Chapter 17: Spontaneity, Entropy and Free Energy

Sample Questions

Section 17.1

1. Recognize the meaning of a spontaneous process

What is meant by a spontaneous process? Is the tendency to achieve minimum energy
the only driving force for spontaneous processes?
A process is said to be spontaneous if it occurs without external or outside interference.
No, maximum randomness is the other driving force for spontaneous processes.

2. Know that minimizing energy and maximizing randomness are the driving forces for
spontaneous processes
What are the driving forces for spontaneous processes?
The driving forces for spontaneous processes are minimizing energy and maximizing
randomness

3. Recognize what entropy represents or means

What is the entropy related to?
Entropy is a thermodynamic function that is related to randomness or disorder.

4. Predict when a chemical will have higher entropy

When will water have higher entropy, at 25C or at 80C?
At 80C, water will have greater entropy. Entropy increases with an increase in
temperature.

Section 17.2

5. Know the statement of the second law of thermodynamics

State the second law of thermodynamics.
The second law of thermodynamics states that in any spontaneous process there is always
an increase in the entropy of the universe.

Section 17.3

6. Calculate Ssurrounding for a particular reaction

Consider the following process: C(s) + O2(g)  CO2(g) H = -394 kJ.
Calculate the value of Ssurrounding at 25C and 1atm.
∆
∆ =- = = 1.32 kJ/mol K = 1320 J/mol K
Section 17.4

7. Know the mathematical definition of free energy

What mathematical relation defines the function, G, free energy?
G = H - TS

8. Applying the formula: ΔG° = ΔH° – T ΔS°

Consider the following process:
H2O(s) H2O(l) ΔH° = 6.03 kJ
Knowing that the freezing point of water is 0 °C, calculate the value of ΔS°.
At freezing point ΔG°= 0
ΔH° – T ΔS° = 0
H° 6030
ΔS° =  =  = 22.1 J/K
T 273

9. Applying the formula: ΔG° = ΔH° – T ΔS° to find freezing point/boiling point of a
substance
Consider the following process:
C2H5OH(l) C2H5OH(g) ΔH° = 39.0 kJ
Knowing that ΔS° vaporization = 111.5 J/mol.K, calculate the boiling point of ethanol.
At boiling point ΔG°= 0
H 0 39000
T boiling =  = = 349.8 K
S vaporization
o
111.5

Section 17.5

10. Predict the sign of S for a given reaction

Predict the sign of S for the following reactions:
NH4Cl(s) NH3(g) + HCl(g) S is positive
2NO2(g) N2(g) + 2O2(g) S is positive
2IBr(g) I2(g) + Br2(g) S is positive
(NH4)2CO3(s) 2NH3(g) + H2O(g) + CO2(g) S is positive
C6H6(s) C6H6(l) S is positive

11. Know the statement of the third law of thermodynamics

State the third law of thermodynamics.
The entropy of a perfect crystal at 0K is zero.

12. Calculate ΔS° given S° values

Consider the following process:
CO(g) + ½ O2(g) CO2(g)
a) Calculate ΔS° at 298K, given the following S° values, in J.K–1:
CO: 198; CO2: 213; O2: 205;
S = Sf of products - Sf of reactants
S = (213) – 198 – (1/2)(205) = -87.5 J.K-1
b) Is the sign of ΔS° expected?
Yes, the negative sign shows the process is moving towards less randomness.

Section 17.6
13. Know the definition of the standard free energy change, G
How is the standard free energy change, G defined?
Standard free energy is the change in free energy when reactants in their standard states
are changed to products in their standard state.

14. Calculate ΔG°, ΔH° and ΔS° for a particular reaction

Consider the following process:
C2H6(g) + 7/2O2(g)  2CO2(g) + 3H2O(l)
Calculate ΔG° and ΔH° at 298 K, given the following data:
Substance C2H6(g) O2(g) CO2(g) H2O(l)
ΔH°f,(kJ/mol) –85 0 –394 –286
S°, (J/K.mol) 230 205 214 70

G = H - TS

S = nSf of products - Sf of reactants = (2)(214) + (3)(70) – (230) – (7/2)(205) = -309.5 J/K
H = Hf of products - Hf of reactants = (3)(-286) + (2)(-394) – (-85) = -1561 kJ
G = -1561000 – (298)(-309.5) = -1468.77 J = -1.47 kJ

