Entropy, Free Energy,

and Equilibrium
Chemical Thermodynamics
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Gibbs Free Energy and Chemical Equilibrium

Spontaneous process:
Equilibrium process:
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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 oC and ice melts above 0 oC
• 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
• Một thác nước chảy xuống đồi
• Một miếng đường tan trong một tách cà phê
• Ở 1 atm, nước đóng băng dưới 0 oC và băng tan trên 0 oC
• Nhiệt chảy từ vật nóng hơn sang vật lạnh hơn
• Khí mở rộng trong bóng thủy tinh được bơm chân không 2
• Sắt tiếp xúc với oxy và nước tạo thành gỉ
 spontaneous

nonspontaneous

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Does a decrease in enthalpy mean a reaction proceeds
spontaneously?

Spontaneous reactions

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

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

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

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

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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 5

 Entropy
S = k ln W W = number of microstates
Wf
DS = Sf - Si DS = k ln (k is the Boltzmann constant)
Wi
Wf > Wi then DS > 0 Wf < Wi then DS < 0

Distributing four particles among two boxes will result in 24

= 16 different microstates

“most probable distribution”

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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

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

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Example: Br2(l) Br2(g) Example: I2(s) I2(g)

DS > 0 DS > 0

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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 60 0C to 80 0C
Randomness increases Entropy increases (DS > 0)
(d) Subliming dry ice
Randomness increases Entropy increases (DS > 0)

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 Entropy

State functions are properties that are determined by the state

of the system, regardless of how that condition was achieved.
Examples:
energy, enthalpy, pressure, volume, temperature, entropy

Review

Potential energy of hiker 1 and hiker 2

is the same even though they took
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different paths.
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 (Nhiệt động lực học)

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

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 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 25 0C.
aA + bB cC + dD

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

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

What is the standard entropy change for the following

reaction at 25 0C? 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 14
 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.

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 Entropy Changes in the Surroundings (DSsurr)

Exothermic Process Endothermic Process

DSsurr > 0 DSsurr < 0

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Entropy Changes in the System and Surroundings
Why does crystallization of a solute occur?
1. Entropy of system: DSsys < 0

‘solute disorder(initial) > solute disorder(final)’

2. Entropy of surrounding: DSsurr > 0
‘solvent disorder(initial) < solvent disorder(final)’
3. Entropy of universe: DSsurr + DSsys > 0

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Entropy Changes in the System and Surroundings
Why is burning hydrogen gas in air (to form liquid water) a
spontaneous reaction?

1. Entropy of system: DSsys < 0, easily quantified

• Three gas molecules (intial) > Two molecules (final)

2. Entropy of surrounding: DSsurr > 0

• Surrounding air absorbs the energy (heat and sound)
liberated during the reaction:
• Quantification of the influence of the surroundings on the
reaction is usually not a trivial problem.

3. Entropy of universe: DSsurr + DSsys > 0 18

 Gibbs Free Energy
DSuniv = DSsys + DSsurr

DSsurr = -DHsys/T DSuniv = DSsys + -DHsys/T

TDSuniv = TDSsys + -DHsys

DG = -TDSuniv = DHsys - TDSsys

Spontaneous process: DSuniv > 0

DG = -TDSuniv = DHsys - TDSsys < 0

Nonspontaneous process: DSuniv < 0

DG = -TDSuniv = DHsys - TDSsys > 0

Nonspontaneous process: DSuniv = 0 , DG = 0 19

 Gibbs Free Energy

For a constant temperature and constant pressure 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.

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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.

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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/mol

Is the reaction spontaneous at 25 0C?

DG0 = -6405 kJ/mol < 0

spontaneous

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DG = DH - TDS

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 Temperature and Spontaneity of Chemical Reactions

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

Equilibrium Pressure of CO2

DH0 = 177.8 kJ/mol

DS0 = 160.5 J/K·mol
DG0 = DH0 – TDS0
At 25 oC, DG0 = 130.0 kJ/mol
DG0 = 0 at 835 oC

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 Gibbs Free Energy and Phase Transitions

DG0 = 0 = DH0 – TDS0

H2O (l) H2O (g)

DH 40.79 kJ/mol
DS = =
T 373 K

= 1.09 x 10-1 kJ/K·mol

= 109 J/K·mol
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 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

At Equilibrium

DG = 0 Q=K

0 = DG0 + RT lnK
DG0 = - RT lnK

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 Free Energy Versus Extent of Reaction

DG0 < 0 DG0 > 0

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DG0 = - RT lnK

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 Coupled Reactions

Example: Alanine + Glycine Alanylglycine

DG0 = +29 kJ K<1

ATP + H2O + Alanine + Glycine ADP + H3PO4 + Alanylglycine

DG0 = -2 kJ K>1
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 Mechanical Analog of Couple Reactions

Make the smaller weight move upward (a nonspontaneous

process) by coupling it with the falling of a larger weight.
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The Structure of ATP and ADP in Ionized Forms

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