Entropy, Free Energy,

and Equilibrium
Chapter 18

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 Entropy, Free Energy,
and Equilibrium
Chapter Two Contains:
2.1 The Three Laws of Thermodynamics
2.2 Spontaneous Processes
2.3 Entropy
2.4 The Second Law of Thermodynamics
2.5 Gibbs Free Energy
2.6 Free Energy and Chemical Equilibrium
2.7 Thermodynamics in Living Systems
 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

nonspontaneous

18.2
 spontaneous

nonspontaneous

18.2
 Does a decrease in enthalpy mean a reaction proceeds
spontaneously?

Spontaneous reactions

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) DH0 = -890.4 kJ

H+ (aq) + OH- (aq) H2O (l) DH0 = -56.2 kJ

H2O (s) H2O (l) DH0 = 6.01 kJ

H2O
NH4NO3 (s) NH4+(aq) + NO3- (aq) DH0 = 25 kJ

18.2
Entropy (S) is a measure of the randomness or disorder of a
system.

order S disorder S

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

Sf > Si DS > 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) DS > 0

18.3
 Entropy

W=1

W = number of microstates
S = k ln W W=4
DS = Sf - Si
Wf
DS = k ln
Wi

Wf > Wi then DS > 0

W=6
Wf < Wi then DS < 0

18.3
 Processes that
lead to an
increase in
entropy (DS > 0)

18.2
 2.1 How does the entropy of a system change for each of
the following processes?

(a) Condensing water vapor

Randomness decreases Entropy decreases (DS < 0)
(b) Forming sucrose crystals from a supersaturated solution
Randomness decreases Entropy decreases (DS < 0)
(c) Heating hydrogen gas from 600C to 800C
Randomness increases Entropy increases (DS > 0)
(d) Subliming dry ice
Randomness increases Entropy increases (DS > 0)

18.3
 Entropy

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

Potential energy of hiker 1 and hiker 2

is the same even though they took
different paths.
18.3
First Law of Thermodynamics
Energy can be converted from one form to another but
energy cannot be created or destroyed.
Second Law of Thermodynamics
The entropy of the universe increases in a spontaneous
process and remains unchanged in an equilibrium process.

Spontaneous process: DSuniv = DSsys + DSsurr > 0

Equilibrium process: DSuniv = DSsys + DSsurr = 0

18.4
 Entropy Changes in the System (DSsys)
The standard entropy of reaction (DS0rxn ) is the entropy
change for a reaction carried out at 1 atm and 250C.
aA + bB cC + dD

DS0rxn = [ cS0(C) + dS0(D) ] - [ aS0(A) + bS0(B) ]

DS0rxn = S nS0(products) - S mS0(reactants)

2.2 What is the standard entropy change for the following

reaction at 250C? 2CO (g) + O2 (g) 2CO2 (g)

S0(CO) = 197.9 J/K•mol S0(CO2) = 213.6 J/K•mol

S0(O2) = 205.0 J/K•mol
DS0rxn = 2 x S0(CO2) – [2 x S0(CO) + S0 (O2)]
DS0rxn = 427.2 – [395.8 + 205.0] = -173.6 J/K•mol
18.4
 Entropy Changes in the System (DSsys)
When gases are produced (or consumed)

• If a reaction produces more gas molecules than it

consumes, DS0 > 0.
• If the total number of gas molecules diminishes,
DS0 < 0.
• If there is no net change in the total number of gas
molecules, then DS0 may be positive or negative
BUT DS0 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, DS is negative.

18.4
 Entropy Changes in the Surroundings (DSsurr)

Exothermic Process Endothermic Process

DSsurr > 0 DSsurr < 0

DSsurr a -DHsys

DSsurr a DSsurr

N2(g) + 3H2(g) 2NH3(g)

18.4
Example 2.3 Is the following reaction is spontaneous at
25oC, where DSsys is -199kJ/mol.
N2(g) + 3H2(g) 2NH3(g)

DSsurr = 311 J/[Link]

DSuniv = DSsys + DSsurr

DSuniv = -199 + 311 = 112 J/[Link]

Because DSuniv is positive, we predict that the reaction is

spontaneous at 25oC.
Third Law of Thermodynamics
The entropy of a perfect crystalline substance is zero at the
absolute zero of temperature.

S = k ln W
W=1
S=0

18.3
 Gibbs Free Energy
Spontaneous process: DSuniv = DSsys + DSsurr > 0

Substituting -DHsys / T for DSsurr we write

DSuniv = DSsys >0
 For a constant-temperature process:
Gibbs free DG = DHsys -TDSsys
energy (G)

DG < 0 The reaction is spontaneous in the forward direction.

DG > 0 The reaction is nonspontaneous as written. The
reaction is spontaneous in the reverse direction.
DG = 0 The reaction is at equilibrium.
 The standard free-energy of reaction (DG0rxn) is the free-
energy change for a reaction when it occurs under standard-
state conditions.
aA + bB cC + dD
DGrxn
0
= [ cDG0f (C) + dDG0f (D) ] - [ aDG0f (A) + bDG0f (B) ]
DGrxn
0
= S nDG0f (products) - S mDG0f (reactants)

Standard free energy of

formation (DG0f ) is the free-energy
change that occurs when 1 mole
of the compound is formed from its
elements in their standard states.
DG0f of any element in its stable
form is zero.

