111EQUATION CHAPTER 1 SECTION 1CHAPTER 1

BALANCE EQUATIONS AND LAWS OF

THERMODYNAMICS

1.0 SCOPE AND OBJECTIVE

In this chapter, the basic ideas in classical thermodynamics are
reviewed. They include

introduction of basic concepts such as: system and environment;

state and state properties;

definition of thermodynamic variables such as: volume, energy,

entropy, temperature, and pressure; and process variables such as
heat and work;

derivation of balance equations of energy and entropy and their

relation to First and Second Laws of Thermodynamics respectively;
and

lastly, detailed explanations of the implications of Second Law of

Thermodynamics such as: reversibility and spontaneity, friction and
dissipation, efficiency and free energy.
Students are expected to have a basic understanding of the above

concepts and able to apply energy and entropy balance equations to

solve problems.

1.1

BASIC CONCEPTS

1.1.1 SYSTEM, ENVIRONMENT

AND

UNIVERSE

In all scientific studies, a system must first be defined. A

system is something: a lump of material, or a boundary of space in
which we focus our interests. Everything outside this system are
secondary concerns, they are lumped into the environment. In
thermodynamics, the union of the system and environment is often
referred to the universe.

Figure 1. 1 System, environment, and universe

1.1.2 OPEN

AND

CLOSE SYSTEMS

In chemical engineering thermodynamics two types of systems are

commonly used:

the control-volume system: which is a fixed volume in space with

fixed position and boundary, but variable mass; i.e. it can exchange
mass with the surrounding. A control volume system is also known
as an "open" system

the control-mass system: which is a fixed mass of material with

variable position, boundary, and volume, i.e.: it can exchange mass

with the surrounding. A control mass system is also known as an

close" system.
It should be pointed out that in classical thermodynamics, the
systems of interest are continuous lumps of materials instead of
collection of molecules and atoms.

Figure 1. 2: Open and close systems

1.1.3 CONTINUOUS MEDIA
In classical thermodynamics, the subjects of interests are lumps of
continuous materials, as opposed to statistical thermodynamics, in
which systems are collection of

molecules and atoms. It is postulated

that average properties of the system can be defined and measured,

while fluctuations of this average properties due to inter- and intramolecular movements can be neglected.

To satisfy this assumption,

the number of molecules in a continuous system must be large. The

question is how large?
In statistics it is well known that the sampled variance is inversely
proportional to the square root of number of samples. Therefore, for a
sample of

1,000,000 , the sampled variance is approximately

1/1000

or

0.1 . Hence we need at least a million molecules in the system

before it can approach a continuous system.

Consider gold at room temperature, the density is

There are

19300
100 0 6.02 1023=3.35 10 28
197

molecules will occupy 1 1.69 102 3 m3

cube will be approximately

molecules.

19300

kg
3 .
m

One million

of volume. The length of this

26 nm .

Calculations for water and

methane also shows that the continuity assumption may break down as
the material become nano-sized.

Table 1. 1: Limits of continuity for difference materials

Gold
Water
Methan
e
density [kg/m3]
19300
1000
656
mol. wt.
197
18
16
number in cubic
5.90E+2 3.35E+2 2.46E+
meter
8
8
28
volume of 1 million
1.69E2.99E4.06E[m3]
23
23
23
length of volume [nm]
26
31
34
1.1.4 THERMODYNAMIC STATES PROPERTIES

AND

THERMODYNAMIC STATE

In thermodynamics, we postulates that for a closed system or a

fixed mass of materials, there are certain directly or indirectly
measurable characteristics of the material

( X 1 , X 2 , X 3 ) , known as

thermodynamic state properties or variables.

It is

also postulated

that

the classical or macroscopic

thermodynamic state properties will not change if a subset of these

variables

( X1 , X2 , X3 X F)

are fixed;

is the degrees of freedom of

the thermodynamic states.