15. Calculate ΔG° for a particular reaction given ΔG°f

Consider the following process:
C2H6(g) + 7/2O2(g)  2CO2(g) + 3H2O(l)
Calculate ΔG° at 298K, given the following data:
Substance C2H6(g) O2(g) CO2(g) H2O(l)
ΔG°f (kJ/mol) –33 0 –394 –237

G = Gf of products - Gf of reactants = (2)(-394) + (3)(-237) – (-33) = -1.47 kJ

Section 17.7

16. Know how ΔG varies with pressure

Give the mathematical relation between ΔG, ΔG° and P at a particular temperature.
G = Go + RTln(P)
ΔG = ΔG° + RTln(Q)

17. Apply G = G + RTlnQ

Consider the following process: 2NO2 (g) ⇆ N2O4(g).
G of the above reaction has been calculated from individual Gf values, and found to be
– 5.0 kJ/mol. Calculate G for the above reaction, at 27C, where the pressure of NO2 is 3
atm, and that of N2O4 is 1 atm. Use R = 8.3 J/K.mol.
G = G + RTlnQ = G + RTln = -5000 + (8.3)(300)(ln = - 10471 J = - 1.1 kJ

Section 17.8
18. Application on G = -RTlnK
Consider the following process: 2NO2 (g) ⇆ N2O4(g).
G of the above reaction has been calculated from individual Gf values, and found to be
– 5.0 kJ/mol. Calculate the equilibrium constant for the above reaction at 25C.
Use R = 8.3 J/K.mol.

G = -RTlnK - 5000 = - (8.3)(298)lnK K = 7.6

 

 
 Basic Questions
Basic Question 1
17.1 Predict the sign of ΔS of a given process T, G

Predict the sign of the entropy change, ΔS, for the following processes:
a) PCl5(g)  PCl3(g) + Cl2(g)
1 mole of a gas is producing 2 moles of gases  disorder increases.
ΔS◦ is positive.

b) 2H(g)  H2(g)
2 moles of gases are producing 1 mole of gas  disorder decreases.
ΔS is negative.

c) Fluorine gas, an oxidizing agent, is bubbled into a solution of potassium bromide at 25C.
The balanced equation for the reaction occurring is: F2(g)+2Br-(aq)  2F-(aq)+Br2(aq)

Predict the sign of S for the reaction at 25C. Justify your prediction.
The sign of S is negative.
One of the reactants, F2, is a gas at 25C, but there are no gaseous products. Gases have
high entropies, so the entropy of the reactants is greater than the entropy of the products,
making S negative.

Basic Question 2
17.5 ° ° ° G
Application on ∆ =Σ Σ

Consider the following process: Zn(s) + ½O2(g)  ZnO(s)

a) Calculate ΔS at 298K, given the following S values, in J.K-1 mol-1:
ZnO: 44; Zn: 42; O2: 205.

° ° °
S = - - = (44) – (42) – ( = -100.5J/mol K

17.1 Predict the sign of ΔS° of a given process G

b) Is the sign of ΔS expected?

yes, because 1 mole of solid and 0.5 mole of gas are becoming 1 mole of solid.
Basic Question 3
Consider the following process: 2NO2(g)  N2O4(g). Given the following data:

Substance ΔHf (kJ/mol) S (J/K.mol)

NO2(g) 33 240
N2O4(g) 9 304

6.4 ° ° ° G
Application on ∆ =Σ ∆ , Σ ∆ ,

a. Calculate ΔHat 298K

H = ∆ ° , - 2∆ °
, = (9) –2(33) = - 57 kJ

17.4 ° ° ° G
Application on ∆ =Σ Σ

b. Calculate ΔS at 298K

S = ∆ ° - 2∆ ° = 304 – 2(240) = - 176 J/mol K

17.6 Application on G = H - TS G

ΔG° = ΔH° - TΔS° = - 57 - (298)(-176 × 10-3 ) = = -4.6kJ

Basic Question 4
17.4 Predict whether a reaction is spontaneous or not given its S, H and t G

Consider the following process: H2O(s) → H2O(l) ΔH = 6.03 kJ

Given ΔS° = 22.1 J/K.mol, show that the melting of ice becomes spontaneous at 0°C.
Given ΔS° = 22.1 J/K.mol, ΔH = 6.03 kJ, T = 0C + 273 = 273K
RTF: rxn is spontaneous
G = ΔH - T ΔS = (6.03) – (273)(22.1 × 10-3) = - 3.3 × 10-3kJ
Since G is negative then the process is spontaneous.

