Chapter 17

THERMODYNAMICS
Entropy, Free Energy,
and Equilibrium

Energy change and flow from one

system to another
Chemistry 2 (1420103)

Spontaneous Physical and Chemical Processes

A waterfall runs downhill
A lump of sugar dissolves in a cup of coffee
At 1 atm, water freezes below 0 0C and ice melts above 0 0C
Heat flows from a hotter object to a colder object
A gas expands in an evacuated bulb
Iron exposed to oxygen and water forms rust
spontaneous
Spontaneous changes take place without
assistance. Example: a car slowly rusts

nonspontaneous

spontaneous

nonspontaneous

Does a decrease in enthalpy (H) mean a reaction

proceeds spontaneously?

Spontaneous reactions

Delta H in KJ per mole

CH4 (g) + 2O2 (g)

CO2 (g) + 2H2O (l) H0 = -890.4 kJ

H+ (aq) + OH- (aq)

H2O (l) H0 = -56.2 kJ

H2O (s)
NH4NO3 (s)

H2O (l) H0 = 6.01 kJ

H2O

NH4+(aq) + NO3- (aq) H0 = 25 kJ

Entropy (S) is a measure of the randomness or disorder of a

system.
order

disorder

S = Sf - Si
If the change from initial to final results in an increase in randomness

Sf > Si

S > 0

For any substance, the solid state is more ordered than the
liquid state and the liquid state is more ordered than gas state
Ssolid < Sliquid << Sgas
H2O (s)

H2O (l)

S > 0

Thermodynamics
State functions are properties that are determined by the state
of the system, regardless of how that condition was achieved.
energy, enthalpy, pressure, volume, temperature, entropy
It is independent of
pathway

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.

Processes that
lead to an
increase in
entropy (S > 0)

How does the entropy of a system change for each of the

following processes?

(a) Condensing water vapor

Randomness decreases

Entropy decreases (S < 0)

(b) Forming sucrose crystals from a supersaturated solution

Randomness decreases
Entropy decreases (S < 0)
(c) Heating hydrogen gas from 600C to 800C
Randomness increases

Entropy increases (S > 0)

(d) Subliming dry ice

Randomness increases

Entropy increases (S > 0)

8

First Law of Thermodynamics

Energy can be converted from one form to another but
energy cannot be created or destroyed.
The change in internal energy is defined in terms of
heat (q) and work (w)
E E final Einitial q w
q0
q0
w0
w0

Heat is absorbed by the system

Heat is released by the system
Work is done on the system
Work is done by the system

Internal energy is a state function which means

that its value does not depend on how the change
from one state to another was carried out
9

Second Law of Thermodynamics

The entropy of the universe (total) increases in a
spontaneous process and remains unchanged in an
equilibrium process.
Spontaneous process:

Stotal = Ssys + Ssurr > 0

Equilibrium process:

Stotal = Ssys + Ssurr = 0

10

Entropy Changes in the System (Ssys)

The standard entropy of reaction (S0rxn) is the entropy
change for a reaction carried out at 1 atm and 250C.
aA + bB
S0rxn =

cC + dD

[ cS0(C) + dS0(D) ] - [ aS0(A) + bS0(B) ]

S0rxn = nS0(products) - mS0(reactants)

What is the standard entropy change for the following
reaction at 250C? 2CO (g) + O2 (g)
2CO2 (g)
S0(CO) = 197.9 J/Kmol
S0(O2) = 205.0 J/Kmol

S0(CO2) = 213.6 J/Kmol

S0rxn = 2 x S0(CO2) [2 x S0(CO) + S0 (O2)]

S0rxn = 427.2 [395.8 + 205.0] = -173.6 J/Kmol

11

Entropy Changes in the System (Ssys)

When gases are produced (or consumed)

If a reaction produces more gas molecules than it

consumes, S0 > 0.

If the total number of gas molecules diminishes,

S0 < 0.

If there is no net change in the total number of gas

molecules, then S0 may be positive or negative
BUT S0 will be a small number.
What is the sign of the entropy change for the following
reaction? 2Zn (s) + O2 (g)
2ZnO (s)

The total number of gas molecules goes down, S is negative.

12

Entropy Changes in the Surroundings (Ssurr)

Exothermic Process
Ssurr > 0

Endothermic Process
Ssurr < 0
13

Third Law of Thermodynamics

The entropy of a perfect crystalline substance is zero at the
absolute zero of temperature.

14

Gibbs Free Energy

Spontaneous process:

Suniv = Ssys + Ssurr > 0

Equilibrium process:

Suniv = Ssys + Ssurr = 0

For a constant-temperature process:

Gibbs free
energy (G)

G = Hsys -TSsys

G < 0

The reaction is spontaneous in the forward direction.

G > 0

The reaction is nonspontaneous as written. The

reaction is spontaneous in the reverse direction.

