Entropy, Enthalpy, Gibbs Free Energy

and the Spontaneity of Reactions

Examples of Spontaneous Process/Reactions

• Melting of Ice
• Freezing of water
• Gasoline burning
• Block of wood dropped into the ground

– A spontaneous process might need a little “push”

to proceed.
 2nd Law of Thermodynamics and Entropy

• All real processes occur spontaneously in the

direction that increases the entropy of the
universe. ∆Suniv > 0
• ∆Suniv = ∆Ssys + ∆Ssurr > 0

• Entropy is affected by: Temperature, phase

changes, dissolving a solid or liquid, dissolving
a gas and atomic size.
Spontaneous Exothermic Reactions
1. C6H12O6 (s) + 6 O2 (g)  6 CO2 (g) + 6 H2O (g) +
heat
• 6 moles of gas yields 12 moles of gas and heat
∆Ssys > 0, ∆Ssurr > 0, ∆Suniv > 0

2. CaO (s) + CO2 (g)  CaCO3 (s) + heat

• Gas has been transformed to solid
∆Ssys < 0, ∆Ssurr >> 0, ∆Suniv > 0
 Spontaneous Endothermic Reactions

1. Melting of ice
• ∆Ssys increases even more outweighing ∆Ssurr!
∆Ssys >> 0, ∆Ssurr < 0, ∆Suniv > 0

2. Dissolving of Ionic Compounds

NaCl (s) + H2O (l)  Na+ (aq) + Cl- (aq)
• ∆Ssys increases even more outweighing ∆Ssurr!
∆Ssys >> 0, ∆Ssurr < 0, ∆Suniv > 0
 FAQs About Entropy
• How do we define entropy quantitatively?

• What about for irreversible processes?

• Like Internal Energy (U), is entropy (S) a state

function?

• When will change in entropy (∆S) be equal to zero?

 V1
V2
- Probability of finding a gas molecule in V1 is
Wi= Vi/Vf

- Probability of finding a gas molecule in V2 is

Wf= Vf/Vf = 1
- Probability of finding N gas molecule in V1 is
Wi= (Vi/Vf)N

- Probability of finding N gas molecule in V2 is

Wf= (1)N
Spontaneous process progresses in direction of increase
probability

entropy is defined as
S=k ln W “Boltzmann’s equation”
S = Sf - Si
*Higher probability (w)
= k ln Wf – k ln Wi means more ways
= k ln (Wf/Wi)
*More ways lead to higher
disorder
For gas expansion

S = k ln (1)N/(Vi/Vf)N = k ln (Vf/Vi)N
= Nk ln (Vf/Vi) = nR ln (Vf/Vi)
 Using 1st law
reversible isothermal expansion of gas from Vi Vf

w = -nRT ln Vf/Vi
U = 0
qrev = nRTln Vf/Vi

qrev/T = nRln (Vf/Vi)

We can see that

S = qrev/T
 Change in Enthalpy (∆H)
• The heat transferred/released at constant
pressure.

• ∆U = Q + W
• Q = ∆U - W @ constant P, W = -P∆V
• Q = ∆U + P∆V = ∆H

• Enthalpy (H) is the thermal energy at constant

pressure.
 Gibbs Free Energy (G)
• The useful energy available from the system.
• G = H – TS

• Change in free energy (∆G) is a measure of the

spontaneity of the process.
– Neglects two separate measurements of
spontaneity: ∆Ssys and ∆Ssurr
• ∆Suniv = ∆Ssys + ∆Ssurr * ∆Ssurr = -∆Hsys/T

• ∆Suniv = ∆Ssys - ∆Hsys/ T

• (∆Suniv = ∆Ssys - ∆Hsys/ T) x T

• -T ∆Suniv = ∆Hsys - T∆Ssys *G = H – TS

• ∆Gsys = ∆Hsys - T∆Ssys
• ∆G < 0  spontaneous
• ∆G > 0  non-spontaneous
• ∆G = 0  at equilibrium
∆G and the Work a System Can do
• The maximum work is done by a spontaneous
process only if the work is carried out
reversibly.

• But in any real process, work is performed

irreversibly, so we can never obtain the
maximum work.
 KEYPOINTS
• A spontaneous reaction (∆Gsys < 0) will occur and
can do work on the surroundings. However W <
Wmax because some of ∆G is released as heat.

• A non-spontaneous reaction (∆Gsys > 0) will not

occur unless the surroundings do work on it.
However W > Wmin because some of ∆G used is
lost as heat.