OCC CHM 122 Problem Set Chapter 19 ANSWER KEY

1. Consider a reaction that has positive ΔH and negative ΔS. Comment briefly on spontaneity of this reaction.
Discuss possible effect of temperature on spontaneity.

A reaction is spontaneous if ∆Suniv > 0. Relationship ∆Grxn = −T∆S rxn implies that for a spontaneous
process ∆Grxn<0. ∆G depends on both, ∆H and ∆S, and, in some cases, on temperature. The equation
that describes this relationship is: ∆G = ∆H −T∆S. If a reaction is endothermic (∆H > 0) and the
change in entropy for the reaction is negative, change of Gibbs free energy is positive no matter what
the temperature is, so the reaction is nonspontaneous at all temperatures. Having in mind that absolute
temperature is always positive, a negative ∆S makes the enthalpy factor T∆S negative, and and it actually
turns positive because of negative sign in front of it in the equation ∆G = ∆H −T∆S. Therefore, a positive
∆H and negative ∆S result in a positive ∆G (i.e. the reaction is nonspontaneous) at any temperature.

2[113]. Consider the changes in the distribution of nine particles into three interconnected boxes shown here.
Which has the most negative ΔS? Give brief reasoning.

Entropy is proportional to the number of possible microstates of a system, i.e. the number of
energetically equivalent ways component of a system can be arranged. In a simplified assumption
entropy can be considered as measure of disorder (randomness of arrangement) of the components of
a system. We are looking for the change that decreases the randomness of the components of the
system. Change (b) obviously results in highest rate of decrease in randomness since particles in the
final state are much less dispersed than in the initial state.

OCC CHM 122 PS Ch. 19 ANSWER KEY Professor Miodragovic 1

3. Consider the following chemical equation of reaction occurring at constant P. Use the information here to
determine the value of ΔSsurr at 398 K. Predict whether or not this reaction will be spontaneous at this
temperature.

4 NH3(g) + 3 O2(g) → 2 N2(g) + 6 H2O(g) ΔH = -1267 kJ

A reaction is spontaneous only if ∆Suniv > 0. ∆Suniv = ∆Ssys + ∆Ssurr

We already determined that ∆Ssurr > 0. Let us consider ∆Ssys:
1) All the participants in the reaction are in the same physical state (gaseous), so there is no change in
physical state;
2) On the reactant side of the balanced chemical equation there are 7 moles of gases, and total number
of moles of gases on the product side is 8.
Therefore, the reaction occurs with increasing number of moles of gases, so ∆Ssys > 0.
Since both, ∆Ssurr and ∆Ssys are positive, it follows that ∆Suniv = ∆Ssys + ∆Ssurr > 0 and the reaction is
spontaneous.

4. Place the following in order of increasing molar entropy at 298 K. Give brief reasoning.

CO2 (g) C3H8 (g) CO (g)

Entropy increases with increasing complexity of particles (molecules) of a system. C3H8 is obviously
the most complex molecule among the three listed above, and SO is the simplest one since it is
composed from only two atoms. Therefore, the entropy increases in order:

CO < CO2 < C3H8

5. Given chemical equation below calculate above what temperature the following reaction becomes
nonspontaneous?

2 H2S(g) + 3 O2(g) → 2 SO2(g) + 2 H2O(g) ΔH = -1036 kJ; ΔS = -153.2 J/K

A reaction is spontaneous if ∆Suniv > 0, i.e. ∆Grxn < 0 and nonspontaneous if ∆Grxn > 0. Therefore, a
borderline when a reaction switches between being spontaneous and nonspontaneous is when ∆Grxn = 0
(which characterizes a system in dynamic equilibrium – a reversible process). Temperature at which a
reaction is in equilibrium can be determined by substituting zero for ∆Grxn in the equation
∆G = ∆H −T∆S:
∆H −T∆S = 0 ; solving for T gives:

Please notice that the value for ∆S is previously converted from J/K to kJ/K to enable the units for ∆S and
∆H to be properly cancelled out.

OCC CHM 122 PS Ch. 19 ANSWER KEY Professor Miodragovic 2

6. Place the following in order of decreasing standard molar entropy. Give brief reasoning.

NaCl(s) Na3PO4(aq) NaCl (aq)

NaCl(s) is the most ordered system; it is an ionic solid with a rigid regular arrangement of ions in form
of a crystal lattice, so its particles possess the least freedom of motion and energy is least dispersed.
The other two systems are aqueous solutions and both have much higher entropies than NaCl(s). Both
Na3PO4(aq) and NaCl (aq) are strong electrolytes, i.e. they are completely dissociated in dilute aqueous
solutions. However, Na3PO4(aq) yields much more ions (4 moles of ions per each mole of formula
units) than NaCl(aq) (2 moles of ions per each mole of formula unit); thus, aqueous solution of Na3PO4
more energetically equivalent ways to arrange its components (particles) and, consequently, has higher
entropy than NaCl(aq).
Therefore, standard molar entropy decreases in order Na3PO4 (aq) > NaCl (aq) > NaCl(s)

7. Calculate ΔS°rxn for the reaction presented by the following chemical equation. The S° for each species is
shown below the reaction.

