UNIT 6

THERMODYNAMICS

content concerning
It is the only physical theory of universal framework of the
which I am convinced that, within the
Objectives applicability of its basic concepts, it will never be
overthrown.

After studying this Unit, you will Albert Einstein

be able to

explain the terms: system and

surroundings:
discriminate between close,
open andisolated systems:
explain internal energy, work Chemical energy stored by molecules can be released as heat
and heat; during chemical reactions when a fuel like methane, cooking
state first law of gas or coal burns in air. The chemical enerpy may also be
thernnodynamics and express used to do mechanical work when a fuel burns in an engine
it mathematically;
calculate energy changes as
or to provide electrical energy through a galvanic cell like
work and heat contributions dry cell. Thus, various forms of energy are interrelated and
in chemical systems; under certain conditions, these may be transformed from
explain state functions: U, H. One form into another. The study of these energy
correlate AU and AH; transformnations forms the subject matter of thermodynamics.
measure experimentally AU The laws of thermodynamics deal with energy changes of
and AH: macroscopic systems involving a large number of molecules
define standard states for AH: rather than microscopic systemscontaining a few molecules.
calculate enthalpy changes for Thermodynamics is not concerned about how and at what
various types of reactions; rate these energy transformations are carried out, but is
State and applv Hess's law of
Constant heat summation:
based on initial and final states of a system undergoing the
difterentiate between extensive
change. Laws of thermodynamics apply only when a system
andintensive properties;
is in equilibrium or moves from one equilibrium state to
define spontaneous and non another equilibrium state. Macroscopic properties like
spontaneous processes; pressure and temperature do not change with time for a
explain entroPy as system inequilibrium state. In this unit, we would like to
Lhernodynamic state function answer some of the important questions through
andapply it for spontaneity: thermodynamics, like:
explain Gibbs energy change
How do we determine the energy changes involued in a
establish relationship belween chemical reaction/process? Will it occur or not?
AG and spontanelty, AG and
equilibrium constant. What drives a chemical reaction/process?
To what extent do the chemical reactions proceed?
 155
THERMODYNAMICS

6.1 THERMODYNAMIC TERMS be real or imaginary. The wall that separates

the system from the surroundings is called
We are interested in chemical
eactions and the
boundary. This is designed to allow us to
energy changes accompanying them. For this control and keep track of all movements of
thermodynamic
we need to know certain below. matter and energy in or out of the system.
terms. These are discussed
6.1.2 Types of the System
6.1.1 The System and the Suuroundings We, further classify the systems according to
to that the movements of matter and energy in
or out
A system in thermodynamics refers
are
part of universe in which observations of the system.
made and remaining universe constitutes the 1. Open System
surroundings. The surroundings include In an open system, there is
exchange of energy
everything other than the system. System and and matter between system and surroundíngs
the surroundings together constitute the Fig, 6.2 (a)]. The presence of reactants in an
system".
universe.
open beaker is an example of an open surface
The universe =The system +The surroundings Here the boundary is an imaginary
However, the entire universe other than enclosing the beaker and reactants.
the system is not affected by the changes 2. Ciosed SysteT
taking place in the system. Therefore, for exchange of
In a closed system, there is no
all practical purposes, the surroundings matter, but exchange of energy is possible
are that portion of the remaining universe between system and the
surroundings
which can interact with the system. reactants in a
[Fig. 6.2.(b)]. The presence of
Usually, the region of space in the closed vessel made of conducting material e.g.,
neighbourhood of the system constitutes of a closed
Copper or steel is an examnple
its surroundings.
systern.
For example, if we are studying the
reaction between two substances A and B SuTOundngs
Suroundngs
the
kept in a beaker, the beaker containing
room
Matter
reaction mixture is the system and the
where the beaker is kept is the surroundings
Matter
(Fig. 6.1).
Systern
Suroundngs Energy

