Thermodynamics I

Thermodynamics 101
Aiko Huckauf
Preface
Introduction
Whats it all about?
Classical Thermodynamics
Thermodynamics 101
Statistical Thermodynamics
Fundamental Laws
0. Thermodynamic Equilibrium
1. Conservation of Energy
2. Increase of Entropy
3. Zero Temperature
Presentation given in the course of the

Masters Programme Environmental Management
Module 2.1.1 Ecosystem Analysis
Ecosystem Relevance
Closing Remark
References
Aiko Huckauf
Ecology Centre Kiel
2006-05-24
Thermodynamics 101
Aiko Huckauf
Preface
Preface
Introduction
Whats it all about?
Fundamental Laws
Thermodynamics is a terrible game:
3. Zero Temperature
0. You have to play.
Ecosystem Relevance
1. You cannot win.
Closing Remark
2. You cannot break evenexcept on a very cold day.
References
3. It does not get that cold.
Thermodynamics 101
Aiko Huckauf
Preface
Preface
Introduction
Whats it all about?
Fundamental Laws
Thermodynamics is a terrible game:
3. Zero Temperature
0. You have to play.
Ecosystem Relevance
1. You cannot win.
Closing Remark
2. You cannot break evenexcept on a very cold day.
References
3. It does not get that cold.
Thermodynamics 101
Aiko Huckauf
Introduction
Whats it all about?
Preface
Introduction
Whats it all about?
There are two different approaches to thermodynamics:
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Classical Thermodynamics is the branch of

physics concerned with the conversion of
different forms of energy.
Statistical thermodynamics is the branch of
physics that describes the thermodynamic
behavior of macroscopic systems on basis of
the properties of their molecular constituents.
Thermodynamics 101
Aiko Huckauf
Introduction
Classical Thermodynamics: How does it work?
Preface
Introduction
Whats it all about?
Fundamental Laws
As a phenomenological theory, it deals with

I
macroscopic objects (which contain a large

number of particles) and their
macroscopic properties (state variables like mass,

volume, pressure, temperature, energy, entropy,
and enthalpy)
that can be observed and measured in experiments
from which one can abstract and set up axioms

based on the empirical findings (phenomenology).
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Thermodynamics 101
Aiko Huckauf
Introduction
Classical Thermodynamics: How does it work?
Preface
Introduction
Whats it all about?
Fundamental Laws
As a phenomenological theory, it deals with

I
macroscopic objects (which contain a large

number of particles) and their
macroscopic properties (state variables like mass,

volume, pressure, temperature, energy, entropy,
and enthalpy)
that can be observed and measured in experiments
from which one can abstract and set up axioms

based on the empirical findings (phenomenology).
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Thermodynamics 101
Aiko Huckauf
Introduction
Classical Thermodynamics: What is it good for?
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
At its origins, during the

Industrial Revolution,
thermodynamics was
concerned with (steam)
engines and their efficiency.
Thermodynamics 101
Aiko Huckauf
Introduction
Classical Thermodynamics: Its Fathers
Preface
Introduction
Whats it all about?
Fundamental Laws
Sadi Carnots Reflections on the Motive Power of

Fire (1824) analyse the efficiency of steam engines
and mark the start of thermodynamics as a modern
science.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
William Thomson (1st Baron Kelvin aka Lord

Kelvin) invents the absolute temperature scale in
1848 and coins the term thermodynamics in
1849.
Rudolf Clausius ber die bewegende Kraft der
Wrme (1850) serves as a milestone of
thermodynamics. Clausius specifies the second law
idea of Carnot and later, in 1865, introduces the
macroscopic concept of entropy.
Thermodynamics 101
Aiko Huckauf
Introduction
Classical Thermodynamics: What Are Its Limits?
Preface
Introduction
Whats it all about?
Problems with classical thermodynamics:

I Many questions remain open:
I
Fundamental Laws
Why do all gases behave similarly?