Common thermodynamic state properties include: temperature,
pressure, composition, density, internal energy, enthalpy, entropy, heat
capacity etc. Students should be reminded that transport properties
such as thermo-conductivity, viscosity, diffusion coefficients etc., i.e.
properties we learned in transport courses are also thermodynamic
state properties.
Although

properties

such

as

thermo-conductivity,

viscosity,

diffusion coefficients are properties related to transport of heat,

momentum and material; they are nevertheless properties of the
thermodynamic state.
Since thermodynamic states properties depend on the definition of
state variables, they do not depend on how such states are reached.
1.1.5 MACRO-

AND

MICRO- STATES

The macroscopicthermodynamic state of a system (e.g., the

condition that a system has specified values of volume, temperature
and number of molecules) provides only a partial, incomplete
description from a molecular point of view.
The most complete description that is possible about a system is a
statement of its wave function, which describe coordinates of the
elementary particles, we have a specification of the quantum state of
the system.
For a macroscopic system (~ 1024 electrons and nuclei), the

number of quantum states, which may be compatible with the same

total energy, volume, and composition is astronomical.
A less detailed description would be the coordinates, velocities and
orientations of molecules, i.e. the classical micro-state. The number of
classical microstates consistent with a macrostate is still astronomical.
For example, an ideal gas may be represented by a box of particles
with no interaction with each other, and that linear momentum is
always conserved in collision. The macroscopic thermodynamic state
is defined since volume, temperature and the number of molecules, are
fixed. However, the particles can be arranged in different positions and
move around with different velocities.

Figure 1. 3: A box of non-interacting particles

1.1.6 INTENSIVE

AND

EXTENSIVE VARIABLES

The multitude of thermodynamic properties can be divided into two

categories.

Some of them, e.g. temperature, pressure, density,

viscosity, thermoconductivity, etc. are independent of the total mass

of material in the system. They are known as intensive variables.

On the other hand, some of them, e.g. the total volume ( V ) is
homogeneous function of the total mass of material ( N ), i.e:
V (kN )=kV ( N ) . They are known as extensive variables.

1.2 THERMODYNAMIC AND PROCESS VARIABLES

1.2.1 VOLUME, INTERNAL ENERGY

AND

ENTROPY

It is not possible for us to define all classical thermodynamic

variables based on other classical thermodynamic variables. We must
starts with some a priori definitions based on our conceptualization of
microstates.
Let us assume that the extensive thermodynamic state of a pure
substance can be defined by three basic extensive thermodynamic
properties.

The first two are intuitive concepts: volume (), and

internal energy ().

Volume is the space within which the molecules can be found.
Internal energy include

intermolecular kinetic energy due to motions of centers of

mass of molecules,

intermolecular potential energy due to attraction and repulsion

between molecules,

intra-molecular kinetic energy due to rotation and vibration of

molecules,

intra-molecular electronic energy due to motion of electrons

around nuclei, and

nuclear energy which will remain unchanged in chemical

processes.

The third thermodynamic quantity is known as entropy ( S ),

which is a measurement of uncertainty of how the molecules and
atoms were arranged in the system.

Mathematically, entropy

can

be expressed as:
2
12\*
S=kN

all microstates

pi ln p i

MER
GEF
ORM

where

pi

AT (.)
i th
are probabilities of finding the system in the

microstate, and k

is the Boltzmann constant, in memory of the

physicists Ludwig Eduard Boltzmann (1844-1906), who laid the

groundwork of statistical mechanics by explaining the relation of
entropy to molecular arrangements1.
The fact that entropy is a measurement of uncertainty in
microstates can explained by the following.

If there is only one

microstate that the system can be found, i.e. we are absolutely certain
about how molecules are arranged, the entropy of the system is zero.
However, this is only a hypothetical situation never found in the real
world and can never be attained according to the Third Law of

1 https://en.wikipedia.org/wiki/Ludwig_Boltzmann

Thermodynamics2.

On the other hand, if the system can be found in a

lot of microstates with equal probabilities, then the above equation is

simplified to
3
13\*
pi =

MER
GEF
ORM
AT (.)
4
14\*
MER

S=kNln

GEF
ORM
AT (.)

where

is the number of possible micro-states; some times known

as degeneracy of the system.

2 https://en.wikipedia.org/wiki/Third_law_of_thermodynamics

Figure 1. 4: The epitaph of Boltzmanns grave

1.2.2 TEMPERATURE

AND

PRESSURE

We have assumed that the extensive macroscopic thermodynamic

state can be defined by the three variables
extensive

macroscopic

V ,U , S . However since

thermodynamic

variables

must

be

homogeneous in nature, the intensive thermodynamic states can be

defined using two variables only.
number of molecules

Hence for a closed system with

fixed, the macroscopic thermodynamic state

is defined by two of the above three variables. For example, we can

define our thermodynamic state using

and

only and write

5
15\*
MER

U=U ( S , V )
GEF
ORM
AT (.)

