LECTURE 11: 2nd AND 3rd LAW OF The 3rd Law of Thermodynamics

THERMODYNAMICS
- For a perfectly crystallin material, the
PART 1: PROPERTIES OF THE absolute entropy approaches zero
ENTROPY AND THE THIRD LAW OF as the absolute temperature
THERMODYNAMICS approaches zero.
- S = 0 (at T = 0K)
Relating Entropy (S) and Probability ()
Standard Molar Entropies, S°
- The standard or absolute entropy of
any substance refers to the entropy
change for the following process
involving one mole of the substance:
- For an isolated system, processes o Initial State: Perfect Crystal
tend to proceed in directions that at 0K, 1 bar
maximizes its probability up until a o Final State: Substance at
state with maximum probability 298K, 1 bar (behaving ideally
which is the equilibrium state if gaseous)
- S = S ()
- Total Entropy of System:
S = S1 + S 2
- The standard entropy of elements is
- Total probability of System:
not assigned a conventional value of
 = 1 x 2 zero!
- Since:
S(1 +2) = S(1) + S(2) = k ln1 +
k ln2
- Therefore: S = k ln 
Ludwig-Boltzmann definition of Entropy

- S = k ln 
o Where k = Boltzmann’s
Constant: R/NA = 1.38 x 10-23
J/K
o Where  is the number of
ways particles can be
arranged in the system
- For an Isolated System, energy is
conserved; it is the distribution of
energy which is related to entropy,
that determines the direction of
spontaneity
Entropy and Microstates
- System continuously loses heat?
o T0; S0;  = 1 - Experimental Determination:
o Measure Cp vs. T
o S = k ln  = k ln(1) = 0
 o Extrapolate Cp values to From Debye Extrapolation: Cp = aT3
absolute zero
o Integrate Cp/T from 0 to 298K
o Add ∆Strs for each phase
transition
Entropy Change in Vaporization
- Liquid  Vapor
- At Boiling point: T=Tb
- ∆H°vap = heat of vaporization

Standard Reaction Entropy, S°rxn

- For many liquids, the entropy of
vaporization at the normal boiling
point has approx. the same value: - Dependence with Temperature:
85J/k mol
- Trouton's rule fails for associated
liquids such as water, alcohols, and
amines (H-bonding). It also fails for
substances with boiling points of 150
K and below

- Calculating S°:

- If ΔCP is temperature-independent:

PART 2: SPONTANEITY AND

EQUILIBRIUM
Sample:
Criteria for Spontaneity
- For Isolated Systems: dSsys ≥0
o dSsys > 0; irreversible, spont.
o dSsys = 0; reversible, spont.
 o dSsys < 0; non-spont.
- For Non-Isolated Systems:
𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 𝑑𝑆𝑠𝑦𝑠𝑡𝑒𝑚 + 𝑑𝑆𝑠𝑢𝑟𝑟𝑜𝑢𝑛𝑑𝑖𝑛𝑔 ≥ 0
o 𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 > 0; irrev, spont.
o 𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 = 0; rev, spont.
o 𝑑𝑆𝑢𝑛𝑖𝑣𝑒𝑟𝑠𝑒 < 0; non-spont.
- Generalized criteria for spontaneity:
The Clausius Inequality.

Calculations of Gibbs Free Energy:

- Express 2nd Law in terms of other

system state function to find an
alternative criterion for spontaneity
at convenient conditions
o (isolated) At constant v, u:
(dS)v,u ≥ 0
o At dV=0, dS=0; (dU)v,s ≤ 0
o At dP=0, dS=0; (dH)P, S ≤ 0
o At constant T and V;
(dA)T,V ≤ 0 [Helmholtz Energy
(A)]
o At constant P and T;
(dG)P,T ≤ 0[Gibbs Free
Energy (G)] PART 3: MAXWELL THERMODYNAMICS
RELATIONS
Review: z = z (x, y); Total differential of z is:
Fundamental Thermodynamic functions for
closed systems.

Combining 1st and 2nd Law of (For Helmholtz Energy, A)

Thermodynamics:
dU = dq + dw
dqrev = T dS
dw = – P dV
dU = T dS – P dV
U (S, V)

(From Gibbs Free Energy, G)

(From Internal Energy, U)

THE SHORTCUT: THERMODYNAMIC

(From Enthalpy, H)
Z