Can temperature be negative?
What is this entropy thing, by the way?
3. Zero Temperature
Ecosystem Relevance
All constants and parameters have to be derived

from experiments. We have no clue about their
possible values.
It provides no information about the states or even

the existence of molecules.
It has only weak if any predictive power: We can

build a refrigerator, but we cannot design a proper
cooling fluid for itwe can only choose from those
we know.
Closing Remark
References
Thermodynamics 101
Aiko Huckauf
Introduction
Classical Thermodynamics: What Are Its Limits?
Preface
Introduction
Whats it all about?
Problems with classical thermodynamics:

I Many questions remain open:
I
Fundamental Laws
Why do all gases behave similarly?

Can temperature be negative?
What is this entropy thing, by the way?
3. Zero Temperature
Ecosystem Relevance
All constants and parameters have to be derived

from experiments. We have no clue about their
possible values.
It provides no information about the states or even

the existence of molecules.
It has only weak if any predictive power: We can

build a refrigerator, but we cannot design a proper
cooling fluid for itwe can only choose from those
we know.
Closing Remark
References
Thermodynamics 101
Aiko Huckauf
Introduction
Statistical Thermodynamics in a Nutshell
Preface
Introduction
Whats it all about?
The statistical approach is a first principle theory that

I
derives macroscopic properties (state variables and

functions)
from the constituent particles and the interactions

between them
by connecting thermodynamic functions to

atomistic phenomena (including quantum
mechanics).
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
It thus
I
gives thermodynamics a molecular interpretation

and
serves as a bridge between macroscopic and

microscopic system properties.
Thermodynamics 101
Aiko Huckauf
Introduction
Preface
Introduction
Whats it all about?

I

functions)

between them

mechanics).
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
It thus
I

and

Thermodynamics 101
Aiko Huckauf
Introduction
Preface
Introduction
Whats it all about?

I

functions)

between them

mechanics).
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
It thus
I

and

Thermodynamics 101
Aiko Huckauf
Introduction
Preface
Introduction
Whats it all about?

I

functions)

between them

mechanics).
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
It thus
I

and

Thermodynamics 101
Aiko Huckauf
Introduction
Statistical Thermodynamics: Its Fathers
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
James Clerk Maxwell describes the velocity

distribution of molecules in 1860, laying the
foundation for what is nowadays known as
Maxwell-Boltzmann kinetic theory of
gases.
Ecosystem Relevance
Closing Remark
References
In 1877, Ludwig Boltzmann shows the

logarithmic connection between entropy and
probabilitywhich is still the best definition
of entropy we have.
Thermodynamics 101
Aiko Huckauf
The Fundamental Laws of Thermodynamics

Preliminary Remark
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Classical thermodynamics is, like plane geometry, based

on axioms and postulates.
Only, in thermodynamics these are called laws.
Thermodynamics 101
Aiko Huckauf

Zeroth Law: Thermodynamic Equilibrium
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
When two systems are each in thermal

equilibrium with a third, they are in thermal
equilibrium with each other.
Closing Remark
References
I Thermal equilibrium means: The temperature gradient
between the two systems is zero, i. e. both systems are at the

same temperature.
Thermodynamics 101
Aiko Huckauf

Zeroth Law: Thermodynamic Equilibrium
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
When two systems are each in thermal

equilibrium with a third, they are in thermal
equilibrium with each other.
Closing Remark
References
I Thermal equilibrium means: The temperature gradient
between the two systems is zero, i. e. both systems are at the

same temperature.
Thermodynamics 101
Aiko Huckauf

First Law: Conservation of Energy
Preface
Introduction
Whats it all about?
Fundamental Laws
Energy (and hence matter) can neither be

created nor destroyed.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
I Energy can be transferred from one system to another.

I Energy can be transformed from one manifestation into
another: chemical, mechanical, thermal, electrical,

gravitational potential energy etc.
I The internal energy of an isolated system is constant: dU = 0.
I The internal energy of a closed system can only be changed
through heat transfer or work: dU = q + w.
Thermodynamics 101
Aiko Huckauf

First Law: Conservation of Energy
Preface
Introduction
Whats it all about?
Fundamental Laws
Energy (and hence matter) can neither be

created nor destroyed.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
I Energy can be transferred from one system to another.