Given this definition of thermodynamic state of a closed system, two

important intensive properties: temperature and pressure, can be
defined as:
6
16\*
U
S

MER

( )

T=

GEF

ORM
AT (.)
7
17\*
U
V

( )

P=

MER
S

GEF
ORM

AT (.)
Microscopically, temperature is that it is proportional kinetic energy
of each molecule; while pressure is average momentum transfer
between the molecules and the wall of the container.
Furthermore, the above equations results in
8
18\*
MER
dU =TdSPdV

GEF
ORM
AT (.)

Note

that

the

above

equation

is

the

results

of

definition

of

thermodynamic state. It has nothing to do with the First and Second

Law of thermodynamics3.
Given these variables, other thermodynamic potential variables,
such as enthalpy4, Helmholtz free energy5, Gibbs free energy6 can be
defined, e.g.:
9
19\*
MER
H=U + PV

GEF
ORM
AT (.)
10
110\
*
A=U TS

MER
GEF
ORM
AT (.)

3 Sometimes, equation 18 was derived in the following way. According to the First
Law of thermodynamics for a closed system dE=Q+ W (see section 1.3.1). If
kinetic and potential energy are negligible, we have d E=dU ; furthermore, if the
process is reversible and no shaft work, Q=TdS and W =PdV , hence we
have dU =TdSPdV . But since changes of thermodynamic properties only
depend on the initial and final thermodynamic states and equation 18 involves only
thermodynamic properties, it is valid for all changes. This is a very roundabout way
of deriving equation 18. Here the equation is the direct results of the definition of
temperature and pressure.
4 https://en.wikipedia.org/wiki/Enthalpy
5 https://en.wikipedia.org/wiki/Helmholtz_free_energy
6 https://en.wikipedia.org/wiki/Gibbs_free_energy

11
111\
*
MER

G=H TS

GEF
ORM
AT (.)
1.2.3 HEAT
Heat is transfer of energy between systems with different
temperatures. Systems are at the same temperature when there is no
heat flow between them.
The Zeroth Law of Thermodynamics stated7
"if two systems, A and B, are in thermal equilibrium and a third
system C is in thermal equilibrium with system A then systems B and C
will also be in thermal equilibrium (in thermal equilibrium is a transitive
relation; moreover, it is an equivalence relation). Since A, B, and C
are all in thermal equilibrium, it is reasonable to say each of these
systems shares a common value of some property. We call this
property temperature."
Please note that the aforementioned statement of the Zero th Law
has

introduced

three

quantities:

heat,

temperature in a convoluted manner.

temperature.

thermo-equilibrium

and

It does not really define

We do not need this any more if we accept the

definition of temperature in equation 16 based on the statistical

7 https://en.wikipedia.org/wiki/Zeroth_law_of_thermodynamics

definitions of

U ,V

and S. Thermo-equilibrium between two systems

is then defined as the two having the same temperature, and heat flow
is defined as the energy transferred between two system with different
temperatures. The Zeroth law of thermodynamic is no longer needed,
or it may be re-interpreted as:
There will be energy transfer between two system caused by
different temperatures.

The energy transferred induced by different

temperatures is known as heat.

1.2.4 INTERNAL PRESSURE, EXTERNAL PRESSURE, WORK

AND

SHAFT-WORK

Any system will sustain external forces acting it by the environment.

These forces will act on the surfaces and induces surface stresses
(Figure 1. 5).

The external pressure

Pext

acting on the system, or

hydrodynamic pressure, is defined as the average of the normal

stresses acting on the surface of the system:
12
112\*
1
ext
P = ( xx + yy + zz )
3

MERG
EFOR
MAT
(.)

Figure 1. 5: Surface stresses acting on a system

It should be distinguished from the pressure defined in equation 17

which is sometimes called internal pressure

, or thermodynamic

pressure.
The workdone by these external forces will cause the system to
change in shape or volume (Figure 1. 6).

Figure 1. 6: PV-work and Shaft-work

The part of work required to change the volume is given by

ext

P dV

and is known as the PV-work. The rest of the work is known as shaft
work.
13
113\*
MERG

W =Pext dV +W shaft

EFOR
MAT
(.)

1.2.5 PROCESS

AND

EXCHANGE

Notice heat is the transfer of energy between two systems, or the

system and the surrounding; and work is the result of external force on
the system. Hence they are exchange quantities which are dependent
on

the

process,

i.e.

interaction

between

the

system

and

its

environment that changes the thermodynamic state of the system.

They are not thermodynamic state variables which are characteristic of
the system.
As shown in Figure 1. 7, a control mass or closed system can only
exchange heat and work with its environment, while a control volume
or open system can exchange mass, heat and work with its
environment.