G = 0

The reaction is at equilibrium.

15

18.4

The standard free-energy of reaction ( G0rxn) is the freeenergy change for a reaction when it occurs under standardstate conditions.
aA + bB

cC + dD
0
Grxn
= [ cG0f (C) + dG0f (D) ] - [ aG0f (A) + bG0f (B) ]
0
Grxn
= nG0f (products) - mG0f (reactants)

Standard free energy of

formation (G0f ) is the free-energy
change that occurs when 1 mole
of the compound is formed from its
elements in their standard states.
G0f of any element in its stable
form is zero.
16

What is the standard free-energy change for the following

reaction at 25 0C?
2C6H6 (l) + 15O2 (g)

12CO2 (g) + 6H2O (l)

0
Grxn
= nG0f (products) - mG0f (reactants)
0
Grxn
= [ 12Gf0 (CO2) + 6Gf0 (H2O)] - [ 2Gf0 (C6H6)]
0
Grxn
= [ 12x394.4 + 6x237.2 ] [ 2x124.5 ] = -6405 kJ

Is the reaction spontaneous at 25 0C?

G0 = -6405 kJ < 0
spontaneous
17

G = H - TS

18

Temperature and Spontaneity of Chemical Reactions

CaCO3 (s)

CaO (s) + CO2 (g)

H0 = 177.8 kJ
S0 = 160.5 J/K
G0 = H0 TS0
At 25 0C, G0 = 130.0 kJ
G0 = 0 at 835 0C

19

Gibbs Free Energy and Phase Transitions

G0 = 0 = H0 TS0

H2O (l)
S =

H2O (g)
H
40.79 kJ
=
T
373 K
= 109 J/K

20

Gibbs Free Energy and Chemical Equilibrium

G = G0 + RT lnQ
R is the gas constant (8.314 J/Kmol)
T is the absolute temperature (K)
Q is the reaction quotient
At Equilibrium
G = 0

Q=K

0 = G0 + RT lnK
G0 = RT lnK
21

G0 < 0

G0 > 0

22

G0 = RT lnK

At equilibrium, Q = K, and G = 0.
The equation becomes
0 = G + RT lnK
Rearranging, this becomes
G = RT lnK
or,
K = eG/RT

23

EXTRA Examples

24

Predicting Relative S0 Values of a System

1. Temperature changes
S0increasesasthetemperaturerises.
2. Physical states and phase changes
S0increasesasamoreorderedphasechangestoalessorderedphase.
3. Dissolution of a solid or liquid
S0ofadissolvedsolidorliquidisusuallygreaterthantheS0ofthepuresolute.However,
theextentdependsuponthenatureofthesoluteandsolvent.

4. Dissolution of a gas
Agasbecomesmoreorderedwhenitdissolvesinaliquidorsolid .
5. Atomic size or molecular complexity
Insimilarsubstances,increasesinmassrelatedirectlytoentropy.
Inallotropicsubstances,increasesincomplexity(e.g.bond
flexibility)relatedirectlytoentropy.

Entropy Changes in the System

S0rxn - the entropy change that occurs when all reactants
and products are in their standard states.

S0rxn = S0products - S0reactants

The change in entropy of the surroundings is directly
related to an opposite change in the heat of the system
and inversely related to the temperature at which the
heat is transferred.

Ssurroundings = -

Hsystem
T

Sample Problem 1 Calculating the Standard Entropy of Reaction, S0rxn

PROBLEM: Calculate S0rxn for the combustion of 1mol of propane at 250C.
C3H8(g) + 5O2(g)

3CO2(g) + 4H2O(l)

PLAN: Use summation equations. It is obvious that entropy is being lost

because the reaction goes from 6 mols of gas to 3 mols of gas.
SOLUTION:

Find standard entropy values in the Appendix or other table.

S = [(3 mol)(S0 CO2) + (4 mol)(S0 H2O)] - [(1 mol)(S0 C3H8) + (5 mol)(S0 O2)]
S = [(3 mol)(213.7J/mol*K) + (4 mol)(69.9J/mol*K)] - [(1 mol)(269.9J/mol*K) +
(5 mol)(205.0J/mol*K)]
S = - 374 J/K

Sample Problem 2
PROBLEM:

PLAN:

Calculating G0rxn from G0f Values

Use G0f values to calculate Grxn for the reaction in Sample

Problem 20.4:

4KClO3(s)
3KClO4(s) + KCl(s)

Use the G summation equation.

