Your names________________________________________________________________________________________

December 10, 3002

Problem Set on Thermodynamics
1. Consider the following chemical reaction:
N2(g) + 2 O2(g) → 2NO2(g)

a) Using the tables provided below, calculate the standard enthalpy, standard entropy and standard free energy
change (∆Ho, ∆So, and ∆Go, respectively) for the above reaction at 60 °C:

∆H0 = 2 ∆H0f(NO2(g))-( ∆H0f(N2(g)) + 2∆H0f(O2(g)) = 2 x 33.84-2 x 0 – 2 x 0 = 67.68 kJ/mol

∆S0 = 2 S0(NO2(g))-( S0(N2(g)) + 2S0(O2(g)) = 2 x 240.45 – 191.50-2 x 205.0 =-120.5 J/mol-K
∆G0 = ∆H0 - T ∆S0 = 67.68 - 333 (-0.1205) = 107.807 kJ/mol

Note that both ∆H0 and ∆S0 are unfavorable. This reaction is non-spontaneous at any temperature, under standard
conditions.

b) Calculate the equilibrium constant for this reaction at 60 oC.

∆G0 = -RT lnK; K = e-∆G0/RT= e-107807/8.31x333 = 1.2 x 10-17

very small number- equilibrium favors reactants

c) Will an increase in temperature produce an increase or decrease in the mole fraction of NO2(g) at equilibrium?
Explain.

The reaction is endothermic (∆H0<0); increasing temperature will favor formation of products

d) At what temperature if any will this reaction have an equilibrium constant equal to 1? You may assume that
∆H° and ∆S° are temperature-independent.

K = 1 occurs when ∆G° = 0; therefore, ∆H° - T∆S° = 0, or T = ∆H° / ∆S° = 67680/(-120.5) = -561.66 K , which physically
means that there is no temperature at which K can be equal to 1.

In other words, both the enthalpic and entropic terms are unfavorable (endothermic reaction with negative entropy change-
always non spontaneous at standard conditions).
Your names________________________________________________________________________________________

2. Is it possible for ∆Ho and ∆H to have different signs for a given reaction? Explain. Would the same be
possible for ∆Go and ∆G? Explain.

∆Ho and ∆H cannot have different signs for the same reaction: they reflect energy of chemical bonds. Exo- or
endo- thermicity is associated with a particular reaction rather than with a set of conditions.

3. The reaction
N2(g) + 3H2 (g)
2NH3 (g)
is spontaneous at room temperature but becomes nonspontaneous at much higher temperatures. From this fact
alone, obtain the signs of ∆Ho and ∆So, assuming that ∆Ho and ∆So do not change with temperature. Explain your
reasoning.

The contribution of the entropy term is higher at higher temperatures, and the fact that the reaction becomes
nonspontaneous at higher temperatures means that ∆So<0. Reaction was spontaneous at lower temperatures,
meaning that ∆Ho <0 favoring the spontaneity. Therefore, ∆Ho <0 and ∆So<0

Appendix 1. Thermodynamic quantities for selected substances at 298.15 K (25 oC)

Substance ∆Hof ∆Gof So

(kJ/mol) (kJ/mol) (J/mol-K)
Carbon
C(s, graphite) 0 0 5.69
CO(g) -110.5 -137.2 197.9
CH3OH(l) -238.6 -166.23 126.8
CH3COOH(l) -487.0 -392.4 159.8
Hydrogen
H(g) 217.94 203.26 114.60
H2(g) 0 0 130.58
Nitrogen
N2(g) 0 0 191.50
N(g) 472.7 455.5 153.3
NO(g) 90.37 86.71 210.62
NO2(g) 33.84 51.84 240.45
N2O(g) 81.6 103.59 220.0
Oxygen
O2(g) 0 0 205.0
O(g) 247.5 230.1 161.0
H2O(l) -285.83 -237.13 69.91
H2O(g) -241.82 -228.57 188.83