Figure 1. 7: Exchanges with the environment of closed and open

systems
In thermodynamics, an isolated system is defined as a close
system that has no exchange in heat and work with its environment.
Since the universe has no environment, it cannot exchange anything.
An universe is an isolated system.

1.3 BALANCE

EQUATIONS

AND

LAWS

OF

THERMODYNAMICS
1.3.1 ENERGY BALANCE

AND

FIRST

OF

THERMODYNAMICS

The total energy in a system include internal energy

energy

KE

and potential energy

U , kinetic

PE .
14
114\*
MERG

E=U + KE+ PE
EFOR
MAT
(.)
The kinetic and potential energies are related to the velocity and
position of the center of mass of the system. The kinetic and potential
energies of movement of molecules relative to the center of mass were

included in the internal energy

U .

The accumulation of total energy in a close system with variable

volume

is therefore given by:

15
115\*
MERG

dE
ext dV
j+ W
shaft
= Q
P
k
dt
dt
j
k

EFOR
MAT
(.)

where

j , and
Q

shaft
W
k

exchanged between

are various sources of heat or shaft-work

the system and the environment.

We have

adopted the convention that input to the system is positive.

The corresponding accumulation of total energy in an open system
with fixed volume and boundary is therefore given by:
16
116\*
MERG

KE i + PE i
dE
ext
j + W
shaft
= n i U i+
+ Pi V i + Q
k
dt
MW i
i
j
k

EFOR
MAT

n i

(.)
are the molar flow rates of various streams of material exchange

with the environment.

Ui ,

MW i

molecular weight of these streams.

are the molar internal energy and

KE i

and

PE i

and potential energy of these streams. The terms

are the kinetic

Pext
i Vi

represents

the work required pushing these streams into the control-volume

system.
The above balance equations simply stated the fact that:
energy accumulation=energy input energy output

Since there is no source or sink, we are implying that total energy is

conserved, which constitute the First Law of Thermodynamics8.
1.3.2 ENTROPY BALANCE

AND THE

SECOND LAW

OF

THERMODYNAMICS

The entropy balance of a closed system is shown here.

17
117\*
MERG

dS
Q
dS
= sj + gen
dt
dt
j Tj

EFOR
MAT

(.)
The term on the left is the accumulation of entropy in the system, while
the first term on the right is the entropy brought into and out of the
system by heat exchange with the surrounding.

T sj

are the

temperatures of the surrounding sources or sinks at the points of

exchange. The second term

d S gen
dt

is the entropy generated during

the process.
The corresponding entropy balance equation for an open system is
8 If there is only one heat source and work source, and by omitting the time
derivative; we can recover the more common but limited form of the First Law of
Thermodynamics (for a closed system) that is found in many undergraduate
textbooks dE=Q+ W , where W =Pext dV +W shaft .

given by:
18
118\*
MERG

dS
Q
dS
= ni Si + sj + gen
dt
dt
i
j Tj

EFOR
MAT

(.)
The first term on the right hand side represents the entropy brought
into/out-of the system by the material input/output streams.
Note

that

the

above

equations

are

not

the

Second

of

Thermodynamics, they are only an accounting equation of entropy

change.

However, the inclusion of the term

d S gen
dt

expressed the

important concept that unlike energy, entropy is not a conserved

quantity. The Second Law of Thermodynamics states that entropy can
be generated but not destroyed:
d S gen
0
dt

19
119\*
MERG
EFOR

It should be pointed out that the entropy of a system can increase

or decrease, it is only the entropy generated in the process that is
positive.

There are many ways of expressing the Second Law of

Thermodynamics9,10, but equation 119 offers the most concise way of

stating it with the least qualifications.
1.3.3 REVERSIBILITY
Entropy can only be generated but not destroyed in a process, a
process in which no entropy is generated is known as a reversible
process:
20
120\*
MERG

d S gen
=0 Processis reversible
dt

EFOR
MAT

(.)
To illustrate the concept of reversibility, we shall use the adiabatic
expansion of a mass of gas against and external pressure

Pext

with no

shaft work as an example (Figure 1. 8). Under what condition is the

expansion reversible?
9 If there is only one heat exchange Q and the system has an uniform
temperature T , equations 117 and 119 reduce to the more common form of the
Second Law of Thermodynamics for a closed system

dS Q

.
dt T

10 It is very common to give the Second Law of Thermodynamic as The entropy of

the universe cannot decrease. While this is indeed true, a more precise way to put it
is The entropy of an isolated system cannot decrease. It is certainly not true that
The entropy of a system cannot decrease. Increase in entropy in an open system,
self-organization is very important phenomenon in biological and social systems.