SOLUTION: G0rxn = mG0products - nG0reactants

G0rxn = (3mol)(-303.2kJ/mol) + (1mol)(-409.2kJ/mol) (4mol)(-296.3kJ/mol)

G0rxn = -134kJ

Sample Problem 2

Calculating G0rxn from Enthalpy and Entropy Values

continued
S0rxn = mS0products - nS0reactants
S0rxn = (3 mol)(151 J/mol*K) + (1 mol)(82.6 J/mol*K) (4 mol)(143.1 J/mol*K)
S0rxn = -36.8 J/K
G0rxn = H0rxn - T S0rxn
G0rxn = -144 kJ - (298K)(-36.8 J/K)(kJ/103 J)
G0rxn = -133 kJ

Gibbs Free Energy (G)

G, the change in the free energy of a system, is a
measure of the spontaneity of the process and of the
useful energy available from it.

G0system = H0system - TS0system

G < 0 for a spontaneous process
G > 0 for a nonspontaneous process
G = 0 for a process at equilibrium

G0rxn = mG0products - nG0reactants

Sample Problem 3
PROBLEM:

Determining the Effect of Temperature on G0

An important reaction in the production of sulfuric acid is the

oxidation of SO2(g) to SO3(g):
2SO2(g) + O2(g)

2SO3(g)

At 298K, G0 = -141.6kJ; H0 = -198.4kJ; and S0 = -187.9J/K

(a) Use the data to decide if this reaction is spontaneous at 250C, and predict
how G0 will change with increasing T.
(b) Assuming H0 and S0 are constant with increasing T, is the reaction
spontaneous at 900.0C?
PLAN:

The sign of G0 tells us whether the reaction is spontaneous

and the signs of H0 and S0 will be indicative of the T effect.
Use the Gibbs free energy equation for part (b).

SOLUTION: (a) The reaction is spontaneous at 250C because G0 is (-).

Since H0 is (-) but S0 is also (-), G0 will become less
spontaneous as the temperature increases.

Sample Problem 3

Determining the Effect of Temperature on G0

continued
(b) G0rxn = H0rxn - T S0rxn
G0rxn = -198.4kJ - (1173K)(-187.9J/mol*K)(kJ/103J)
G0rxn = 22.0 kJ; the reaction will be nonspontaneous at 900.0C

Free Energy, Equilibrium, and Reaction Direction

If Q/K < 1, then ln Q/K < 0; the reaction proceeds to the right (G < 0)
If Q/K > 1, then ln Q/K > 0; the reaction proceeds to the left (G > 0)
If Q/K = 1, then ln Q/K = 0; the reaction is at equilibrium (G = 0)

G = RT ln Q/K = RT lnQ - RT lnK

Under standard conditions (1M concentrations, 1atm for gases), Q = 1
and ln Q = 0 so

G0 = - RT lnK

Sample Problem 4

Calculating G at Nonstandard Conditions

PROBLEM: The oxidation of SO2, which we considered in Sample Problem 20.6

2SO2(g) + O2(g)

2SO3(g)

is too slow at 298K to be useful in the manufacture of sulfuric acid. To

overcome this low rate, the process is conducted at an elevated temperature.
(a) Calculate K at 298K and at 973K. (G0298 = -141.6kJ/mol of reaction as
written using H0 and S0 values at 973K. G0973 = -12.12kJ/mol of reaction
as written.)
(b) In experiments to determine the effect of temperature on reaction
spontaneity, two sealed containers are filled with 0.500 atm of SO2, 0.0100
atm of O2, and 0.100 atm of SO3 and kept at 250C and at 700.0C. In which
direction, if any, will the reaction proceed to reach equilibrium at each
temperature?
(c) Calculate G for the system in part (b) at each temperature.
PLAN: Use the equations and conditions found on slide

Sample Problem 4

Calculating G at Nonstandard Conditions

continued
SOLUTION: (a) Calculating K at the two temperatures:
(G /RT )

G = -RTlnK so K e
0

At 298, the exponent is -G0/RT

K e(G

/RT )

=-

/RT )

(8.314J/mol*K)(298K)

= 57.2

= e57.2 = 7x1024

At 973, the exponent is -G0/RT

K e(G

(-141.6kJ/mol)(103J/kJ)

= e1.50 = 4.5

(-12.12kJ/mol)(103J/kJ)
(8.314J/mol*K)(973K)

= 1.50

Sample Problem 4

Calculating G at Nonstandard Conditions

continued
pSO32

(b) The value of Q =

(pSO2)2(pO2)

(0.100)2
(0.500) (0.0100)
2

= 4.00

Since Q is < K at both temperatures the reaction will shift right; for 298K
there will be a dramatic shift while at 973K the shift will be slight.
(c) The nonstandard G is calculated using G = G0 + RTlnQ
G298 = -141.6kJ/mol + (8.314J/mol*K)(kJ/103J)(298K)(ln4.00)
G298 = -138.2kJ/mol
G973 = -12.12kJ/mol + (8.314J/mol*K)(kJ/103J)(973K)(ln4.00)
G298 = -0.9kJ/mol