Entropy and Gibbs Energy

CHAPTER 9
ENTROPY AND GIBBS ENERGY

The Laws of Thermodynamics
The First Law of Thermodynamics
The law of conservation of energy:
In a thermodynamic system, the total energy
remains constant
(No)
(yes)
The internal energy can change as the result of
transfers of energy into or out of the system
Whenever a thermodynamic system undergoes a

physical or chemical change, the change of internal
energy (∆U) of the system = the difference between
the heat absorbed and work done.
• Heat
• Work done by the expansion of a gas:
Enthalpy (H)
When the system undergoes a physical/chemical change

at constant pressure (isobaric process):
The change in enthalpy at constant pressure

is equivalent to heat
The work done by the expansion of a gas:

Enthalpy of chemical reactions ()
• ΔH is negative: exothermic reaction
• ΔH is positive: endothermic reaction
Exothermic reaction
C (s) + O2 (g)  CO2 (g)
standard enthalpy of formation of CO2

Standard enthalpy of formation
The change in enthalpy when 1 mole of a substance is
formed from its pure elements under standard
conditions (at 25 oC, 1 atm).
C (s) + O2 (g)  CO2 (g) CO2
2C (s) + 2O2 (g)  2CO2 (g) 2x CO2

Using the standard enthalpy of formation values, you
can calculate the standard enthalpy of any chemical
reaction:
Calculate the standard enthalpy of the reaction above,
knowing that the standard enthalpies of formation for
these substances are: NH3(g), -45.9; CO2(g), -393.5;
NH2CONH2(aq), -319.2; and H2O(l), -285.8 (kJ/mol).
kJ/mol
Hess’s law
The enthalpy of a specific reaction is equal to the sum

of the enthalpies of reaction for any set of reactions
which in sum are equivalent to the overall reaction
(under the same conditions).
Using the Hess’s law, prove that:
Entropy (S)
the degree of randomness/state of disorder of a system
∆ 𝑆=𝑆 𝑓𝑖𝑛𝑎𝑙 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙

Entropy (S)
the degree of randomness/state of disorder of a system
∆ 𝑆=𝑆 𝑓𝑖𝑛𝑎𝑙 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙

The Third Law of Thermodynamics
A substance that is perfectly crystalline at 0 K has an

entropy of zero.
Do you expect the entropy to increase or decrease
in the following reactions?
Standard entropy of NH3(g), CO2(g), NH2CONH2(aq), H2O(l):

193; 214; 174; 70 (J.mol-1.K-1 )
Fe (s) + O2 (g)  Fe2O3 (s)
A spontaneous process is a physical or chemical change

that occurs by itself and requires no external energy to
make it happen.
A non-spontaneous process requires external energy
to make it happen.
The Second Law of Thermodynamics
The total entropy of a system and its surroundings

always increases for a spontaneous process.
• ∆Suniverse > 0: the process is spontaneous

• ∆Suniverse < 0: the process is non-spontaneous
Diffusion is a process driven by entropy
Low entropy High entropy

Gibbs free energy (G)
• ∆G < 0  ∆Suniverse >0: the process is spontaneous

• ∆G > 0  ∆Suniverse <0 : the process is non-spontaneous
• ∆G = 0: the process is at equilibrium
exergonic = spontaneous endergonic = non-spontaneous
Standard free energy of formation
The change in free-energy when 1 mole of a substance
is formed from its pure elements under standard
conditions (at 25 oC, 1 atm and 1 M for species in
solution).
Calculate the standard free energy of the following reaction:
-175 0 -394 -229

(kJ/mol)
A reversible reaction goes in which direction?
Equilibrium constant (Keq)
𝐾 eq
Relationship between Free energy change of reaction
() and Equilibrium constant (Keq)
The free energy change of a reaction () depends on the

concentrations of both its reactants and its products.
For a reaction at equilibrium, = 0
o
∆ G =− R . T . ln K eq 𝐾 eq
Example: Calculate the equilibrium constant Keq
at 25°C for the reaction
kJ/mol
(R = 8.314 J mol-1 K-1)

Free energy change during a reaction
(The energy barrier between S and P)
activation
energies
𝒐
∆𝑮
A higher activation energy corresponds to a slower reaction

How Biological Systems Deal With The Laws Of
Thermodynamics
A living organism is an open system
Living organisms exchange matter and energy with

its surroundings
Creating and Maintaining Order
Requires Energy
The synthesis of macromolecules (nucleic acids, proteins,
polysaccharides…): non-spontaneous processes
Coupling of Reactions
Many important biochemical processes are
thermodynamically unfavorable, or non-spontaneous.
a non-spontaneous reaction + a spontaneous reaction (coupling)
 the overall process is spontaneous
(kJ/mol)
Enzymes (catalysts) Increase The Reaction Rate
𝐨
∆𝐆
The reaction reaches equilibrium much faster

Enzymes (catalysts) Increase The Reaction Rate
The catalyst does not affect reaction equilibrium

SUMMARY
Following the laws of thermodynamics, living organisms

extract energy from their surroundings and employ it to
maintain life and do useful work.

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CHAPTER 9

ENTROPY AND GIBBS ENERGY

Whenever a thermodynamic system undergoes a

When the system undergoes a physical/chemical change

The change in enthalpy at constant pressure

The work done by the expansion of a gas:

standard enthalpy of formation of CO2

C (s) + O2 (g)  CO2 (g) CO2

2C (s) + 2O2 (g)  2CO2 (g) 2x CO2

The enthalpy of a specific reaction is equal to the sum

∆ 𝑆=𝑆 𝑓𝑖𝑛𝑎𝑙 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙

∆ 𝑆=𝑆 𝑓𝑖𝑛𝑎𝑙 − 𝑆𝑖𝑛𝑖𝑡𝑖𝑎𝑙

A substance that is perfectly crystalline at 0 K has an

Standard entropy of NH3(g), CO2(g), NH2CONH2(aq), H2O(l):

A spontaneous process is a physical or chemical change

The total entropy of a system and its surroundings

• ∆Suniverse > 0: the process is spontaneous

Low entropy High entropy

• ∆G < 0  ∆Suniverse >0: the process is spontaneous

-175 0 -394 -229

The free energy change of a reaction () depends on the

For a reaction at equilibrium, = 0

(R = 8.314 J mol-1 K-1)

A higher activation energy corresponds to a slower reaction

Living organisms exchange matter and energy with

The reaction reaches equilibrium much faster

The catalyst does not affect reaction equilibrium

Following the laws of thermodynamics, living organisms

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