(a) Open System (b)Closed Systemn

System Sunoundngs

Fig. 6.1 System and the surroundings

by
Note that the system may be defined
Matter

physical boundaries, like beaker or test tube,

Energ
or the system mnay simply be defined by a set
of Cartesian coordinates specifying a
particular volume in space. It is necesSsary to (c) Isolated System
think of the system as separated from the Fig. 6.2 Open, closed and isolated systems.
surroundings by some sort of wall which may
boundary.
systemn then uwalls of the beakers wll act as
We could have chosen only the reactarnts as

2
 156
CHEMISTRY

3. Isolated System a quantity which represents the total energy

In an isolated system, there is no exchange of of the system. It nmay be chemical, electrical,
energy or matter between the system and the mechanical or any other type of energy you
surroundings Fig. 6.2 (c)). The presence of may think of, the sum of all these is the energy
reactants in a thermos flask or any other closed of the system. In thermodynamics, we call it
insulated vessel is an example of an isolated the internal energy, Uof the system, which may
system. change, when
6.1.3 The State of the System heat passes into or out of the system,
The system must be described in order to make work is done on or by the system,
any useful calculations by specifying matter enters or leaves the system.
quantitatively each of the properties such as These systems are classified accordingly as
its pressure (p), volume (), and temperature
(T) as well as the composition of the system. youhave already studied in section 6.1.2.
We need to describe the system by specifying (a) Work
it before andafter the change. You would recall
from your Physics course that the state of a Let us first examine a change in internal
system in mechanics is completely specified at energy by doing work. We take a system
a given instant of time, by the position and containing some quantity of water in a
thermos flask or in an insulated beaker. This
velocity of each mass point of the system. In
thermodynamics, a different and much simpler would not allow exchange of heat between the
concept of the state of a system is introduced. system and surroundings through its
It does not need detailed knowledge of motion boundary and we call this type of system as
of each particle because, we deal with average adiabatic. The manner in which the state of
measurable properties of the system. We specify such a system may bechanged willbe called
the state of the system by state functions or adiabatic process. Adiabatic process is a
statevariables. process in which there is notransfer of heat
The state of a thermodynamic system is between the system and surroundings. Here,
described by its measurable or macroscopic the wall separating the system and the
(bulk) properties,We can describe the state of surroundings is called the adiabatic wall
a gas by quoting its pressure (p), volume (V). (Fig 6.3).
temperature (T), amount (n) etc. Variables like
p, V, T are called state variables or state surroudings
functionsbecause their values depend only
on the state of the system and not on how it is
reached. In order to completely define the state
of a system it is not necessary to define all the
properties of the system; as only a certain Matter q=0
number of properties can be varied
indeperndently. This number depends on the Energy
nature of the system. Once these minimum
number of macroscopic properties are fixed,
others automatically have definite values.
The state of the surroundings can never Fig. 6.3 An adiabatic system which does not
be completely specified: fortunately it is not permit the transfer of heat through its
necessary to do so. boundary.
6.1.4 The Internal Energy as a State Let us bring the change in the internal
Function energy of the system by doing some work on
When we talk about our chemical system it. Let us call the initial state of the system as
losing or gaining energy, we need to introduce state A and its temperature as T,. Let the
 157
THERMODYNAMICS

internal energy of the system in state A be the change in temperature is independent of

the wute taken. Volume of water in a pond,
called [Link] can change the state of thesystem
in two different ways. for example, 1s a state function, because
change in volumne of its water is independent
Oneway: We do some mechanical work, say of the route by which water Is filled in
the
1kJ, by rotating a set of small paddles and pond, either by rain or by tubewell or by both,
thereby churning water. Let the new state be
called B state and its temperature, as T,. It is (b) Heat
a
found and the change in We can also change the internal energy of
that Tp
temperature, AT = B Let the system by transfer of heat from
the
internal surroundings to the system or vice-versa
energy of the system in state B be U, and the
change in internal energy, AU =U-U, without expenditure of work. This exchange
temperature
Second way: We now do an equal amount of energy, which is a result of
difference is called heat, q. Let us consider
(i.e., lkJ) electrical work with the help of an change in temperature
immersion rod and note down the temperature bringing about the same before in
(the same initial and final states as
change. We find that the change in through
section 6.1.4 (a) by transfer of heat
temperature is same as in the earlier case, say, thermally conducting walls instead of
T,-T; adiabatic walls (Fig. 6.4).
In fact, the experiments in the above
manner were done by J. P. Joule between surroundings
1840-50 and he was able to show that a given
amount of workdone on the system, no matter
how it was done (irrespective of path) produced
the
the same change of state, as measured by
change in the temperature of the system. matter

