Raffles Junior College

H2 Chemistry 2010/2011
Tutorial 5b Chemical Energetics II
Mrs Jeannie Tan / Mr Eric Gwee

1. Self-Check
a) Define what is meant by
(i)
entropy
(ii)
Gibbs free energy change of reaction (using the equation: G H = TS)
b) State whether each of the terms above are positive or negative for a spontaneous reaction.
c) Attempt the following TYS questions:
(i)

N02/III/16 [Explaining spontaneity using entropy/free energy]

(ii)

N02/III/15 [Gibbs free energy calculation]

(iii)

N04/III/16 (ai,ii) [Gibbs free energy calculation]

(iv)

Modified from N05/III/15 [Gibbs free energy calculation & application]

D-glucose exists in 2 forms, the -form which has an optical rotation of +113.4o and
the -form which has an optical rotation of +19.0o. The two forms exist in equilibrium
in aqueous solution.
-glucose (aq)

2.

3.

-glucose (aq)

a)

Given that the optical rotation of an aqueous solution of glucose was found to
be +52.2o, show that the mixture contains 35.2% of the -form.
[2]

b)

Given that Ho = 2.10 kJ mol 1 and Go = 1.51 kJ mol 1, calculate the value of
So of the conversion at 298K.
[2]

c)

Based on the values for Ho, So or Go, deduce whether -glucose is more or
less extensively hydrated in the aqueous solution than the -form.
[2]

For each of the following processes, state, giving a reason in each case, whether the
change in entropy of the system is positive or negative.
Assume that the temperature is 298 K and the pressure is 1 atm unless otherwise stated.
a)

H2O (l) at 298 K H2O (l) at 308 K

b)

H2O (s) at 273 K H2O (l) at 273 K

c)

Cl2 (g) 2Cl (g)

d)

Na+ (g) + Cl (g) NaCl (s)

e)

1 mole of Ar (g) is pumped into a sealed vessel of volume 48 dm3 containing 1 mole
of Ne (g) at r.t.p.

Use the standard entropies given, calculate the entropy change, S, for the reaction below:
N2 (g) + 3 H2 (g)
2 NH3 (g)
Substance
S / J mol-1 K-1
o

H2 (g)
130.6

N2 (g)
191.5

NH3 (g)
192.5

-1

-1

[Ans: 198.3 J mol K ]

1

4.

Given the following data for the reaction:

Substance
o

-1

S / J mol K

CaCO3 (s)
-1

CaO (s)

92.9

39.7

CaCO3 (s)

CaO (s) + CO2 (g)

CO2 (g)

Temperature/K
-1

J mol K

213.6

a) Calculate the entropy change in the system,

-1

300

1200

593

148

, for the above reaction.

b) Predict whether the decomposition of CaCO3 is feasible at the following temperatures.

(i)
300 K
(ii)
1200 K
[Ans: .
= +160 J mol-1 K-1]
5.

The reaction NH3 (g) + HCl (g)

NH4Cl (s) proceeds spontaneously at 25 C even
though there is a decrease in disorder in the system (gases converted to a solid). Explain.
Substance
S / J mol-1 K-1
/ kJ mol-1
o

6.

Substance

NH3 (g)
192.5

HCl (g)
186.7

NH4Cl (s)
94.6

-46.2

-92.3

-314.4

MgCO3 (s)

MgO (s)

CO2 (g)

1012

569

394

/ kJ mol-1
a)

Use the standard

reaction below:

given above, calculate the free energy change,

MgCO3 (s)

MgO (s) +

, for the

CO2 (g)

Will the above reaction take place spontaneously?

b)

Given that the

of the above reaction is +101 kJ mol-1, and the So for the
reaction is +159 J mol-1 K-1, estimate the temperature at which the reaction will take
place spontaneously.
-1

[Ans: +49 kJ mol , T = 635 K or 362 C]

7.

Vaporization and transport of tungsten normally limit the life of the tungsten filament lamp.
The quartz-iodine lamp contains small quantities of iodine which react with deposited
tungsten:
W (s) + I2 (g)
WI2 (g) (on quartz envelope)
The WI2 vapour then decomposes and deposits tungsten on the filament. The iodine is
then liberated for further scavenging.
a) Find Go for the above equation at 350oC, the normal temperature of the quartz
envelope. Assume that H and S are independent of temperature.
b) Hence, find the minimum temperature of the filament at which WI2 will decompose.
Substance
S / J mol-1 K-1
/ kJ mol-1
o

W (s)
33.50

I2 (g)
260.60

WI2 (g)
251.00

62.43

8.37
-1

[Ans: G623K = 43.9 kJ mol , T = 1643 K]

8.