C2H2(g) + H2(g) → C2H4(g)

S°(J/mol∙K) 200.9 130.7 219.3

8. Estimate ΔG°rxn at 387 K for the reaction presented by the following chemical equation.

HCN(g) + 2 H2(g) → CH3NH2(g) ΔH°= -158.0 kJ; ΔS°= -219.9 J/K

9. Calculate the ΔG°rxn using the following information.

4 HNO3(g) + 5 N2H4(l) → 7 N2(g) + 12 H2O(l) ΔG°rxn = ?

ΔG°f (kJ/mol) -73.5 149.3 -237.1

G0 = −3297.7 kJ

OCC CHM 122 PS Ch. 19 ANSWER KEY Professor Miodragovic 3

10. Use Hess's law to calculate ΔG°rxn using the following information.
ClO(g) + O3(g) → Cl(g) + 2 O2(g) ΔG°rxn = ?

(1) 2 O3(g) → 3 O2(g) ΔG°rxn = +489.6 kJ

(2) Cl(g) + O3(g) → ClO(g) + O2(g) ΔG°rxn = -34.5 kJ

Reverse (2) ClO(g) + O2(g) → Cl(g) + O3(g) ΔG°rxn = +34.5 kJ

2
+ (1) 2 O3(g) → 3 O2(g) ΔG°rxn = +489.6 kJ
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ClO(g) + O3(g) → Cl(g) + 2 O2(g) ΔG°rxn = +524.1 kJ

11. Calculate the ΔG°rxn using the following information.

4 HNO3(g) + 5 N2H4(l) → 7 N2(g) + 12 H2O(l) ΔG°rxn = ?

ΔH°f (kJ/mol) -133.9 50.6 -285.8
S°(J/mol∙K) 266.9 121.2 191.6 70.0

Standard molar enthalpies of formation and standard molar entropies as tabulated are related
to T = 298 K. If no other temperature in a problem is specified, it is assumed that temperature is
298 K.

≈ − 3.98 · 103 kJ
12. Calculate ΔGrxn at 298 K under the conditions shown below for the reaction represented by the following
chemical equation:

2 Hg(g) + O2(g) → 2 HgO(s) ΔG° = -180.8 kJ

P(Hg) = 0.025 atm, P(O2) = 0.037 atm

≈ −154 kJ

OCC CHM 122 PS Ch. 19 ANSWER KEY Professor Miodragovic 4

13. What is true if ln K is negative? Give brief reasoning.
A) ΔGorxn is positive and the reaction is spontaneous in the forward direction.
B) ΔGorxn is negative and the reaction is spontaneous in the forward direction.
C) ΔGorxn is negative and the reaction is spontaneous in the reverse direction.
D) ΔGorxn is positive and the reaction is spontaneous in the reverse direction.
E) ΔGorxn is zero and the reaction is at equilibrium.
∆G⁰ = −RTlnK, so if lnK<0 then ∆G⁰ >0 (because both T and Rare always positive). A positive value
of ∆G⁰ means that the direct reaction is nonspontaneous; consequently, the reverse reaction is
spontaneous (∆G⁰reverse rxn < 0).
One can also consider the following: if lnK<0 => K<1 => the reversed reaction is favored, i.e.
spontaneous at standard conditions (for a system in standard state Q=1, so if K<1 then Q>K, so reverse
reaction is spontaneous). Therefore, ΔGorxn is positive for the direct and negative for the reverse reaction.

14. Which of the following chemical equations represents reaction with the largest equilibrium constant (K) at
298 K? Give brief reasoning.
A) CaCO3(s) → CaO(s) + CO2(g) ΔG° =+131.1 kJ
B) 2 Hg(g) + O2(g) → 2 HgO(s) ΔG° = -180.8 kJ
C) 3 O2(g) → 2 O3(g) ΔG° = +326 kJ
D) Fe2O3(s) + 3 CO(g) → 2 Fe(s) + 3 CO2(g) ΔG° = -28.0 kJ
E) It is not possible to determine without more information.

The reaction with largest negative ∆G⁰ is thermodynamically the most favored, so it will proceed
farthest towards product formation and, consequently, will have the largest equilibrium constant.

∆G⁰ = −RTlnK => =>

15. Use the standard free energies of formation given below to calculate the equilibrium constant (K) for the
reaction at 298 K represented by the following chemical equation:

2 HNO3(aq) + NO(g) → 3 NO2(g) + H2O(l) K=?

ΔG°f (kJ/mol) -110.9 87.6 51.3 -237.1

∆G⁰rxn = +51 kJ

OCC CHM 122 PS Ch. 19 ANSWER KEY Professor Miodragovic 5