18.5
 ΔH ΔS ΔG

Change in enthalpy Change in entropy Change in Gibbs free

energy
Δ H˂ 0 exothermic Δ S˂ 0 order Δ G˂ 0 Spontaneous
Δ H˃ 0 endothermic Δ S˃ 0 disorder Δ G˃ 0 Non-spontaneous
KJ/mol J / [Link] KJ/mol
State function State function State function
ΔHo formation of stable ΔSo = 0 for perfect ΔGo formation of stable
element at 25oC and 1 crystalline substance element at 25oC and 1 atm.
atm. = 0 at 0K =0
Example 2.4 What is the standard free-energy change for
the following reaction at 25 0C?

2C6H6 (l) + 15O2 (g) 12CO2 (g) + 6H2O (l)

DGrxn
0
= S nDG0f (products) - S mDG0f (reactants)

DGrxn
0
= [12DG0f (CO2) + 6DG0f (H2O)] - [ 2DG0f (C6H6)]

DGrxn
0
= [ 12x–394.4 + 6x–237.2 ] – [ 2x124.5 ] = -6405 kJ

Is the reaction spontaneous at 25 0C?

DG0 = -6405 kJ < 0

spontaneous

18.5
DG = DH - TDS

18.5
 Temperature and Spontaneity of Chemical Reactions

CaCO3 (s) CaO (s) + CO2 (g)

ΔH 0 = 177.8 kJ Equilibrium Pressure of CO2

ΔS 0 = 160.5 J/K

ΔG 0 = ΔH 0 – T ΔS 0
At 25 0C, Δ G 0 = 130.0 kJ

ΔG 0 = 0 at 835 0C

The nearest highest temperature

Above 835oC causes the reaction
To be spontaneous as written

18.5
 Gibbs Free Energy and Phase Transitions

DG0 = 0 = DH0 – TDS0

H2O (l) H2O (g)

DH 40.79 kJ
DS = =
T 373 K
= 109 J/K

18.5
Example 2.5:
The molar heats of fusion and vaporization of benzene are 10.9
kJ/mol and 31.0 kJ/mol, respectively. Calculate the entropy
changes for the solid to liquid and liquid to vapor transitions
for benzene. At 1 atm pressure, benzene melts at 5.5°C and
boils at 80.1°C.

for the solid to liquid

Δ H 10.9 kJ/mol
ΔS = = = 0.0391 kJ/K =39.1 J/K. mol
T 278.5K

For liquid to vapor

You try it
Example 2.6: At what temperatures is the following process
spontaneous at 1 atm? What is the normal boiling point of Br2?
(DS° =93.0 J K-1mol-1, DH = 31.0 K J mol-1)
Br2 (l)  Br2 (g)
DG°= DH° - TDS°

The system is at equilibrium DG° = 0

DH° = TDS°
T = DH°/DS° = 31x1000J/ 93J/[Link]
= 333.33K = 60.33°C
 Gibbs Free Energy and Chemical Equilibrium

DG = DG0 + RT lnQ

R is the gas constant (8.314 J/K•mol)

T is the absolute temperature (K)

Q is the reaction quotient Q = [Products] / [Reactants]

At Equilibrium

DG = 0 Q=K

0 = DG0 + RT lnK
DG0 = - RT lnK Equilibrium constant

18.6
Free Energy Versus Extent of Reaction

DG0 < 0 DG0 > 0

18.6
DG0 = - RT lnK

18.6
Example 2.7:
Using data listed in Appendix 3, calculate the equilibrium
constant (KP) for the following reaction at 25°C:

DG 0 = - RT lnK
Example 2.8:
The equilibrium constant ( KP) for the reaction
is 0.113 at 298 K, which corresponds to a standard free-
energy change of 5.40 kJ/mol. In a certain experiment, the
initial pressures are PNO2= 0.122 atm and PN2O4 = 0.453 atm.
Calculate ΔG for the reaction at these pressures and predict
the direction of the net reaction toward equilibrium.

Spontaneous from left to right

 Example: For the reaction; NH4Cl (g)  NH3 (g) + HCl (g)
,DS°= 285J/K , DH°= 177KJ and DG° = 91.9KJ at 25°C.
i) Is the reaction spontaneous at 25°C?
ii)Assume that DH and DS do not change with temperature;
calculate DG at 500°C.
iii) Is the reaction spontaneous at 500°C ?
i) since DG° is +ve value (+91.9KJ) the reaction is
nonspontaneous.
 ii) DG = DH° - T DS°
T = 500 + 273 = 773K

DG = 177 – 773x285/1000 = 177 – 220.3 = - 43.3 KJ.

iii) since DG is –ve value ( -43.3KJ) at 500°C, the reaction is
spontaneous.