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Lecture 4: Combining First and Second Laws of Thermodynamics (Fundamental Equations)

This document summarizes fundamental equations relating thermodynamic state functions using the first and second laws of thermodynamics. It discusses how the fundamental equation can be expressed in terms of natural variables like U(S,V) or H(S,p). It also outlines the criteria for spontaneity in terms of entropy change and how the Helmholtz and Gibbs free energies relate to maximum work for closed systems under different conditions. Finally, it demonstrates calculating entropy changes for reversible and irreversible processes using the fundamental equations.

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Chegg Bolthe
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72 views13 pages

Lecture 4: Combining First and Second Laws of Thermodynamics (Fundamental Equations)

This document summarizes fundamental equations relating thermodynamic state functions using the first and second laws of thermodynamics. It discusses how the fundamental equation can be expressed in terms of natural variables like U(S,V) or H(S,p). It also outlines the criteria for spontaneity in terms of entropy change and how the Helmholtz and Gibbs free energies relate to maximum work for closed systems under different conditions. Finally, it demonstrates calculating entropy changes for reversible and irreversible processes using the fundamental equations.

Uploaded by

Chegg Bolthe
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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Download as PDF, TXT or read online on Scribd
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Lecture 4: Combining First and

Second laws of Thermodynamics


(Fundamental Equations)

Arti Dua

Department of Chemistry

IIT Madras

!
Fundamental Equations

Fundamental equations relates states function like U, S, T, P, H,V... using first and
second laws.

First Law:
Need to express it in terms of a state function

Second Law:

For Reversible Process:

Fundamental Equation :

Valid for irreversible processes since it only depends on state variables.


Natural variables for U are S and V: U(S,V)

H(S, p)
Criteria for Spontaneity
Recall:

For constant volume,



non-expansion work

For an isolated system (defined in terms of the independent variables U,V and N),

the direction of spontaneous change is the direction of increasing entropy for an

irreversible process

Criteria for Spontaneity

At constant pressure

For an isolated system (defined in terms of the independent variables H, p and N),

the direction of spontaneous change is the direction of increasing entropy for an

irreversible process

Criteria for Spontaneity

Helmholtz Energy:
Gibbs Energy:

At constant Temperature:

For a closed system, defined in terms of the independent variables (T, V, N) or (T, p,N),

the direction of spontaneous change is the direction of decreasing Helmholtz or Gibbs

energies, respectively.

The Gibbs Energy

It’s an important quantity in chemistry because p and T are under our control.

At constant temperature and pressure, chemical reactions are spontaneous in the


direction of decreasing Gibbs energy
Fundamental Equations

Helmholtz Energy:
Gibbs Energy:

For a closed system we have introduced all the state functions

Fundamental Equations:
Helmholtz Free Energy and Maximum Work

For reversible process


At constant temperature

Maximum Work
Gibbs Free Energy and Maximum Non-Expansion Work

At constant temperature

Use H = U + pV
For reversible process

At constant pressure

Maximum Non-Expansion Work

can be used to assess the electrical work.


Calculation of entropy change for reversible and irreversible processes
from fundamental equations
dU = T dS pdV Fundamental equation
Adiabatic reversible expansion !
of an ideal gas dU p
dS = + dV
T T
Surroundings
CV dT dV Ideal gas
gas (V1) dS = + nR
T V
Isolated system ✓ ◆ ✓ ◆
T2 V2
Ssys = CV ln + nR ln
V1 !T1V2 V1
✓ ◆ ✓ ◆ 1
V 1 ! V2 T2 V1 On a reversible adiabat
Since =
T1 V2
Surroundings
=) Ssys = 0
gas (V2)
Suniverse = 0 For a reversible process in an isolated system
Isolated system
=) Ssurr = 0
Calculation of entropy change for reversible and irreversible processes
from fundamental equations
Free expansion !
of an ideal gas! dU = T dS pdV Fundamental equation
(irreversible process)
0
dU p dw = 0, dq = 0
dS = + dV
Surroundings T T =) dU = 0

gas (V1) ✓ ◆
dV
dS = nR Ideal gas
Isolated system V
✓ ◆
V2
Ssys = nR ln
V 1 ! V2 V1
Surroundings Since no heat is transferred and
Ssurr = 0 work is done by the surroundings
gas (V2)
✓ ◆
Isolated system V2
=) Suniverse = nR ln
V1
Entropy of an isolated system (universe) increases in
an irreversible process (Second law)
Calculation of entropy change for reversible and irreversible processes
from fundamental equations

Reversible isothermal ! dU = T dS pdV Fundamental equation


expansion an ideal gas! 0
dU p dU = 0 for an ideal gas
dS = + dV
Surroundings T T at constant T
gas (V1) ✓ ◆
Closed system
dV Ideal gas
dS = nR
V
Constant T ✓ ◆
V2
V 1 ! V2
Ssys = nR ln
V1
Surroundings ✓ ◆
V2 Since surroundings do work
Ssurr = nR ln
gas (V2) V1 on the system

Closed system

Constant T
=) Suniverse = 0

Entropy of an isolated system (universe) is zero


a reversible process (Second law)

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