Determine Entropy changes in chemical reactions.

The standard entropy changes ∆ S ° in chemical reactions can be

determined from the tabulated S° values for the reactants and products at 298 K.
It is similar to the standard change in enthalpy. But there is one important
difference which is that H° and G° for elements are assumed to be zero. S° on
the other hand is not assigned a conventional value of zero. The characteristic
value of the entropy of each element at 25°C and 1 atm pressure is known from
the third law. For example, in the reaction
Fe2O3 (s) + 3H2 (g) → 2Fe (s) + 3H2O (I),
the standard entropy change is given by,
∆ S ° = S°(final) - S°(initial)

Then
ΔS° = 2 S° (Fe, s) + 3 S° (H2O, 1) - S° (Fe2O3, s) - 3 S° (H2, g)
We know the value of standard entropies of Fe, H2O, Fe2O3, & H2 which were
substituted here,
ΔS° = R [2(3.28) + 3(8.4131) - 10.51 - 3(15.7041) J
= -25.82R = -25.82(8.314 J/K mol)
= - 214.7 J/K mol.
Since the entropy of gases is much larger than the entropy of condensed phases,
there is a large decrease in entropy in this reaction; a gas, hydrogen, is
consumed to form condensed materials. Conversely, in reactions in which a gas
is formed at the expense of condensed materials, the entropy will increase
markedly.
Let us take another example,
Cu2O (s) + C(s) → 2 Cu(s) + CO(g)
The standard entropy will be,
∆ S ° (298) = + 158 J/K mol
From the value of ΔS° for a reaction at any particular temperature To, the value
at any other temperature is easily obtained by applying the above discussed
equation,
∆ S ° = S°(products) - S°(reactants)

Differentiating the above equation with respect to temperature with constant

pressure, we have

( ∂ ∆∂TS ° ) =( ∂ S ° ( products
p ∂T
)
) −(
p
∂ S ° ( reactants )
∂T ) p

C°p ( products) C°p (reactants)

=
T
- T
°
∆ Cp
= T

Writing the above equation in differential form and integrating between the
reference temperature To and any other temperature T, we obtain
T T
∆ C op T
∆ C op
∫ d( ∆ S ¿¿ o)=∫ T dT ¿∆ ST =∆ S T +∫ T dT
o o
o
T0 T 0 T 0

which is applicable to any chemical reaction so long as none of the reactants or

products undergoes a change in its state of aggregation in the temperature
interval To to T.
Problem
1. The standard entropies (S°) at 298 K of N 2 (g), H2 (g) and NH3 (g) are
191.6 JK–1 mol–1, 130.5 JK–1 mol–1 and 195.8 JK–1 mol–1, respectively.
The standard heat of formation of NH3 (g) is –46.15 kJ mol–1.
Calculate the standard free energy of formation of NH3 (g).
ΔG° = ΔH° – TΔS°
ΔS° can be calculated from S° data.
1 3
N 2 ( g )+ H 2 ( g ) ⇌ NH 3 (g)
2 2
o 1 o 3 o
ΔS° = S NH (g)− 2 S N ( g )− 2 S H (g)
3 2 2

ΔS° = 195.8 – (95.8 + 1.5 × 130.5)

= -95.8 JK-1 mol-1
ΔG° = -46.5 ×103 – 298(-95.8)
 = -46.15 + 28.55
= -17.6 KJ mol-1
2. Given that the standard molar entropies for H2 (g), Cl2 (g) and
HCl(g) are 130.5 JK–1, 223.01 JK–1 and 186.69 JK–1 respectively and
the standard heat of formation of HCl (g) is –92.3 kJ/mol, calculate
ΔG° for the formation of HCl at 298 K and predict whether the
reaction is spontaneous or not.
∆ S o=So − ( 12 S o
H2
1
+ S oCl
2 2 )
ΔS° = 186.69 – (65.25 + 111.51)
= -9.93 JK-1 mol-1
ΔG° = -92.30 – 298(-9.93 × 103)
= 95.62 kJ mol-1
Hence the reaction is spontaneous at 298 K.
3. The standard entropy change for the formation of HCl (g) is 9.916 J
K–1. Calculate the entropy change for the formation of HCl(g) at 400
K from the following data. The molar heat capacities in J K –1 for
HCl(g), H2 (g) and Cl2 (g) in the temperature interval are given by the
following equations:
Cp of HCl(g) = 28.16 + 1.8 × 10–3T
Cp of H2 (g) = 29.08 – 0.84 × 10–3T
Cp of Cl2 (g) = 31.72 + 10.12 × 10–3T
The formation of HCl(g) from its constituent elements is represented as:
1 1
H ( g )+ Cl 2 ( g ) ⇌ HCl( g)
2 2 2
We know that,
T
∆ C op
+∫
o o
∆ S =∆ S
T 298 dT
298 T
° 1
∆ C p = 28.16 + 0.0018 T - ¿
2
¿−2.24−0.00284
T T
o
∆ S = 9.916 -
T ∫ 2.24 d ln T −¿ ∫ 0.00284 dT ¿
298 298

400
= 9.916 – 2.24 × 2.303 log 298 −0.00284 (400-298)
= 9.916 – 0.66 – 0.29
= 8.96 JK-1