I Energy can be transformed from one manifestation into
another: chemical, mechanical, thermal, electrical,

gravitational potential energy etc.
I The internal energy of an isolated system is constant: dU = 0.
I The internal energy of a closed system can only be changed
through heat transfer or work: dU = q + w.
Thermodynamics 101
Aiko Huckauf

Second Law: Increase of Entropy
Preface
Introduction
Whats it all about?
Fundamental Laws
The total entropy change (system +

surroundings) is always greater than or equal
to zero for any change of state of the system:
S > 0.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
I The entropy of an isolated system never decreases.

I Heat does not spontaneously flow from colder into warmer
systems (but always in the opposite direction).

I Energy of all types spontaneously flows from being localised or
concentrated to becoming more dispersed or spread out, if it is

not hindered.
I There are as many variations of the second law as there are
thermodynamicists.
Thermodynamics 101
Aiko Huckauf

Second Law: Increase of Entropy
Preface
Introduction
Whats it all about?
Fundamental Laws
The total entropy change (system +

surroundings) is always greater than or equal
to zero for any change of state of the system:
S > 0.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
I The entropy of an isolated system never decreases.

I Heat does not spontaneously flow from colder into warmer
systems (but always in the opposite direction).

I Energy of all types spontaneously flows from being localised or
concentrated to becoming more dispersed or spread out, if it is

not hindered.
I There are as many variations of the second law as there are
thermodynamicists.
Thermodynamics 101
Aiko Huckauf
Preface
Introduction
Whats it all about?
Fundamental Laws

What Is Entropy Anyway?
Classically, entropy measures the spontaneous dispersal
of energy: how much energy is spread out in a process
(and cannot be used to do thermodynamic work), or
how widely spread out it becomesat a specific
temperature: dS > q/T.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Statistically, it measures the amount of uncertainty that

would remain about the exact microscopic state of the
system, given a description of its macroscopic properties:
P
S = k i Pi ln(Pi ), where k is the Boltzmann constant
and Pi the probability of the ith microstate to be
occupied).
I Entropy is not disorder or a measure thereof. Rearranging objects does
not change their entropy.

I Classical entropy is always connected with energy in general, and
specifically with energy that is being or has been dispersed.

I Statistical entropy is not defined in terms of energy (nor vice versa),
but in terms of probability spread out in state-space.
Thermodynamics 101
Aiko Huckauf
Preface
Introduction
Whats it all about?
Fundamental Laws

What Is Entropy Anyway?
Classically, entropy measures the spontaneous dispersal
of energy: how much energy is spread out in a process
(and cannot be used to do thermodynamic work), or
how widely spread out it becomesat a specific
temperature: dS > q/T.
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Statistically, it measures the amount of uncertainty that

would remain about the exact microscopic state of the
system, given a description of its macroscopic properties:
P
S = k i Pi ln(Pi ), where k is the Boltzmann constant
and Pi the probability of the ith microstate to be
occupied).
I Entropy is not disorder or a measure thereof. Rearranging objects does
not change their entropy.

I Classical entropy is always connected with energy in general, and
specifically with energy that is being or has been dispersed.

I Statistical entropy is not defined in terms of energy (nor vice versa),
but in terms of probability spread out in state-space.
Thermodynamics 101
Aiko Huckauf

Third Law: Zero Temperature
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Absolute zero cannot be reached by any

procedure in a finite number of steps.
Ecosystem Relevance
Closing Remark
References
I All processes cease as temperature approaches zero.

I As temperature approaches zero, so does the entropy.
Thermodynamics 101
Aiko Huckauf

Third Law: Zero Temperature
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Absolute zero cannot be reached by any

procedure in a finite number of steps.
Ecosystem Relevance
Closing Remark
References
I All processes cease as temperature approaches zero.