A dissociation reaction is given as follows:

PCl5 (g)

PCl3 (g) + Cl2 (g)

At 472 K, G = +5.77 kJ mol , but at 524 K, it has changed to 4.31 kJ mol-1.

o

a)
b)

-1

Calculate the value of S. Assume that H and S are independent of temperature.

Do you expect Go to become more exergonic at a higher temperature?
-1

-1

[Ans: S = +194 J mol K ]

9. Give explanations as to whether the following reactions are feasible:

a)

X (s) Y (s) + Z (g)

Ho = +250 kJ mol 1

b)

2 X (g) + Y (g) 2 Z (g)

Ho = 100 kJ mol 1

c)

X (l) Y (l) + Z (g)

Ho = 200 kJ mol 1

d)

2 X (s) + 2 Y (g) Z (g)

Ho = +50 kJ mol 1

10. Challenging
For each of the following reactions described below,
(i) Write an equation.
(ii) Explain, by considering the changes in enthalpy (H) and entropy (Ssys), why the reaction
is spontaneous under standard conditions.
a)

The decomposition of solid nitrogen triiodide, NI3 to produce N2(g) and purple
vapour is highly exothermic and explosive.

b)

The solution cools down when ammonium nitrate crystals are dissolved in water.

c)

When ammonium thiocyanate crystals, NH4SCN(s) and hydrated barium hydroxide,

Ba(OH)210H2O is mixed, a cold colourless solution is formed and a pungent gas
can be detected.

Suggested Solutions to Tutorial 5b : Chemical Energetics II

1. Self-Check
a) (i) Entropy is a measure of the randomness or disorder of matter and energy of a
system.
(ii) Gibbs free energy change of reaction is the difference between enthalpy change of
the reaction (H) and the product of the temperature (in Kelvins) and the change in
entropy of the system (TS).
b) For a spontaneous reaction, Suniv
c)(i)

> 0 and G < 0

TYS questions: N02/III/16 [Explaining spontaneity using entropy/free energy]

(a) At 273 K, ice and water are in equilibrium and the process of ice melting into
water is reversible. So Go = 0
Hence So = Ho/T = 6000/273 = 21.98 J mol 1 K 1

At 298 K, using Go = Ho TSo

Go = 6000 (298)(21.98) = 0.55 kJ mol 1

Since Go < 0 (negative), ice spontaneously changes into water at 298 K.

(b) Using Gmixo = Hmixo TSmixo expression.
The entropy change of mixing, Smixo, is always positive, ie. the process is
favourable. However, as the hydrocarbon chain of the alcohol molecule gets
longer, more hydrogen bonds between water molecules (and also more van der
Waals interactions between hydrocarbon chains of the alcohol) have to be
broken, in order to form a solution. This bond breaking is an endothermic
process, and the H value will increase with increasing hydrocarbon chain. It
will come to a point when H value is more positive than the TS term, so that
now G becomes effectively a positive value. Hence, the mixing process will
become not feasible. Thus ethanol and water mix in all proportions, but butan1-ol and water have only a limited solubility.
(c) The conversion of many small glucose molecules into one large polysaccharide,
like starch molecule, brings about a negative entropy change because there is
now more orderliness with a decrease in the number of moles of molecules.
This polymerization is accompanied by only a small enthalpy change since
approximately the same number of OH bonds are being broken and formed at
the same time.
Since G = H TS, we can see that such a polymerization reaction will bring
about a small negative, if not a positive G value. A positive G value will
mean Stot being negative (since G = TStot). This implies that the process
may not be energetically feasible and is not spontaneous.