Basic Question 5
17.4 Know that for isothermal processes, H = TS T, G

Consider the following process: C6H6(l) → C6H6(g)

Given for the above process ΔHvap = 30.8 kJ/mol, and ΔSvap = 87.2 J/K.mol.
Calculate the boiling point of benzene.
Given: ΔHvap = 30.8 kJ/mol, ΔSvap = 87.2 J/K.mol
RTF: boiling point of benzene

A phase change at equilibrium is isothermal, i.e. occurs at same t, therefore G = 0kJ
.
G = ΔHvap - TΔSvap = (30.8) – T(87.2 × 10-3) = 0kJ  T = = 353K  t =
.
80C
Basic Question 6
17.6 ° ° ° G
Application on ∆ =Σ ∆ , Σ ∆ ,

Consider the following process: CH4(g) + 2O2(g)  CO2(g) + 2H2O(l).

Calculate ΔG°, given the following data:

Substance CH4 (g) O2 (g) CO2(g) H2O(l)

ΔG°f, (kJ/mol) – 51 0 – 394 – 237

° ° ° °
ΔG° = ∆ , ∆ , ∆ , ∆ , = (-394) + 2(-237) – (-51) – 2(0) = -817kJ

Basic Question 7
8.10 Draw Lewis structures for given species T, G

Answer the following questions about nitrogen, hydrogen, and ammonia.

a) Draw the complete Lewis electron-dot diagrams for N2 and NH3.

17.1 Find G per given m of named reactant given G of the reaction T, G

b) Calculate the standard free-energy change, ΔG, that occurs when 24.0 g of H2(g) react with
excess N2(g) at 298 K according to the reaction represented below.
N2(g) + 3H2(g) ⇆ 2NH3(g) ΔG298 = −34 kJ mol−1
Given: m of H2 = 24.0 g, ΔG298 = −34 kJ mol−1
RTF: ΔG
.
= = 12.0moles
N2(g) + 3H2(g) ⇆ 2NH3(g) ΔG298 = −34 kJ mol−1
3moles -34kJ
.
12.0moles ΔG298 ΔG298 = = - 136 kJ

8.7 Compare total bond dissociation energy of the reactants to the total bond T, G
dissociation energy of the products given H of the reaction
c) Given that ΔH298 for the reaction is −90.0 kJ mol−1, which is larger, the total bond dissociation
energy of the reactants or the total bond dissociation energy of the products? Explain.
ΔH298 = Σ(bond energy of the reactants) − Σ(bond energy of the products)
Based on the equation above, for ΔH298 to be negative, the total bond energy of the
products must be larger than the total bond energy of the reactants.
 17.1 Predict the sign of ΔS° of a given process T, G

d) Predict the sign of the standard entropy , ΔS298 , for the reaction . Explain your answer.
All of the reactants and products in the reaction are in the gas phase, so the sign of the
entropy change will depend on the number of moles of gaseous particles in the reactants and
products. There are more moles of reactants (four) compared with moles of products (two),
so there is a greater number of microstates in the reactants than in the products. Therefore
the entropy decreases as the reaction proceeds (fewer possible microstates), and the sign of
the entropy change is negative.

e) Assume that ΔH° and ΔS° for the reaction are independent of temperature.

17.4 Explain why there is a temperature at which the reaction changes spontaneity, T, G
using G = H - TS
i. Explain why there is a temperature, above 298 K, at which the reaction changes spontaneity.
State whether the reaction becomes spontaneous or not above this temperature.
ΔG° = ΔH° − TΔS°
As the temperature increases |TΔS°| will at some point exceed |ΔH°|. Because both ΔH° and
ΔS° are negative, the sign of ΔG° will then change from negative to positive. The reaction
will change from spontaneous to not spontaneous.

