SAMPLE PROBLEMS ON GIBBS FREE ENERGY

PROBLEM #1

Calculate delta H and delta S for the following reaction and decide in which direction each of these
factors will drive the reaction.

N2(g) + 3 H2(g) → 2 NH3(g)

Solution:

Using a standard-state enthalpy of formation and absolute entropy data table, we find the following
information:

Compound ∆H f ⁰(kJ/mol) S⁰(J/mol-K)

N2(g) 0 191.61

H2(g) 0 130.68

NH3(g) -46.11 192.45

The reaction is exothermic (∆H < 0), which means that the enthalpy of reaction favors the products of
the reaction:

∆H⁰ = ∑Hf⁰ (products) – ∑Hf⁰ (reactants)

= [2 mol NH3 x 46.11 kJ/mol] - [1 mol N2 x 0 kJ/mol + 3 mol H2 x 0 kJ/mol]

= -92.22 kJ

The entropy of reaction is unfavorable, however, because there is a significant increase in the order of
the system, when N2 and H2 combine to form NH3.

∆S⁰ = ∑S⁰ (products) – ∑S⁰ (reactants)

= [2 mol NH3 x 192.45 J/mol-K] - [1 mol N2 x 191.61 J/mol-K + 3 mol H2 x 130.68 J/mol-K]

= -198.75 J/K

PROBLEM #2

Calculate ∆H and ∆S for the following reaction:

NH4NO3(s) + H2O(l) → NH4+ (aq) + NO3- (aq)

Solution

Using a standard-state enthalpy of formation and absolute entropy data table, we find the following
information:
Compound ∆Hf⁰ (kJ/mol) S(J/mol-K)

NH4NO3(s) -365.56 151.08

NH4+ (aq) -132.51 113.4

NO3- (aq) -205.0 146.4

This reaction is endothermic, and the enthalpy of reaction is therefore unfavorable:

∆H⁰ = ∑Hf⁰ (products) - ∑Hf⁰ (reactants)

= [1 mol NH4 x 132.51 kJ/mol + 1 mol NO3- x -205.0 kJ/mol] - [1 mol NH4NO3 x -365.56 kJ/mol]

= 28.05 kJ

The reaction leads to a significant increase in the disorder of the system, however, and is therefore
favored by the entropy of reaction:

∆S⁰ = ∑S⁰ (products) - ∑S⁰(reactants)

= [1 mol NH4 x 113.4 J/mol-K + 1 mol NO3- x 146.4 J/mol-K] - [1 mol NH4NO3 x 151.08 J/mol-K]

= 108.7 J/K

To decide whether NH4NO3 should dissolve in water at 25o C we have to compare the ∆H⁰ and T∆S⁰ to
see which is larger. Before we can do this, we have to convert the temperature from ⁰C to kelvin:

TK = 25⁰C + 273.15 = 298.15 K

We also have to recognize that the units of ∆H⁰ for this reaction are kilojoules and the units of ∆S⁰ are
joules per kelvin. At some point in this calculation, we therefore have to convert these quantities to a
consistent set of units. Perhaps the easiest way of doing this is to convert ∆H⁰ to joules. We then
multiply the entropy term by the absolute temperature and subtract this quantity from the enthalpy
term:

∆G⁰ = ∆H⁰ - T∆S⁰

= 28,050 J - (298.15 K x 108.7 J/K)

= 28,050 J - 32,410 J

= -4360 J

At 25⁰C, the standard-state free energy for this reaction is negative because the entropy term at this
temperature is larger than the enthalpy term:

∆G⁰= -4.4 kJ

The reaction is therefore spontaneous at room temperature.

PROBLEM #3

Use the values of ∆H and ∆S calculated in Problem #1 to predict whether the following reaction is
spontaneous at 25⁰C:

N2(g) + 3 H2(g) → 2 NH3(g)

Solution

According to Problem #1, this reaction is favored by enthalpy but not by entropy:

∆H⁰ = -92.22 kJ (favorable)

∆S⁰ = -198.75 J/K (unfavorable)

Before we can compare these terms to see which is larger, we have to incorporate in our calculation the
temperature at which the reaction is run:

TK = 25⁰C + 273.15 = 298.15 K

We then multiply the entropy of reaction by the absolute temperature and subtract the T ∆S⁰ term from
the ∆H⁰ term:

∆G⁰ = ∆H⁰ - T ∆S⁰

= -92,220 J - (298.15 K x -198.75 J/K)

= -92,220 J + 59,260 J

= -32,960 J

∆G⁰ = -32.96 kJ

According to this calculation, the reaction should be spontaneous at 25⁰C.