NENG 301

Lecture 2 The structure of

thermodynamics (DeHoff, Chap. 2)
All hail the mighty Glow Cloud

Learning objectives for Chapter 2

At the end of this chapter you will be able to:
Understand the general statements of the laws of thermodynamics
Understand the basic terminology of thermodynamics as
presented and used in this chapter and be able to give examples of
each: system, surroundings, state of a system, state function
Understand the classification of thermodynamic systems into
different categories
Know the meaning of the terms heat and work from a
thermodynamic perspective
Understand the difference between exact and inexact differentials
Understand the classification of thermodynamic relationships: the
laws of thermodynamics; definitions; coefficient relationships;
Maxwell relations; and conditions for equilibrium
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General statements of the laws of

thermodynamics as applied to the universe
There exists a property of the universe, called its energy (U),
which cannot change no matter what processes occur in the
universe
There exists a property of the universe, called its entropy (S),
which can only change in one direction no matter what
processes occur in the universe
A universal absolute temperature scale exists and has a
minimum value, defined to be absolute zero, and the entropy
of all substances is the same at that temperature
Dont worry for now: we will have a lot to say
about these in Chapter 3
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Again: important (if obvious) concepts

System: any region of the universe, large or small,
that is being considered in our analysis
Boundary: the interface between the system and
its surroundings
Surroundings: regions outside the boundaries of
the system but can alter the system by interacting
with it
Properties: Physical characteristics that define the
condition of the system and its surroundings

This is a system.
The subset of the universe in
focus in a particular application
of thermodynamics is usually
called the system
At any given instant of
observation the condition of
the system is described by an
appropriate set of properties
Limitations on changes in these
properties are set by the nature
of its boundary

This is a system that goes through a process

The subset of the universe in focus in a particular application of

thermodynamics is usually called the system
At any given instant of observation the condition of the system is
described by an appropriate set of properties
Limitations on changes in these properties are set by the nature
of its boundary
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Classification of systems
Thermodynamic systems can be classified into several categories:
1. unary (one chemical component) versus multicomponent (two
or more chemical components in multicomponent systems,
the chemical composition may vary
2. homogeneous (single phase) versus heterogeneous (two or more
phases, eg. ice/water)
3. closed (no exchange of matter by the system across its boundary
with the surroundings) versus open (exchange of matter by the
system with the surroundings) [note: also isolated]
4. non-reacting versus reacting (specifically chemical reactions)
5. simple versus complex
o simple: only energy exchanges involve thermal, mechanical or
chemical changes
o complex: gravitational, electrical, magnetic or surface factors
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A typical thermodynamic system

Cross-section through a MOSFET (metal oxide semiconductor field

effect transistor) thin film device shows it to be a multicomponent,
multiphase system in which chemical reactions and the influence of
an electric field are important
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More definitions
State functions (or state variables): a system is said
to be in a certain state when all of its properties
have these specific values depend on the current
condition of the system and not on how the system
got there

temperature
pressure
volume
chemical composition
(internal) energy
entropy
others.
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Simple Exercise

If Z is a state function that depends

on other state functions X and Y,
Z = Z (X,Y), show:
(

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Still more definitions

Process: processes are described by quantities that
only have meaning for changing systems
Consider a transition from state A to state B:
represented by a curved path in the X-Y plane
The change in Z (or DZ) is
independent of the path
There are two very important
types of processes:
work done on the system
as it changes
heat absorbed by the
system as it changes
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What is Thermodynamics?
The study of energy transformations and the relationships among
physical properties of substances which are affected by these
transformations.
-- K. Wark, Thermodynamics, 5th Edition (1988)

Thermodynamics is mainly concerned with transformations of

heat into mechanical work and the opposite transformations of
mechanical work into heat.
-- E. Fermi, Thermodynamics (1937)

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Work
The easiest way to discuss work
is through classical mechanics
Consider the application of a
force F: if the point of
application of the force moves,
then the force does work
The increment of work done by
the displacement is:

w F dx
F=Pext A
w Pext A dx Pext dV

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Work

Work, like energy, can take various forms: mechanical, electrical,

gravitational, etc.
All have in common the fact that they are the product of two factors,
an intensity term and a capacity term.
the simplest form of mechanical work arises when an object
moves a certain distance against an opposing force.
example: electrical work is done when a body having a certain
charge moves through a potential difference
Type of work

intensity factor

capacity factor

formula

mechanical

force

change in distance

f x

gravitational

gravitational potential
(a function of height)

mass

mgh

electrical

potential difference

quantity of charge

QV

surface

surface energy/tension

change in area

g DA
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Heat
Heat and work are both measured in energy units, so
they must both represent energy
Energy can take many forms: mechanical, chemical,
electrical, radiation (light), and thermal, or heat
Heat is a form of energy, but it differs from all the
others in one crucial way: complete conversion of heat
into other forms of energy is impossible
Thermal energy can be transferred from one body (i.e.,
one system) to another (we often refer to this as a
"flow" of heat)
Heat can only flow spontaneously from a system at a
higher temperature to one at a lower temperature
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Heat and Work

