2nd + 3rd Law

Wednesday, August 19, 2015

12:29 PM

2nd Law of Thermodynamics

In text form:
Kelvin: No process exists where it only converts Q completely into W
Clausius: No process exists where heat goes from low T to higher T

Formula Form:
Total entropy change is always positive

Entropy
A system will always go from ordered to disordered
Classical (From Heat Engine Analysis)

Microscopic (Boltzmann)

Relating Entropy to Conservation of Energy

Special Cases which we can use to calculate

At phase transition ( T and P are constant)

For Ideal Gases (Derived from dQ = dU + PdV)

form

form

Notes Page 1

Heat Engines

Definitions
Reservoir Unlimited capacity for absorbing / rejecting heat without

Entropy (Of resevoirs)

Work Done (On / by the engine)

Efficiency (With ref to engine)

Note that the maximum occurs when

Also note that max efficiency is independent of

Carnot Heat Engines

Notes Page 2

Carnot Heat Engines

These are engines which have the highest efficiency (

and represent a reversible process.

Process
System is initially at
1.
2.
3.
4.

Adiabatic Compression to Heat System,

Isothermal expansion,
from Hot Reservoir
Adiabatic Expansion to Cool System,
Isothermal compression,
to Cold Reservoir

All processes in the engine are reversible

Proof of Efficiency
Consider an engine with

As a result, to produce the same amount of work

, you require less heat

Suppose you run this engine, taking the work produced and using it to run the Carnot engine in reverse.

The amount of heat leaving the cold reservoir is

The amount of heat entering the hot reservoir is

This means that the sole result of this machine is for heat to leave the cold reservoir and enter the hot
reservoir which violates the
law.
Notes Page 3

reservoir which violates the

law.

Carnot Equation

This is derived by

for the engine and applying the concept

Entropy Balances
Closed Systems

Open Systems
+ Change in

In other words,
// General Form

// Uniform Temp

// Steady State

// Closed System

// Integrated over time

Calculations
Use this step by step process
1. Mass Balance
2. Energy Balance
3. Entropy Balance

Notes Page 4

= 0.

3rd Law of Thermodynamics

In text form
All substances lose their energy at

In formula form
@

Notes Page 5