Figure 1. 8: The adiabatic expansion of a mass of gas against and

external pressure Pext with no shaft work
According to 117, since there is no heat exchange with the
surrounding and the process is reversible, we have
21
121\*
dS
Q
dS
= sj + gen =0
dt
dt
j Tj

MERG
EFOR
MAT

(.)
In other words, the systems entropy remain constant, the process is
isentropic. In addition, if we assume that the changes in kinetic and
potential energy are negligible equation 115 reduces to
dU + KE+ PE
dV
j + W
shaft
= Q
P ext
k
dt
dt
j
k

22
122\*

But according to equation 18, we have

23
123\*
dV

dt

MERG

dU
dS
=T P
dt
dt

EFOR
MAT
(.)

Hence
24

=Pext
ext dV

=P
P
dV
dt
dt

dU

=P
dt

124\*
MERG
EFOR
MAT

(.)
For an expansion to occur adiabatically the internal pressure is equal to
external pressure. However, if the internal pressure is equal to external
pressure, how can there be any expansion?
The above questions can be answered if we examine an irreversible
adiabatic expansion with no shaft work, we have
dS
Q
dS
= sj + gen
dt
dt
j Tj

25
125\*

The energy balance in 122 have not changed, but equation 123
becomes
26
dV

dt

d S gen
P
dt
dU
dS
=T P
dt
dt

=T
dV
dt

126\*
MERG
EFOR
MAT
(.)
27

Pext
P

d S gen
T
=
dt

127\*
MERG
EFOR
MAT

(.)
Hence the Second Law of Thermodynamics stipulated that when
internal pressure is greater than the external pressure, the system
must expand:

Pext
P

dV
0
dt

28
128\*
MERG
EFOR

when internal pressure is less than the external pressure, the system
must contract:
29
129\*

P ext

dV
0
dt

MERG
EFOR
MAT

(.)
Hence the reversible expansion is the hypothetical limiting case when
the internal pressure is infinitesimally greater than external pressure
and the expansion rate is infinitesimally small.
We can extend the above observation to all other reversible
processes.

All reversible processes are hypothetical limiting cases

when there are only infinitesimally small gradient, be it temperature,

pressure, concentration or other, that drives the process and the
process rate is infinitesimally small.
1.3.4 EXAMPLETANK EMPTYING
So far, we have only introduce concepts. In this example, we shall
see how the balance equations and laws of thermodynamics can be
used to solve problems. The example (Figure 1. 9) is as follows:

Figure 1. 9: Adiabatic emptying of a tank

An ideal gas is withdrawn from a tank
Pi

and initial temperature

the outside pressure

Po

Ti

with initial pressure

until the pressure inside

Pf

equals

through a well-insulated valve.

The

evacuation process is so fast that it can be regarded as adiabatic. We

would like to know

How much gas is left inside the cylinder?

What is the final temperature of the cylinder at this time?

If we draw a control volume around the tank as shown in Figure 1. 10

Figure 1. 10: Control volume around the tank

There is no heat or work exchange with the surrounding.

The only

exchange is the gas flowing out of the tank. Hence we have:

30
130\*
MERG
KE i+ PE i
dE d ( U + KE+ PE ) dn U
dn
d U dn
j+ W
shaft
=
=
=U + n
=
U+
+ PV + Q
k
dt
dt
dt
dt
dt
dt
MW i
j
EFORk

MAT
(.)
31
131\*
n

MERG

dU
dn
=P V
dt
dt

EFOR
MAT

For

an

ideal

gas,

the

internal

energy

is

only

dependent

(.)
on

temperature11
32
132\*
n

MERG

dU
dT
dn
dn
=nC V
=P V =RT
dt
dt
dt
dt

EFOR
MAT
(.)
33
133\*
MERG

CV dT 1 dn
=
RT dt n dt

EFOR
MAT
(.)
34
134\*

ln

MERG

nf C V
Tf
=
ln
ni
R
Ti

( )

( )

EFOR
MAT
(.)

Pf V
RTf
T
= f
Pi V
Ti
RTi

( )

35
CV
R

CV
+1
f R

Pf
T
=
Pi
Ti

Tf
Ti

( ) ( )( ) ( )

CP
R

135\*
MERG
EFOR
MAT

11 We shall introduce the ideal gas model and other theory of states in the next
chapter.

By now one must realize that the temperature-pressure relation

obtained using control volume approach is the same as an adiabatic
reversible expansion of a fixed mass of gas.