Consider a gas in a cylinder that is subjected it to two processes:
compress from Pi, Vi to Pf, Vf
heat from Ti to Tf

Mass
Mass
Piston

Piston
Pi, Vi

Ti

P f, V f

mechanical
stops

Tf

Exact and inexact differentials

An ordinary (exact) differential, when integrated, yields a
finite difference given by the limits of integration:

x2

dx x2 x1 Dx
In other words: an exact differential integrates to a finite
difference, independent of the path of the integration
x1

In contrast, an inexact differential integrates to a total

quantity which depends on the path of integration taken:
2
Q Q
1

The cyclic integration of an exact differential is exactly zero

for all cycles, while the cyclic integral of an inexact differential
is usually non-zero:
dy 0 (all cycles)
Q 0
exact

inexact

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Exact and inexact differentials

Quantities of heat Q and work W are path dependent and
hence depend on the path taken by a given process
The terms DQ and DW in this case are meaningless
If DW meant anything it would mean W2 - W1

The system in either the initial state or the final state does not
have any work W1 or W2, nor does it have any heat Q1 or Q2

Work and heat appear during a change in state; they are not
properties of the state, but instead are properties of the path
Properties of the state of the system (T, P, V, U) have
differentials which are exact, while differentials of properties
of the path (Q and W) are inexact
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Peculiarities of heat, work and energy

Heat and work both appear at the boundary of a system
Work can be completely converted into heat (by friction, for
example), but heat can only be partially converted to work
conversion of heat into work is accomplished by a heat engine
Heat and work are best thought of as processes by which energy
is exchanged
Energy is measured in terms of its ability to perform work or to
transfer heat
The basic unit of energy is the joule one joule is the amount of
work done when a force of 1 newton acts over a distance of 1 m;
thus 1 J = 1 N-m
The newton is the amount of force required to accelerate a 1-kg
mass by 1 m/sec2, so the dimensions of the joule are kg m2 s2
The other two units in wide use: the calorie and the BTU (British
thermal unit) are defined in terms of the heating effect on water
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Sample homework problems

2.2. It is not an overstatement to say that without state
functions thermodynamics would be useless. Discuss this
assertion.

2.4. Why is heat a process variable?

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If there were no state functions (like T, P, V, composition), i.e.,

properties that depend only upon the current condition of the
system, and not on how it arrived at that condition) then the
behavior of all aspects of matter would depend explicitly upon
the history of the system. There would be no variables that, by
themselves, explicitly describe the current condition of any
system. Thus, even the history experienced by the system could
not be described in terms of some sequence of change of
its properties.

Heat is fundamentally a flow of energy. Heat is transferred

between two systems, or between parts of the same system; this
rearrangement of the distribution of energy is necessarily
accompanied by changes in at least some of the properties of the
systems involved. Such a change is by definition a process.
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More definitions
equations of state or state functions: relationships
between dependent variables of state and
independent variables of state
intensive property: a property that is independent
of the quantity of matter in a system (temperature,
pressure, concentration, etc.)
extensive property: a property that is dependent of
the quantity of matter in a system (volume, heat
capacity)
Note that we can derive intensive properties from
extensive properties (example: mole fraction)
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2.3. Determine which of the following properties of a thermodynamic

system are extensive properties and which are intensive.
a. The mass density.
b. The molar density.
c. The number of gram atoms of aluminum in a chunk of alumina.
d. The potential energy of the system in a gravitational field.
e. The molar concentration of NaCl in a salt solution.
f. The heat absorbed by a the gas in a cylinder when it is compressed

gram atoms: the quantity of an element whose weight in grams is numerically

equal to the atomic weight of the element.
0.450 gram of Fe contains how many atoms?
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Classification of relationships
Just wait and see: you will become familiar with a large
number of thermodynamic relationships!
In order to sort through the coming confusion it will be useful
to classify these relationships
1. Laws of thermodynamics these form the physical basis
for all subsequent relationships
There exists a property of the universe, called its energy (U),
which cannot change no matter what processes occur in the
universe
There exists a property of the universe, called its entropy (S),
which can only change in one direction no matter what
processes occur in the universe
A universal absolute temperature scale exists and has a
minimum value, defined to be absolute zero, and the
entropy of all substances is the same at that temperature 24

2.6. Describe what the notion of equilibrium means to you.

List as many attributes as you can think of that would be
exhibited by a system that has come to equilibrium. Why do
you think these characteristics of a system in equilibrium are
important in thermodynamics?