However, such polymerization still takes place, so this goes to show that the
decrease in entropy during polymerization must be accompanied by processes
which increase the entropy elsewhere. In other words, the released free
energies of other processes in the biological system (G < 0, so Stot > 0), such
as that of the conversion of ATP to ADP, helps to drive the process of
polymerization. This occurs during *photosynthesis or glycolysis. Hence, there
is no contradiction of the Second Law of Thermodynamics.
* In photosynthesis, ATP is produced in the light-dependent cycle and ATP is being used in the
light-independent stage (Calvin cycle) to build up large polysaccharide molecules from smaller
glucose molecules. In glycolysis, glucose is broken down to generate some ATP, and the
products of glycolysis undergo further reactions (Kreb cycle) to bring about more ATP
production. These ATPs can now be used to drive other non-spontaneous reactions.

c)(ii)

TYS questions: N02/III/15 [Gibbs free energy calculation]

(a) (i) C(s) + O2(g) CO(g)
Gfo = Hfo TSfo
137.2 = 110.5 (298) Sfo
Hence, Sfo = [(137.2 110.5) x 1000]/298 = +89.6 J mol 1 K 1

C(s) + O2(g) CO2(g)

Gfo = Hfo TSfo
394.4 = 393.5 (298) Sfo
Hence, Sfo = [(394.4 393.5) x 1000]/298 = +3.0 J mol 1 K 1

(ii) The two values calculated were different. This is mainly because there is an
increase in the number of gaseous molecules from reactants to products in
C(s) + O2(g) CO(g) reaction, and hence the S value should be large
and positive, whereas for C(s) + O2(g) CO2(g) reaction, there is no
change in the number of gaseous molecules, and so the expected S is also
near to zero.
(b) C(s) + CO2(g) 2 CO(g)
C(s) + O2(g) CO(g)
2C(s) + O2(g) 2CO(g)

Go = 137.2 kJ mol 1
Go = 2( 137.2) = 274.4 kJ mol 1

C(s) + O2(g) CO2(g)

CO2(g) C(s) + O2(g)

Go = 394.4 kJ mol 1
Go = +394.4 kJ mol 1

Hence, C(s) + CO2(g) 2CO(g)

Go (298K) = 274.4 +394.4 = +120 kJ mol 1

[Or: Go (298K) = 2Gof(CO) Gof(CO2) = +120 kJ mol 1]

Since Go (298K) is positive, the above reaction is not feasible at 298 K.

Now, using Hess law, for above reaction,
Hro = 2(110.5) (393.5) = 172.5 kJ mol 1

Now Go = Ho TSo
So So (298K) = (Ho (298K) Go (298K) )/298K
= (172.5120)(103)/298 = 176.2 J mol 1 K 1

At 1000 K,
Using
Go = Ho TSo
Go (1000K)
= (172.5 x 103) (1000)(176.2)
= 3.7 kJ mol 1

Since now Go (1000K) is negative, the reaction has now become feasible.
[Assumption:
Ho and So remain constant over temperature range from 298 K to 1000 K.]
c)(iii) TYS questions: N04/III/16 (ai,ii) [Gibbs free energy calculation]
(a) (i) Ho = (+9.2) 2(+33.2) = 57.2 kJ mol 1
So = 304 2(240) = 176 J mol 1 K 1

(ii) N-N bond formation is exothermic (Ho <0)

Two moles of gas reacted to form only one mole of gas. Hence, entropy of
system decreases as the number of particles decreases (So <0)
c)(iv) TYS questions: Modified from N05/III/15
[Gibbs free energy calculation & application]
a)

Let the % composition of the -form be x%,

% composition of the -form would be (100-x)%
Optical rotation of an aqueous solution = [(+113.4o)x + (+19.0o)(100-x)] /100 =
+52.2o
x = 35.2

b)

The mixture contains 35.2% of the -form.

Go = Ho TSo = 2.10 (298)So = 1.51 kJ mol 1

So = 2.0 J mol 1 K 1

c)

-glucose is more extensively hydrated in the aqueous solution than the form.
Ho < 0 (exothermic) more ion-dipole interactions are formed
So < 0 less disorder (more ordering) in aqueous -glucose. Water
molecules are organized into hydration shells around the glucose molecule in a more orderly manner than that for the
aqueous -form
Go is negative

aqueous -glucose is thermodynamically more stable that

the aqueous -form

2a)

H2O (l) at 298 K H2O (l) at 308 K

S > 0. Substances have higher entropy at higher temperature as there are more packets
of energy available to spread out within the system / particles have more energy to move
around, creating more disorder.

b)

H2O (s) at 273 K H2O (l) at 273 K

S > 0. Liquid has higher entropy than that of solid. Particles of liquid are more randomly
arranged than in solid.

c)

Cl2 (g) 2Cl (g)

S > 0. 2 mole of gases has higher entropy than 1 mole of gas.
There are more ways of arranging the particles in the vessel and there are more collisions,
leading to the distribution of energies.

d)

Na+ (g) + Cl (g) NaCl (s)

S < 0. Gaseous ions crystallize to form orderly solid NaCl resulting in a decrease in
entropy of the system. A solid has much lower entropy than a gas.

e)

1 mole of Ar (g) is pumped into a sealed vessel of volume 48 dm3 containing 1 mole of
Ne (g) at r.t.p.