I As temperature approaches zero, so does the entropy.
Thermodynamics 101
Aiko Huckauf
Ecosystem Relevance
Why Bother?
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Based on the macroscopic flow of energy (and matter),

thermodynamics is considered to be well suited to
describe ecosystems from an holistic point of view.
Closing Remark
References
Ecosystem Thermodynamics will be the subject of the

second part of this presentation, to be given on
2006-07-05.
Thermodynamics 101
Aiko Huckauf
Preface
Introduction
Whats it all about?
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References
Thermodynamics is a funny subject. The first

time you go through it, you dont understand it
at all. The second time you go through it, you
think you understand it, except for one or two
small points. The third time you go through it,
you know you dont understand it, but by that
time you are so used to it, it doesnt bother
you any more.
Ascribed to Arnold Sommerfeld (German
physicist and teacher, 18681951)
Thank you for your attention!
Thermodynamics 101
Aiko Huckauf
References
For Further Reading. . .
Preface
Introduction
Whats it all about?
Sven Erik Jrgensen and Felix Mller (Ed.): Handbook of

Ecosystem Theories and Management. CRC Press, Boca
Raton, 2000.
Sven Erik Jrgensen: Integration of Ecosystem Theories:

A Pattern. Kluwer Academic Publishers, Dordrecht,
1992.
Folke Gnthe: The Laws of Thermodynamics. Available

online at http://www.holon.se/folke/kurs/Distans/Ekofys/
fysbas/LOT/LOT.shtml.
David Watson: Energy Concepts for Educators and

Students. Available online at
http://www.ftexploring.com/energy/energy.html.
Fundamental Laws
3. Zero Temperature
Ecosystem Relevance
Closing Remark
References

Thermodynamics I

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Thermodynamics 101

Presentation given in the course of the

Thermodynamics is a terrible game:

0. You have to play.

1. You cannot win.

2. You cannot break evenexcept on a very cold day.

3. It does not get that cold.

Thermodynamics is a terrible game:

0. You have to play.

1. You cannot win.

2. You cannot break evenexcept on a very cold day.

3. It does not get that cold.

There are two different approaches to thermodynamics:

Classical Thermodynamics is the branch of

As a phenomenological theory, it deals with

macroscopic objects (which contain a large

macroscopic properties (state variables like mass,

that can be observed and measured in experiments

from which one can abstract and set up axioms

As a phenomenological theory, it deals with

macroscopic objects (which contain a large

macroscopic properties (state variables like mass,

that can be observed and measured in experiments

from which one can abstract and set up axioms

At its origins, during the

Sadi Carnots Reflections on the Motive Power of

William Thomson (1st Baron Kelvin aka Lord

Problems with classical thermodynamics:

Why do all gases behave similarly?

All constants and parameters have to be derived

It provides no information about the states or even

It has only weak if any predictive power: We can

Problems with classical thermodynamics:

Why do all gases behave similarly?

All constants and parameters have to be derived

It provides no information about the states or even

It has only weak if any predictive power: We can

The statistical approach is a first principle theory that

derives macroscopic properties (state variables and

from the constituent particles and the interactions

by connecting thermodynamic functions to

gives thermodynamics a molecular interpretation

serves as a bridge between macroscopic and

The statistical approach is a first principle theory that

derives macroscopic properties (state variables and

from the constituent particles and the interactions

by connecting thermodynamic functions to

gives thermodynamics a molecular interpretation

serves as a bridge between macroscopic and

The statistical approach is a first principle theory that

derives macroscopic properties (state variables and

from the constituent particles and the interactions

by connecting thermodynamic functions to

gives thermodynamics a molecular interpretation

serves as a bridge between macroscopic and

The statistical approach is a first principle theory that

derives macroscopic properties (state variables and

from the constituent particles and the interactions

by connecting thermodynamic functions to

gives thermodynamics a molecular interpretation

serves as a bridge between macroscopic and

James Clerk Maxwell describes the velocity

In 1877, Ludwig Boltzmann shows the

The Fundamental Laws of Thermodynamics