However, in our

derivation, the Second Law of Thermodynamics was never used! This

is possible because we have already specified the final pressure and
constrained the process to be adiabatic and no shaft work.

But the

question is which mass of gas has under undergone an adiabatic

reversible expansion? This is left as exercise for the readers.

1.4 SECOND LAW REVISITED

1.4.1 IRREVERSIBILITY

AND

SPONTANEITY

Consider an adiabatic chamber partitioned into two equal parts

each containing the same gas A. If we remove the partition the gas will
mix. If we put the partition back in place, we will recover the original
state with two chambers of gas A again. We note that since the initial
and final conditions are the same, and that the process is adiabatic we
have
S= S gen =0
In other words, the process is reversible

Figure 1. 11: Partition and mixing of two chambers of the same gas

However, if the two parts contain two different gases A and B, the
results are quite different.

If we remove the partition the gases will

mix. If we put the partition back in place, we will have two chambers
containing mixtures of A and B, instead of the original state with one
chamber of pure A and one chamber of pure B again.

Figure 1. 12: Partition and mixing of two chambers of two different gas
Again, using theory of ideal gas, we have
S= S gen =R ( n A ln x A +n B ln x B ) >0
The process is irreversible.
Whether the process is irreversible or not depends on how easily can
we return the original state. In this case, the irreversibility is caused by
the spontaneous mixing of the two gases.

Thus we can generalized

that a spontaneous process must be irreversible.

1.4.2 IRREVERSIBILITY

AND

FRICTION

AND

DISSIPATION

Let us consider a simple example of pushing a block from one end

of a table and back (Figure 1. 13).

(a) Initial

(b)Intermediate

(c) Final
Figure 1. 13: Moving a block on a table
We know that how easily it can be done, i.e. how reversible is the
process depends on the friction between the block and the table. Since
the initial and final state were the same, we have
36
136\*
U =0=Q+ W Friction

MERG
EFOR
MAT
(.)

S=0=

Q
+ S gen
T env

37
137\*
MERG
EFOR

38
138\*

S gen=

W Friction
T env

MERGE
FORMA
T (.)

The entropy generated which is index of irreversibility is proportional to

the workdone against friction. In general, friction dissipated as heat
causes irreversibility.
The relation between frictional forces and irreversibility can also be
demonstrated by steady state, adiabatic fluid flow in a pipe (Figure 1.
14).

Figure 1. 14: Fluid flow in a pipe

The energy balance is given by
KE i + PE i ext
dE
j + W
kshaft
=0= n i U i+
+ Pi V i + Q
dt
MW i
i
j
k

39
139\*
MERG
EFOR
MAT

40
140\*
0= H KE PE+

shaft
W
= H KE PE+W shaft
n

MERG
EFOR
MAT
(.)

The

is defined as the difference between outlet and inlet.

shaft

is the total amount of work per unit flow that is required in the system.
The negative signs are there because we define originally input to the
system as positive. The entropy balance is given by:
41
141\*
dS
Q
dS
=0= n i Si + sj + gen
dt
dt
i
j Tj

MERG
EFOR
MAT
(.)
42
142\*

0= S+

1 d S gen
= S +S gen
n dt

MERG
EFOR
MAT

S gen

(.)
is the entropy generated in the process per unit flow. According

to the definition of enthalpy, we have

43
143\*
1
1
dH =TdS+VdP H=T S +V P=T S + P=T S gen + P

MERG
EFOR
MAT
(.)
44
144\*

shaft

1
= KE+ PE+ P+T S gen

MERG
EFOR
MAT

(.)
The above equations can be compared to the Bernoulli equation that
include the viscous loss12 which is obtained by momentum balance:
45
145\*
W

shaft

1
= KE+ PE+ P+ vis

MERG
EFOR
MAT

(.)
The last term is known as the viscous loss of the system which is
12 The Bernoulli equation between two section of the pipe is often given in the
2

following form

P1 v 1
P v
+ + gz 1= 2 + 2 + g z 2 . The last terms on both side of the
2
2

equations represent the kinetic and potential energies per unit mass, which
correspond to KE and PE in equations 144 and 145. However this applied
only to inviscid flow, i.e. the effect of viscosity can neglected and there is no pumping
work added to the system. A more general form should include both viscous loss and
pump, for example, equation 4.74 of Unit Operation of Chemical Engineering, 7 th
Edition, McCabe, Smith and Harriott, McGraw-Hill 2005.

caused by friction between the flow fluid of different velocities and the
friction with the pipe wall. Combining 144 and 145, we can see that
the entropy generation, or irreversibility, is caused by the viscous loss:
46
146\*
MERG

T S gen= vis

EFOR
MAT
(.)