S > 0. As Ar (g) expands to occupy the entire containing vessel, mixing of the two gases
occur, there is an increase in the disorder and hence entropy of the system. The two gases
mix completely and spontaneously.
= 2(192.5) [3(130.6) + 191.5] = 198.3 J mol-1 K-1

3.
4. a)

= (39.7 + 213.6) 92.9 = +160.4 J mol-1 K-1

b)(i)

At 300 K,
Souniv = Sosys + Sosurr = +160.4 593 = 433 J mol-1 K-1
Because Souniv < 0, reaction is not feasible at 300 K.

(ii)

At 1200 K,
Souniv = Sosys + Sosurr = +160.4 148 = 12.1 J mol-1 K-1
Because Souniv > 0, reaction is feasible at 1200 K.
Hence, we have to heat CaCO3 (s) to a high temperature to make it decompose.

5. Sosys = 94.6 (192.5 + 186.7) = 284.6 J mol-1 K-1

(Decrease in entropy of system as gases are converted to a solid.)
Using Hess law, Hor = (314.4) [(46.2) + (92.3)] = 175.9 kJ mol-1
Go = Ho TSo = (175.9) 298 (284.6/1000) = 91.1 kJ mol-1
Go < 0, there is an increase in entropy in the universe, even though it shows a decrease in
entropy of the system, hence the reaction is spontaneous, predicted by the 2nd Law of
Thermodynamics.
6

a)

Sum of

of reactants = 1012 kJ mol-1

Sum of

of products = 569 + (394) = 963 kJ mol-1

So, free energy change,

b)

= 963 (1012) = +49 kJ mol-1

The reaction will not take place spontaneously because

>0
Applying G = H TS
For reaction to be spontaneous, G = H TS = 101 T(0.159)< 0 101< T(0.159).
7


So a temperature of above 635 K or 3620C is needed for the reaction to take place.
(Here, we assume that H and S do not change with temperature.)
7

a)
K-1

b)

Decomposition of WI2 is the reverse reaction so that G > 0.

a)
At 472 K,
At 524 K,
Assuming Ho is constant, So =
b) Change is expected since Ho>0 and So > 0 so that Go = Ho TSo become more
negative as T increases. (or So expected to be positive since reaction results in
greater number of gaseous molecules formed).

9. a) X (s) Y (s) + Z (g)

Ho = +250 kJ mol 1
So >0
This endothermic reaction is thermodynamically feasible when T > H / S

b) 2 X (g) + Y (g) 2 Z (g)

Ho = 100 kJ mol 1
So <0
This exothermic reaction is thermodynamically feasible when T < H / S

c) X (l) Y (l) + Z (g)

Ho = 200 kJ mol 1
Reaction is feasible. (G < 0 for all temperatures)

So >0

d) 2 X (s) + 2 Y (g) Z (g)

Ho = +50 kJ mol 1
Reaction is not feasible. (G > 0 for all temperatures)

So <0

10. a)

2 NI3 (s) N2 (g) + 3 I2 (g)

H < 0

S > 0. As 4 moles of gases are produced, there is a very large increase in entropy of the system.
This reaction is also exothermic (formation of NN bond). Hence, highly explosive!
b)

NH4NO3 (s) NH4 (aq) + NO3 (aq)

H > 0

S > 0. Aqueous ions are formed from ions held fixed in an orderly crystalline lattice, resulting in a
large increase in entropy of the system. Even though the reaction is endothermic, the increase in
entropy compensates for endothermic H so that G = HTS < 0 even under standard conditions
and NH4NO3 dissolves readily under standard conditions.
c)

2 NH4SCN (s) + Ba(OH)210H2O (s) 2 NH3 (g) + 12 H2O (l) + Ba(SCN)2 (aq) H > 0
S > 0. Increase in disorder as water of crystalisation is lost and more particles are formed after the
reaction. Some of the solid reactants also dissolves to form aqueous solutions. Even though H >
0, the increase in entropy compensates for endothermic H so that G < 0.