5 M

For [S] = 1.0 x 10−4 M, using eq. (7) again,

[2.0 x 103 s−1] x [1.5 x 10−9 M] x [1.0 x 10 −4 ]M

Initial rate =
[5.0 x 10− 5 ] M + [1.0 x 10 − 4 ] M

= 2.0 x 10 −6 M s−1

k1| +k 2
iv. We have Km = = 5.0 x 10−5 M
k1

The enzyme equilibrates with the substrate quickly, that is the first step
|
of equilibration between E, S and [ES] is very fast. This means that k1
is much greater than k2. Therefore, neglecting k2 above,

k1|
= 5.0 x 10 − 5 M
k1
The equilibrium constant K for the formation of ES from E and S is,
K k
= 1| = 2.0 x 10− 5
1M k1

b. From the graph at the new temperature, k2 [E]0 = 6.0 x 10−6 M s−1

6.0 x 10−6 M s −1
i.e., k2 = = 4.0 x 103 s−1
1.5 x 10− 9 M

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Using Arrhenius relation for temperature dependence of rate constant :

E
− a
k = A e RT (10)

where Ea is the molar activation energy.

Ea  1 1 
−  − 
k(T1 ) R  T1 T2 
= e
k(T2 )

k(T2 )
ln
k(T1 )
i.e. Ea = R (11)
1 1
 − 
 T1 T2 
k 2 (310)
Now = 2.0 , R = 8.31 J K−1 mol−1
k1(285)

∴ Ea = 20.4 kJ mol−1

c. i. The fraction of the enzyme that binds with the substrate is, from eq.
(6):
[ES] [S] (12)
=
[E]0 K m + [S]
where [S] is nearly equal to [S]0 in the initial stage of the reaction.

3.0 x 10 −6 mol
Now [S]0 = = 3.0 x 10 − 3 M
1 x 10− 3 L
and Km = 5.0 x 10−5 M

[ES] 3.0 x 10−3 M

∴ = = 0.98
[E]0 (5.0 x 10 −5 + 3.0 x 10 − 3 )M

Nearly the whole of the enzyme is bound with the substrate.

ii. From eq. (7),

Integrating the equation gives,

d[S] k 2 [E]0 [S]

= −
dt K m + [S]

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 33rd International Chemistry Olympiad ∗ Preparatory Problems
[S]
K m ln + [S] − [S]0 = − k 2 [E]0 t (13)
[S]0
If at t = T, [S] = 1/2[S]0,

1
T k 2 [E]0 = K m ln 2 + [S]0 (14)
2
2.0 x 10 −12 mol
Here [E]0 = = 2.0 x 10 −9 M
1.0 x 10− 3 L
k2 = 2.0 x 103 s−1, Km = 5.0 x 10−5 M,

[S]0 = 3.0 x 10−3 M

Substituting these values in eq. (14) gives

T = 384 s

Thus 50% of the antibiotic dose is inactivated in 384 s.

d. i. The differential rate equations for the situation are :

d
[ES] = k1 [E] [S] − k|1 [ES] − k 2 [ES ] (15)
dt

d
[EI] = k 3 [E] [I] − k |3 [EI] (16)
dt

d
[P] = k 2 [ES] (17)
dt

|
where k3 and k 3 are the forward and backward rate constants for the
enzyme-inhibitor reaction.

Applying steady-state approximation to [ES] and [EI],

k1 [E] [S] (18)
[ES] =
k |1 + k 2

k 3 [E] [I]
and [EI] = (19)
k|3
Now [E]0 = [E] + [ES] + [EI] (20)

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Eliminating [E] and [EI] from eqs. (18) to (20) gives :

[E]0 [S]
[ES] = (21)
 [I] 
[S] + K m  1 + 
 K I (1M) 

d[P] k 2 [E]0 [S]

= (22)
dt  [I] 
[S] + K m  1 + 
 K I (1M) 

k |3
Here, K I (1M) = is the equilibrium constant for the dissociation of EI
k3
to E and I.

r
The degree of inhibition is i = 1−
r0

Km [I]
KI (1M)
Using eq. (22), i = (23)
 [I] 
[S] + K m 1 + 
 K I (1M) 

For fixed [I], i decreases with increase in [S] (competitive inhibition).

and for large [S], i → 0, i.e., the inhibitor ceases to play any role.

[I]
ii. For small [S] i =
KI (1M) + [I]

1 3
If r = r0, i =
4 4

i.e., [I] = 3 KI x (1M) = 1.5 x 10−4 M

The inhibitor concentration required to reduce the rate of inactivation by

a factor of 4 is 1.5 x 10−4 M; i.e., 0.15 µmol in a volume of 1.00 mL.

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

5. Schrödinger equation

a.
i. One-dimensional Schrödinger equation for a free particle of mass m:

!2 d2%
= E%
h
− !=
2m dx 2 2Œ

where E stands for the energy of the particle and ψ its wave function.

ii. The boundary conditions are :

ψ (0) = ψ(L) = 0
nΠx
Only %n (x) = sin satisfies the required boundary conditions.
L

Other functions are not possible wave functions of the electron in a

one-dimensional rigid box.

iii.
! 2 d2 nŒx ! 2Œ 2 2 nŒ x
− sin = n sin
2m dx 2 L 2mL2 L

! 2Π2 2 h2n2
∴ En = n =
2mL2 8mL2

iv. Ground state (n = 1)

ψ 1(x)
%1 (x) = sin
Œx 0 L
L x
First excited state (n = 2) ψ 2(x)

%2 (x) = sin 2 Πx
0 L
x
L/2
L ψ 3(x) x
Second excited state (n = 3) 0 L
L/3 2L/3
3Œx
%3 (x) = sin
L
Number of nodes in %n = n −1, apart from the nodes at the end
points.