1.4.3 IRREVERSIBILIT

AND

CARNOT EFFICIENCY

The development of the Second Law of Thermodynamics started

with the study of heat engines. The French engineer/physicist Carnot 13
was the first to theorize that when heat is converted into work in an
engine cycle, there is a limit in the efficiency

, i.e. amount of work

obtained per unit of heat input. Some heat must be rejected as waste
heat.

Moreover, Carnot derived that this limit is determined by the

temperature of the heat source from which we receive useful heat

T H , and the temperature
waste heat

of the heat sink to which we output

TL .

= 1

TL
TH

47
147\*
MERG
EFOR
MAT

13 https://en.wikipedia.org/wiki/Nicolas_L%C3%A9onard_Sadi_Carnot

Consider the following cyclic process, as shown in Figure 1. 15, which

takes in
W
at

QH

amount of heat from a heat source at

amount of work and release

QL

T H , generate

amount of heat from a heat sink

TL .

Figure 1. 15: A General Heat Engine Cycle

Since the engines run in cycles, there is no change in thermodynamic
state in the working fluid. The energy balance and entropy balance are
given by:
48
148\*
U =QH W Q L =0 QH =W +Q L

MERG
EFOR
MAT
(.)

S=

QH QL
T
+ S gen=0 Q L = L Q H +T L S gen
TH TL
TH

49
149\*

50
150\*

W = 1

TL
Q T L S gen
TH H

MERG
EFOR
MAT
(.)

Since the entropy generation is non-negative, we have

51
151\*

T L S gen 0 W 1

TL
Q
TH H

MERG
EFOR
MAT
(.)
52
152\*

max =

W max
TL
1
QH
TH

MERG
EFOR
MAT
(.)

1.4.4 IRREVERSIBILITY

AND

FREE ENERGY/EXERGY

The idea of the maximum amount of work that can be extracted, or

minimum amount of work that is required, can be extended to other

systems.

For example, consider a

closed system held at constant

volume, and isothermal at the temperature

reservoir also at temperature

env

by a surrounding

=T , we can simplify the energy and

entropy balance equations as:

53
153\*
dU + KE+ PE
dV dU shaft
j + W
shaft
= Q
P ext

=Q+ W
k
dt
dt
dt
j
k

MERG
EFOR
MAT
(.)
54
154\*

dS
dS
Q
dS
dS Q
= sj + gen = + gen
dt
dt
dt T
dt
j Tj

MERG
EFOR
MAT

(.)
According to the definition of Helmholtz free energy in equation 110, its
rate of change is given by:
d S gen shaft
d S gen
dA dU
dS
dT shaft
=
T
S
=Q+ W QT
=W T
dt
dt
dt
dt
dt
dt

55
155\*
MERG
EFOR
MAT

We have
56
156\*
shaft = dA +T d S gen
W
dt
dt

MERG
EFOR
MAT
(.)

Since

d S gen
0 ; we can derive that if the system increases in
dt

Helmholtz free energy, the minimum work required is the increase in

Helmholtz free energy:
57
dS
dA

>0 ; gen 0 W
dt
dt

shaft

157\*
d S gen
dA

+T

dt
dt

MERG
EFOR

dA
shaft
W
min =
dt

MAT

(.)
Conversely, if the system decreases in free energy, the maximum
amount of work that can be extracted from the process is the decrease
in Helmholtz free energy:
dS
dA

<0 ; gen 0 W
dt
dt

shaft

shaft
W
max =

dA
dt

d S gen
dA
T

dt
dt

58
158\*
MERG
EFOR

For a closed system held at constant pressure, and isothermal at

the temperature

by a surrounding reservoir also at temperature

T env =T , we have
59
159\*

| |

dG
=
dt

dG
>0
dt
dG
<0
dt

shaft
W
min

W
max

shaft

MERG
EFOR
MAT
(.)

