The Second Law of Thermodynamics

Recall:
Mechanism of Heat Transfer
 If two systems with different temperatures comes into contact

𝑇𝐻 𝑇𝐶
𝑇𝐻 𝑇𝐶
Heat Transfer

𝑇 𝐻 >𝑇 𝐶 𝑇 𝐻 =𝑇 𝐶
 The system/region with a higher temperature will transfer some heat to the system/region with
lower temperature.

 Heat transfer will only decline if the systems in contact are in the same temperature
 Thermal Equilibrium

Zeroth Law of Thermodynamics

 That is why…
However thermodynamic processes that occur in nature are irreversible!

 A coffee in a cup will drop in temperature as time

goes by due to the air around it having less
temperature.
 However you can never observe a cup of coffee
sitting in open air increase its temperature without
adding any heat/work.

Heat Flow
𝑇 𝑐𝑜𝑓𝑓𝑒𝑒 𝑇 𝑎𝑖𝑟

Heat Flow
𝑇 𝑐𝑜𝑓𝑓𝑒𝑒 𝑇 𝑎𝑖𝑟
Common Misconception: Mo gawas ang aircon!

Luh, d mani ni
siya kabalo ug
Sirado lge ang pultahan thermodynamics
ba! Kay mo gawas ang ka uie! Hahaha!
bugnaw sa aircon!
However thermodynamic processes that occur in nature are irreversible!

 Gases always increase its volume.

 Free expansion

 However, you can never see a free gas converging

into a single point or volume.
However thermodynamic processes that occur in nature are irreversible!
Heat Engines
 Convert heat to mechanical work.
 Run by burning coal, oil, or gas [working substance].
Source at relatively high temperature
Recall that for a cyclic process:

𝑈 2 − 𝑈 1 =𝑄 −𝑊 =0
𝑄=𝑊

For one cycle …

𝑄=|𝑄 𝐻|−|𝑄 𝐶|

𝑊 =𝑄=|𝑄 𝐻|−|𝑄 𝐶|
Define “efficiency”:

Discarded heat at relatively low temperature

𝑒=
𝑊
𝑄𝐻
𝑒=1 −
𝑄𝐶
𝑄𝐻 | |
Thermal Efficiency of an Engine
Source at relatively high temperature Thermal Efficiency of an Engine

𝑒=1 −
𝑄𝐶
𝑄𝐻 | |
In order to have a perfect engine (100% efficient):

𝑒=1 −
𝑄𝐶
𝑄𝐻 | | 𝑄𝐶 =0
𝑒=1
No work can be extracted if :

𝑒=1 −
𝑄𝐶
𝑄𝐻 | | 𝑄𝐶 =𝑄 𝐻
𝑒=0

Therefore realistically , hence the efficiency:

Discarded heat at relatively low temperature 𝑒< 1

Internal Combustion Engines
 Gasoline Engines  Mixture of air and gas
 Highly idealize model vapor

 Efficiency depends on the type of gasoline

1
𝑒=1 − ( 𝛾 −1 )
 For ordinary (unleaded)  For high octane (special)
𝑟
Thermal Efficiency in Otto cycle
10 ≥ 𝑟 ≥ 8 13 ≥ 𝑟 ≥10
Refrigerators
 Reverse Heat Engine

Energy Diagram of Heat Engine Energy Diagram of Refrigerators

 |𝑄 𝐶| |𝑄𝐶|
𝐾= =
|𝑊 | |𝑄 𝐻|−|𝑄𝐶|
Coefficient of Performance
 |𝑄 𝐶| |𝑄𝐶|
𝐾= =
|𝑊 | |𝑄 𝐻|−|𝑄𝐶|
Coefficient of Performance
The Second Law of Thermodynamics

It is impossible for any system to

undergo a process in which it
absorbs heat from a reservoir at It is impossible for any process to
a single temperature and have as its sole result the
converts heat completely into transfer of heat from a cooler to
mechanical work, with the a hotter body.
system ending in the same state
in which it began.
The Carnot Cycle
• No perfect engine
• How to get the maximum efficiency
given two reservoirs and ?
• There must be no heat flow (adiabatic)
between the engine and the reservoir

Reflections of the
Said Carnot motives of Fire, a book
published by S. Carnot
regarding his work on
heat engines.
𝑝 Steps of the Carnot Cycle
1) The gas expands isothermally at temperature ,
absorbing heat (ab).
2) It expands adiabatically until its temperature
drops to (bc).
𝑇𝐻 3) It is compressed isothermally at , rejecting
heat (cd).
𝑇𝐶 4) It is compressed adiabatically back to its
𝑉 initial state at temperature (da).

𝑒=1 −
𝑇𝐶
𝑇𝐻
=
| |
𝑇 𝐻 −𝑇 𝐶
𝑇𝐻
Efficiency of a Carnot Engine
 Steps of the Carnot Cycle
1) The gas expands isothermally at temperature ,
absorbing heat (ab).
2) It expands adiabatically until its temperature
drops to (bc).
3) It is compressed isothermally at , rejecting
heat (cd).
4) It is compressed adiabatically back to its
initial state at temperature (da).

𝑒=1 −
𝑇𝐶
𝑇𝐻 | |
=
𝑇 𝐻 −𝑇 𝐶
𝑇𝐻
Efficiency of a Carnot Engine
ENTROPY

• Quantification the tendency of heat energies

to decay over time
• Internal property that changes as heat
energy moves around within a system

Δ𝑄
Δ 𝑆=
𝑇
Entropy

For a system that doesn’t undergo heat change /

reversible thermodynamic process (e.g. Carnot
Cycle):

Rudolf Clausius
Δ 𝑆=0
ENTROPY

• Quantification the tendency of heat energies

to decay over time
• Internal property that changes as heat
energy moves around within a system

Δ𝑄
Δ 𝑆=
𝑇
Entropy

For any non-reversible process / Heat change

occurs (e.g. Real Engines):

Rudolf Clausius Δ 𝑆>0

Therefore, entropy always increase!!!
ENTROPY

• However, it can be though of as how evenly

spread energy is distributed within a system.
• For an isolated system:

Δ 𝑆=𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
• However, in reality it will always increase
unless there is energy outside the system
that will re-establish the temperature
difference

“As one goes forward in time, the net entropy (degree of

disorder) of any isolated or closed system will always increase
(or at least stay the same).
 ENTROPY
(Statistical Interpretation)
Microstate
• position and momentum of
individual particle, and number
of particles

Macrostate
• pressure, volume, & temperature

𝑆=𝑘 ln { Ω } Statistical Mechanics

Entropy in terms of Microstates
Physics Misconception: Entropy the measurement of disorder

 The definition of entropy as a measure of

disorder purely comes from a statistical
standpoint.

 When a system reaches thermal

equilibrium, it reaches a state of
indistinguishability .

IT DOES NOT EXPLAIN HOW MESSY

YOUR ROOM IS or HOW CHAOTIC THE
WORLD HAS BECOME.
 The idea of disorder comes to the fact that all
thermodynamic systems always go to thermal
equilibrium.
 And you can never reset the temperature differential
of a system unless acted upon an external work