17.4 Predict the best conditions of temperature and pressure needed for max yield T, G
of a given reaction given ΔH° and ΔS°
ii. Theoretically, at what temperature and pressure conditions will the best yields of ammonia be
achieved? Explain.
H < 0, S < 0
Low temperatures: The reaction is exothermic. By Le Chatelier’s principle, decreasing the
temperature drives the reaction to the right to produce more heat energy, and thus more
ammonia is produced.
High pressures: By Le Chatelier’s principle, increasing the pressure will shift the reaction
towards the side with lesser moles of gases to decrease the pressure. In this case, the product
has fewer moles of particles than the reactants; thus reaction would shift to the right
increasing the yield.

Basic Question 8
Consider the following process: CaCO3(s)  CaO(s) + CO2(g).

17.7 Application on ΔG = ΔG° + RTlnQ to find ΔG T, G

a) ΔG° of the above reaction has been calculated from individual ΔG°f values, and found
to be 130 kJ/mol. Calculate ΔG for the above reaction where the pressure of CO2(g) is 4 atm. Use
R = 8.3 J/K.mol.
Given: G = 130kJ/mole, R = 8.3 J/K.mol, = 4atm
RTF: G
G = ΔG° + RTlnQ Q=
G = (130) + (8.3 × 10-3)(298)(ln4) = 133 kJ

17.8 Predict the effect of a change in concentration or pressure on G T, G

b) Is the change in the value of ΔG expected from Le Chatelier’s principle?

Yes. increases, by LCP, the equilibrium shifts to the left to decrease it. ΔG becomes
more positive

Basic Question 9
T

Reaction Equation H S G

(kJ mol-1) (J mol-1 K-1) (kJ mol-1)

1 X(s) + H2O(g) ⇆ XO(g) + H2(g) +131 +134 +91

2 XO2(g) + H2(g) ⇆ XO(g) + H2O(g) +41 +42 +29

3 2XO(g) ⇆ X(s) + XO2(g) ? ? ?

Answer the following questions using the information related to reactions 1, 2, and 3 in the table
above.

17.8 Predict the effect on the equilibrium constant value if temperature changes G

a) For reaction 1, write the expression for the equilibrium constant, Kp.
[ XO][ H 2 ]
Kp =
[ H 2O]
b) For reaction 1, will the equilibrium constant, Kp , increase, decrease, or remain the same if the
temperature rises above 298 K ? Justify your answer.
Kp will increase.
If the temperature is increased for an endothermic reaction ( ΔH298 = +131 kJ mol−1), then
by Le Chatelier’s principle the reaction will shift toward products, thereby absorbing
energy. With greater concentrations of products at equilibrium, the value of Kp will increase.
OR
Because ΔG = − RT ln Kp = ΔH298 − T ΔS298
then
∆ ° ∆ °
lnKp = -
An increase in T for a positive ΔH298 results in an increase in lnKp and thus an increase in
Kp .
 17.8 Predict the whether K is greater than or less than 1 given the sign of G G

c) For reaction 2 at 298 K, is the value of Kp greater than 1, less than 1, or equal to 1? Justify
your answer.
A positive ΔG results in a non-spontaneous reaction under standard conditions. This
favors reactants over products as equilibrium is approached starting from standard
conditions, resulting in a Kp less than 1.

d) For reaction 2 at 298 K, which is larger: the total bond energy of the reactants or the total
bond energy of the products? Explain.
for reaction 2: H
Hbond energies of reactants - bond energies of products 
bond energies of reactants bond energies of products

17.8 Compare total bond dissociation energy of the reactants to the total bond G
dissociation energy of the products given H of the reaction
e) Is the following statement true or false? Justify your answer.
“On the basis of the data in the table, it can be predicted that reaction 2 will occur more rapidly
than reaction 1 will occur.”
The statement is false. Thermodynamic data for an overall reaction have no bearing on
how slowly or rapidly the reaction occurs.

f) Consider reaction 3 at 298 K.

