The Carnot Cycle

Carnot Cycle form the perspective of the Pressure Volume diagrams

1
Values of U, q and w

2
Efficiency of Reversible Carnot Engine
w
Efficiency
qh
V2
R (Th Tc ) ln
V1

V2
RTh ln
V1
Th Tc

Th

3
Entropy
Definition
dq rev
T dS 0
Molecular Interpretation of Entropy
Entropy as a measure of disorder; an increase in
entropy means an increase in disorder
Entropy of Fusion
Entropy changes in Chemical Reactions

4
Calculation of Entropy Changes
For transition A B by a reversible path,
B
dq rev
S A B
A
T
fus H
Entropy of Fusion: fus S
T fus

Entropy of vap H
Vaporization: vap S
Tvap

Entropy Change in a trs H

Transition:
trs S
Ttrs
5
Entropy of Ideal Gases
S for Changing T and V
T2 V2
S nC V, m ln nRn
T1 V1

Entropy of Mixing per mole of mixture:

S R ( x1 ln x1 x 2 ln x 2 x3 ln x3 .....)

Entropy of Mixing in terms of Volume:

V1 V2 V1 V2
S n1 R ln n 2 R ln
V1 V2
6
Third Law of Thermodynamics
Entropy changes become zero at the absolute zero

Absolute S S ( products ) S (reac tan ts )

Entropies:

7
Conditions for Equilibrium

dStotal = dSsyst + dSsurr = 0

8
Conditions for Equilibrium
At Constant T and P At Constant T and V
(Gibbs Energy) (Helmholtz Energy)

At constant For constant volume

temperature, conditions,
dG = dH TdS dU TdS = 0

At equilibrium, At equilibrium,
dG = 0 dA = 0

9
Gibbs Energies of Formation

G o f G o ( products ) f G o (reac tan ts )

G o 0 (reaction at equilibrium)
G o negative (spontaneous reaction process)
G o positive (non - spontaneous reaction process)

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Gibbs Energy and Reversible Work
V1 P2
wrev nRT ln nRT ln
V2 P1
V2
q rev nRT ln
V1
q rev V2
S nR ln
T V1
G H TS
V1 P2
nRT ln nRT ln
V2 P1
11
Some Applications of Thermodynamics
Relationships
1. Theory of Joule - Thomson Effect
1 H
-
CP P T

2. Thermal Expansivity (Cubic expanion coefficient)

1 V

V T P
Isothermal compressibility
1 V

V P T
3. Internal Pressure (van der Waals equation)
U a

V T Vm2 12
Fugacity and Activity
For an isothermal process involving 1 mol of ideal gas,
V1 P
G m RT ln RT ln 2
V2 P1
If the initial pressure P1 is 1 bar, the gas is in a standard state and we write its molar Gibbs energy as G om ;
the Gibbs energy at any pressure P is then
G m G om RT ln( P / bar )
If the gas is not ideal, this expression no longer applies.
In order to have a parallel treatment of real gases, a new function known as fugacity is
introduced with a symbol of f .
Hence, fugacity is the pressure adjusted for lack of ideality.
Therefore,
f
G m RT ln 2
f1
Defining the standard state to correspond to unit fugacity ,
G m G om RT ln( f / bar )
The ratio of the fugacity of a substance in any state to the fugacity in the standard sate is known
as the activity and given the symbol a. Hence,
G m G om RT ln a 13