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v.

% 1N (x) = N sin
Œ[
L
∞ 2

∫%
N
1 = 1
(x) dx
−∞
L
Œ[ N2
L
 2Œx
= N2 ∫ sin ∫  1 − cos
2
dx =  dx
L 2 L 
0 0
L
= N2
2
2
∴ N = ( N is chosen to be real )
L

% 1N (x) =
2
sin
Œ[
L L

b. In the example

L = 5 × 1.4 × 10−10 m = 7.0 × 10−10 m

The first three energy levels are:

h2
E1 = = 1.22 × 10 −19 J
8mL2

E2 = 4 E1 = 4.88 × 10 −19 J

E3 = 9 E1 = 10.98 × 10 −19 J

In the ground state, the four electrons will occupy the levels E1 and E2, each
with two electrons.
E3 E3

E2 E2

E1 E1

Ground state Lowest excited state

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

The lowest excitation energy

E3 – E2 = 6.10 × 10 –19 J

c. The condition that ψ(φ) is single valued demands that

% (φ) = % (φ + 2π)
eiλφ = eiλ(φ+2π)

ei 2πλ =1

i.e. λ =m, where m = 0, ±1, ±2, ±3,…….

This shows that angular momentum projection (Lz) cannot be an arbitrary real
number but can have only discrete values: m!, where m is a positive or
negative integer (including zero).

6. Atomic and molecular orbitals

A. Atomic orbitals

a. r
−
i.
% N
1s = Ne ao

∫ % 1s dv = 4 Œ a 3o N 2
2
1 = N

a 3o
= 4 ΠN2 x = Πa 3o N 2 (N chosen to be real)
4

[ŒD ]
1
3 −2
∴ N = o
r

[Π]
1 −
% N
1s =
−
a 3o 2 e ao

ii. Probability of finding an electron between r and r + dr

2r

[ŒD ]
−
3 −1
= 4Πr
2 a0
x 0 e dr

This is a maximum at r = rmax , given by

 −
2r

d  r 2 e a0  = 0
dr  
  r =rmax
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This gives
rmax = a0

The 1s electron is most likely to be found in the neighborhood of r = a0.

b. % 2s =0 at r = 2a0

Nodal surface is a sphere of radius 2a0

Œ
%2p z = 0 at  =
2

Nodal surface is the xy plane.

 1 
%3d = 0 at 3cos2 − 1 = 0, i.e.,  = cos−1  ± 
z2  3

Nodal surfaces are cones with these values of half-angle, one above the xy
plane and the other below it.

(Note: all three wave functions vanish as r → ∞. At r = 0, ψls does not vanish,
but the other two wave functions vanish.)

c. Each electron in n = 1 shell of helium atom has energy − Z2eff × 13.6 eV

Helium ground state energy = − Z2eff × 27.2 eV

Energy of He+ ground state = − 4 × 13.6 = − 54.4 eV

Ionization energy = (− 54.4 + Z2eff × 27.2) eV = 24.46 eV

This gives Zeff = 1.70

B. Molecular orbitals

a. %1 and % 2 are bonding orbitals

~ and %
% ~ are antibonding orbitals
1 2

Bonding orbital
No nodal surface between the nuclei. Electronic energy has a minimum at a
certain internuclear distance. Qualitative reason: electron has considerable
probability of being between the nuclei and thus has attractive potential
energy due to both the nuclei.

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 33rd International Chemistry Olympiad ∗ Preparatory Problems

Antibonding orbital
Nodal surface between the nuclei. Electronic energy decreases monotonically
with internuclear distance. Hence bound state is not possible.

b. Re = 1.32 × 10−10 m
D = −1.36 – (−15.36) = 1.76 eV

c. It will dissociate to a hydrogen atom in 2s state and a bare hydrogen nucleus

(proton).

d. The two electrons occupy the same molecular orbital with the lowest energy.
By Pauli’s principle, their spins must be antiparallel. Hence the total electronic
spin is zero.

e. In the first excited state of H2, one electron is in ψ1 (bonding orbital) and the
other in ψ1 (antibonding orbital). It will dissociate into two hydrogen atoms.

f. Using the aufbau principle, in the ground state two electrons of He2 are in ψ1
(bonding orbital) and two in ψ1 (antibonding orbital). The bond order is
½ (2 −2) = 0
Therefore, bound He2 is unstable and difficult to detect. However, if one or
more electrons are elevated from the antibonding orbital to (higher energy)
bonding orbitals, the bond order becomes greater than zero. This is why it is
possible to observe He2 in excited states.

7. Fission

a.
235
92 U + n → 94
38 Sr + 140
54 Xe + 2n

235
92 U + n → 141
56 Ba + 92
36 Kr + 3n

b. The net nuclear reaction is

235
92 U + n → 94
40 Zr + 140
58 Ce + 2n + 6e − + (Q)

The energy released is

Q = [m N ( 235 U) − m N ( 94 Zr) − m N ( 140 Ce) − m n − 6m e ] c 2

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