i Is ΔS° for the reaction positive, negative, or zero? Justify your answer.
2 moles of gases are producing 1 mole of gas  disorder decreases.
ΔS is negative.
ii. Determine the value of ΔH° for the reaction.
If we add reaction 1 and reaction 2 then flip the final reaction, we will have reaction 3
So, ΔH° for reaction 3 = - ΔH° reaction 1 - ΔH° reaction 2
ΔH° for reaction 3 = -172 kJ
iii. A sealed glass reaction vessel contains only XO(g) and a small amount of X(s).
If a reaction occurs and the temperature is held constant at 298 K, will the
pressure in the reaction vessel increase, decrease, or remain the same over
time? Explain.
The pressure in the flask decreases. The reaction would proceed to the right, forming more
X(s) and XO2(g). Because two moles of XO(g) would be consumed for every mole of XO2(g)
that is produced, the total number of moles of gas in the flask would decrease, thereby
causing the pressure in the flask to decrease.
Basic Question 10 T

Use principles of thermodynamics to answer the following questions.

a) The gas N2O4 decomposes to form the gas NO2 according to the equation below.
N2O4 ⇆ 2NO2

8.8 Predict the sign of ΔH of a given process G

i. Predict the sign of H for the reaction. Justify your answer.

O=N–N=O O=N–O

O O

Bonds broken = 2 N=O + 2N-O + N-N

Bonds formed = 2N=O + 2N-O

H = 2 N=O + 2N-O + N-N - 2N=O - 2N-O = N-N

More bonds are broken than formed. Energy must be absorbed to break bonds, so the
reaction is endothermic and the sign of H is positive.

17.1 Predict the sign of ΔS° of a given process G

ii. Predict the sign of S for the reaction. Justify your answer.
There are two gaseous product molecules for each gaseous reactant molecule, so the product
has more entropy than the reactant. The entropy increases as the reaction proceeds, so the
sign of S is positive.

17.4 Predict the effect of a temperature change on ΔG of a given process G

b) How does G vary with increasing temperature?

G = H – TS.
S is positive, so as T increases, -TS becomes a larger negative number. At higher
temperatures, you are subtracting larger numbers from H to get G, so G decreases with
increasing temperature.
Basic Question 11
T
Consider the following reaction
N2(g) + 3H2(g) ⇆ 2NH3(g) H = -92kJ mol-1, S = - 199J K-1 mol-1

17.6 Application on G = H - TS G

a) Calculate the value of the standard free energy change. ∆Go for the reaction.
Given: H = -92kJ mol-1, S = - 199J K-1 mol-1
RTF: : G
G = H - TS = -92 –(298)(-0.199) = -33kJ mol-1

17.8 Use G = H - TS = -RTlnK to find T when K = 1 G

b) Determine the temperature at which the equilibrium constant Keq for the reaction is equal to
1.00
Given: H = -92kJ mol-1, S = - 199J K-1 mol-1, Keq = 1
RTF: : T
If K = 1, lnK = 0  G = 0
∆ °
H - TS = 0 = 162K
∆ ° .

c) Use both the information above and the table to calculate average enthalpy of the H–H bond
Bond Average Bond Enthalpy (kJ mol–1)
NN 946

N-H 391

HH ?

ΔHo = Σ(bond energy of the reactants) − Σ(bond energy of the products) = -92
= E(N  N) + 3E(HH) – 6E(N-H) = -92
= 946 + 3x – (6)(391) = -92
E(HH) = x = 436 kJ

 
Multiple Choice
T
17.11 Application on G = ∆ H◦ - T∆S◦ G

1. Which of the following is true of a reaction that is spontaneous at higher temperatures?

[-A-] S and H are both negative

[-B-] S and H are both positive
[-C-] S is negative and H is positive
[-D-] S is positive and H is negative
[-E-] S and H are both equal to zero

17.11 Application on G = ∆ H◦ - T∆S◦ G

2. When solid NH4SCN is mixed with solid Ba(OH)2 in a closed container, the temperature drops
and a gas is produced. Which of the following indicates the correct signs for ∆G, ∆H and ∆S for
the process?
∆G ∆H ∆S
[-A-] - - -
[-B-] - + -
[-C-] - + +
[-D-] + - +
[-E-] + - -

A gas is produced from solids  entropy increased  ∆S is positive

Temperature drops  reaction is endothermic  ∆H is positive

Answer: C