For an open system, we can define a term known as exergy or

available energy14
60
160\*
e

B=HT S

MERG
EFOR
MAT

where

(.)
is an arbitrarily defined reference temperature of the

environment, e.g. 300 K is commonly used. If the system is at steady

state, the changes in potential and kinetic energy are neglected, and
the external pressures are equal to the system pressure at the inlet and

14 https://en.wikipedia.org/wiki/Exergy

outlet conditions, we have

61
161\*
MERG
KEi + PE i
dE
ext
j + W
shaft

shaft
= n i U i+
+ Pi V i + Q

0=
n

H
+
Q

k
i
i
j + W k
dt
MW i
i
j
k
i
j
k
EFOR

MAT
(.)
62
162\*

dS
Q
dS
= ni Si + sj + gen
dt
dt
i
j Tj
j d S gen
Q
+
dt
T sj

0= n i S i+
i

MERG

EFOR
MAT
(.)

Multiply equation 162 by

and subtract from 161, we have

63

n i B i +T e
i

dS
T
shaft
Q + W
T e gen
k
s
dt
Tj j k
e

( )

0= n i ( H iT e Si ) + 1

d S gen
Te
shaft
= 1 s Q
+ W
k
dt
Tj j k
j

( )

163\*
MERG
EFOR
MAT
(.)

The term

( )
1

T
T sj

in front of

j
Q

looks exactly like the Carnot

efficiency with the temperature of the environment as heat sink. Hence

we can define the total equivalent work

W tot

as:

64
164\*
W
tot

MERG

( )

T
shaft
1 s Q
+ W
k
Tj j k

EFOR
MAT
(.)

If we define the exergy input-output change as

B :

65
165\*
B n i B i
i

MERG
EFOR
MAT
(.)

we have
66
166\*
B+T e

d S gen
=W tot
dt

MERG
EFOR
MAT

(.)
Then the concepts of maximum work obtained or minimum work
required can also be related to the absolute change of exergy:

| B|=

W tot
min

tot
max

B> 0

67

B< 0

167\*
MERG

Furthermore the thermodynamic efficiency

can be defined as:

68

B
=
W tot

B
dS
B +T e gen
dt
=
dS
BT e gen
tot
W
dt
=
B
B

B>0

168\*
MERG
EFOR

B<0

MAT
(.)

1.4.5 EXAMPLEEXERGY ANALYSIS

AND

THERMODYNAMIC EFFICIENCY

OF

DISTILLATION COLUMN
The following example is used to show how a process can be assessed
using exergy analysis and thermodynamic efficiency. Methanol and
water are separated by a distillation columns.

Results of a specific

design simulated using ASPEN Plus are shown in Figure 1. 16.

Figure 1. 16: Methanol+Water column and Aspen Plus simulation

results

The enthalpies and entropies of the input and output streams are
given.

Assuming an environmental reference temperature of 300 K,

the increase in exergy

can be calculated

69
169\*
B=0.014

MERG
kmol
kJ
kJ
kmol
kJ
2.80e6
+300 K 147
+0.014
2.35e6
+300 K 227
s
kmol
kmol K
s
kmol
EFOR

MAT
(.)
The reboiler output is 371 K, to supply this duty, low pressure steam
(~4 barG, 425 K) is usually used as the heat source. The condenser
operates around 337 K, normal cooling water at 300 K can be used as
the heat sink. Therefore the total equivalent work can be calculated
as:
70
170\*

W tot = 1

300 K
300 K
1002 kW 1
975 kW=293 kW
425 K
300 K

MERG
EFOR
MAT
(.)

Hence the efficiency of the process is merely:

=

16.5 kW
100 =5.6
293 kW

71
171\*
MERG
EFOR

MAT

If

we

examine

many

chemical

processes,

the

(.)
thermodynamic

efficiencies can be quite low. It is our duty as chemical engineers to

find ways to improve these processes.

Exergy and thermodynamic

efficiency analysis do not in themselves tell us how to improve the

process.

But they provide an evaluation criterion so that different

options can be compared and a target can be set 15. Furthermore, we

note that poor efficiency is caused by large irreversibility. Hence, we
should look for waste generated by unnecessary mixing, failure to
recover high temperature heat, failure to use sub-room-temperature
streams as cooling medium and equipments that generate large
frictional dissipation.

1.5 SUMMARY
Important concepts introduced in this chapter include

Open and close systems

State and state function

Balance equations

Laws of Thermodynamics

Implications of Second Law of Thermodynamics

Reversibility and spontaneity

Friction and Dissipation

Efficiency and Free Energy

15 With current technology, a process with a thermodynamic efficiency of 50% is

considered very good and difficult to improve.