Entropy and Free Energy

Chapter 5

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 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

5.1
 spontaneous

nonspontaneous

5.2
 Does a decrease in enthalpy mean a reaction
proceeds spontaneously?

Spontaneous reactions

CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) H0 = -890.4 kJ

H+ (aq) + OH- (aq) H2O (l) H0 = -56.2 kJ

H2O (s) H2O (l) H0 = 6.01 kJ

H2O
NH4NO3 (s) NH4+(aq) + NO3- (aq) H0 = 25 kJ

5.3
 Entropy (S) is a measure of the randomness or disorder of a system.

order S disorder S

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

5.4
• Heating hydrogen gas from 600C to 800C, Randomness
increases, and Entropy will increase (S > 0)
• Sublimation of dry ice (from solid into vapor state),
Randomness increases, and Entropy will increase (S > 0)

5.5
 Processes that lead to an increase in entropy (S > 0)

Melting

Boiling

Formation
of solution

Heating for
higher
temperature
5.6
 If the change from initial to final results in an decrease in
randomness
Sf < Si S < 0

• Condensation of water vapor into liquid state, Randomness

will decrease, and Entropy will decrease (S < 0)
• Forming sucrose crystals from a supersaturated solution,
Randomness will decrease, and Entropy will decrease (S < 0)

5.7
 Entropy is a state function (S = Sfinal – Sintial)
State functions are properties that are determined by the state of the
system, regardless of how that condition was achieved (path).
energy, enthalpy, pressure, volume, temperature, entropy

Potential energy of hiker 1 and hiker

2 is the same even though they took
different paths.
5.8
 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 (system + surrounding) increases
in a spontaneous process (S > 0)and remains unchanged in an
equilibrium process (S = 0).

Spontaneous process: Suniv = Ssys + Ssurr > 0

Equilibrium process: Suniv = Ssys + Ssurr = 0

5.9
 Entropy Changes in the System (Ssys)
When gases are produced (or consumed)
• If a reaction produces more gas molecules than it consumes, (the
number of gas moles of the products is higher than that of
reactants) S 0 > 0. The reaction will be spontaneous
H2O (l) H2 (g) + 1/2 O2 (g)

• If the total number of gas molecules diminishes (the number of

gas moles of the products is lower than that of reactants) , S 0 < 0.
The reaction will be non-spontaneous

2 Zn (s) + O2 (g) 2 ZnO (s)

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

5.10
• If there is no net change in the total number of gas molecules (the
number of gas moles of the products is equal to of reactants) S 0
may be positive or negative BUT S 0 will be a small number.

H2 (g) + Br2 (g) 2 HBr (g)

Entropy Changes in the System (Ssys)

The standard entropy of reaction (S0 rex) is the entropy change

for a reaction carried out at 1 atm and 250C.
aA+bB cC+dD

Srxn
0
= [c S0(C) +d S0(D) ] - [a S0(A) +b S0(B) ]

Srxn
0
= nS0(products) - mS0(reactants)

5.11
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
Srxn
0
= 2 x S0(CO2) – [2 x S0(CO) + S0 (O2)]
Srxn
0
= 427.2 – [395.8 + 205.0] = -173.6 J/K•mol

Calculate the standard entropy changes for the following

reactions at 25°C.

5.12
 Gibbs Free Energy
Spontaneous process: Suniv = Ssys + Ssurr > 0

Equilibrium process: Suniv = Ssys + Ssurr = 0

For a constant-temperature
process:
Gibbs free G = Hsys -TSsys
energy (G)

G “free energy” is the energy available to do work

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.
5.13
G = H - TS

5.14
The standard free-energy of reaction (DG0rex ) is the free-energy
change for a reaction when it occurs under standard-state
conditions.
aA+bB cC+dD
Grxn
0
= [cG0f (C) + dG0f (D)] - [aG0f (A) + bG0f (B)]
Grxn
0
= nG0f (products)- mG0f (reactants)

Standard free energy of formation

(G0) is the free-energy change that
f
occurs when 1 mole of the compound is
formed from its elements in their standard
states.
Gf0 of any element in its stable
form is zero.

5.15
What is the standard free-energy change for the following
reaction at 25 0C?

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

Grxn
0
= nG0f (products)- mG0f (reactants)

Grxn
0
= [ 12Gf0 (CO2) + 6G0f (H2O)] - [ 2Gf0 (C6H6) ]

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

Is the reaction spontaneous at 25 0C?

G0 = -6405 kJ < 0

spontaneous

5.16