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Answer to 2.6.

Attributes of equilibrium:
1. A state of rest: state of the system does not change with time.
2. A stable state: if the state is displaced from the equilibrium state,
it will return to it.
3. A state of internal uniformity; (in the absence of external fields)
gradients of intensive properties vanish.
The equilibrium state is the final state of every process. The
primary goal of thermodynamics is the prediction of the
properties of the final equilibrium state for any given initial
condition of any system. "How far the system is" from the
equilibrium state is a measure of the driving force for processes
changing the system toward equilibrium, and controls the rate
of approach to the final state of rest.
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The Zeroth Law of Thermodynamics

Equilibrium is characterized by a function of thermodynamic

state variables. This function specifies the equation of state.

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Classification of relationships
2. Definitions new parameters, quantities and variables
based on prior ones
Energy:
U = U(S,V)
dU = T dS P dV
Enthalpy: H = U + PV dH = T dS + V dP
Helmholtz free energy: F = U TS dF = S dT P dV
Gibbs free energy: G = U + PV TS = H - TS
dG = S dT + V dP
2. Coefficient relationships describe how the value of state
variable changes during an infinitesimal step in a process:
dZ MdX NdY
X, Y, Z are all

state variables

dX

dY
X Y
Y X
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Coefficient relationships between state functions

If Z is a state function that depends
on other state functions X and Y,
then we can related a change in Z
with respect to X and Y:
dZ MdX NdY
Z
Z

dX
dY
X Y
Y X

If Z = f(X,Y) represents a
surface in (X,Y,Z) space,
then dZ is the sum of the
components in the X and Y
directions
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Coefficient relationships between state

functions apply to an ideal gas
dZ MdX NdY

Z
Z

dX

dY
X Y
Y X

Consider a mole of an ideal gas: PV = RT or V = f(P,T)

Express V as a function of T and P:
RT
1
V
R(T )
P
P
Determine the partial derivatives:
RT V
R
V

2 ;

P
P T
T P P
So the final relationship for dV is:
RT
R
dV 2 dP dT
P
P

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Classification of relationships (cont)

4. Maxwell relationships provide descriptions of partial
derivatives involving state functions

M
N
dZ MdX NdY

X
Y
Where did this come from? Go back to:
Z
Z
M
and
N

X
Now take the derivatives:
Z
Z
M
N

and

X
Y X

X Y

Since the order of differentiation doesnt matter:
Z
Z N
M

X
Y X

X Y
Y

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2.5. Write the total differential of the function

a. Identify the coefficients of the three differentials in this expression

as appropriate partial derivatives.
b. Show that three Maxwell relations hold among these coefficients.

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33

Classification of relationships (cont)

As stated previously: Maxwell relationships provide
descriptions of partial derivatives involving state functions
Some are entirely unimportant, while others are extremely
important, for example:
S V
dG SdT VdP

T
T
P
the isothermal pressure dependence of entropy is
given by the easily-measured thermal expansion

5. Conditions for equilibrium sets of equations that describe

the relations between state functions that must exist when a
system is at equilibrium; these are the relationships that are
used to calculate equilibrium maps
Well have a lot of these!
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Simple Exercise

If Z is a state function that depends

on other state functions X and Y,
Z = Z (X,Y), show:
(

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Group Exercise

Group I: B,C,W (7)

Group II: D, E, F, Y (7)

Group III: G,J, T (7)

Group IV: K, M, U (7)

Group V: N, S (7)

Group VI: P, R (6)

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dX =

Writing the differential dX directly from X = X(Y,Z):

Comparing the coefficients of dY in the two expressions:

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Chapter 2 So what have we learned?

We have three laws of thermodynamics:
energy is conserved
entropy is created
temperature has a zero

We can classify thermodynamic systems into categories:

number of components
number of phases
nature of the system boundary
chemical reactivity
complexity with respect to non-mechanical forces

Thermodynamic relations can be classified as well:

the laws of thermodynamics

definitions
coefficient relationships
Maxwell relations
conditions for equilibrium

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