define a
So, it seems appropriate to systemn
quantity, the internal energy U, whose value energy
as heat
is characteristic of the state of a system,
whereby the adiabatic work, wad required to
bring about a change of stateis equal to the Fig. 6.4 A system which allows heat transfer
of Uin one state
difference between the value
through its boundary.
i.e.,
and that in another state, AU We take water at temperature, T, in a
container having thermally conducting walls,
AU= U, -U, = Wad
say made up of copper and enclose it in a huge
Therefore, internal energy, U, of the system heat reservoir at temperature, T. The heat
is a state function. absorbed by the system (water), q can be
w is
The positive sign exXpresses that ad measured in terms of temperature difference,
positive when work is done on the system. T,-T Inthis case change in internal energy.
Similarly, if the work is doneby the system,wad AU= g, when no work is done at constant
will be negative. volume.
state
Can you name some other familiar state The q is positlve, when heat is transferred
functions? Some of other familiar
functions are V, p, and T. For example, if we from the surroundings to the system and q is
negative when heat is transferred from
bring a change in temperature of the system system to the surroundings.
from 25°C to 35°C, the change in temperature
is 35°C-25°C = +10°C, whether we go straight (c) The general case
up to 35°C or we cool the system for a few Let us consider the general case
in which a
degrees, then take the system to the final change of state is brought about both
by
temperature. Thus, Tis a state function and
158 CHEMISTRY

doing work and by transfer of heat. We write Solution

change in internal energy for this case as: (1) AU= Wad! wall is adiabatic
AU =q + w (6.1) (1) AU=-[Link] conducting walls
For a given change in state, q and w can (ii) A U=q-w, closed system.
vary depending on how the change is carried 6.2 APPLICATIONS
out. However, q +w = AU will depend only on
initial and final state. It will be independent of Many chemical reactions involve the generation
theway the change is carried out. If there is of gases capable of doing mecharnical work or
no transfer of energy as heat or as work the generation of heat. It is important for us to
(isolated system) i.e., if w= 0 and q = 0, then quantify these changes and relate them to the
AU= 0. changes in the internal energy. Let us see how!
6.2.1 Work
The equation 6.1 i.e., AU = q + w is
mathematical statement of the first law of First of all, let us concentrate on the nature of
thermodynamics, which states that Work a systemn can do. We will consider only
mechanical work i.e., pressure-volume work.
The energy of an isolated system is
constant. For understanding pressure-volume
It is commonly stated as the law of work, let us consider a cylinder which
contains one mole of an ideal gas fitted with a
conservation of energy i. e., energy can neither frictionless piston. Total volume of the gas is
be created nor be destroyed. V, and pressure of the gas inside is p. If
Note: There is considerable difference between external pressure is p. which is greater than
the character of the thermodynamic property p. piston is moved inward till the pressure
energy and that of a mechanical property such inside becomes equal to p, Let this change
as volume. We can specify an unambiguous
(absolute) value for volume of a system in a Pressure,
p
particular state, but not the absolute value of
Pex
the internal energy. However, we can measure
only the changes in the internal energy, AUof Area=pa AV
thesystem.
Problem 6.1
Expressthe change in internal energy of V Volume, V
a system whern
No heat is absorbed by the system
(i) Pex
from the suitoundings, butwork (w)
is done on the system. What type of
walldoes the system have ?
(i1) No work is done on the system, but
qamount of heat is taken out from
the system and given to the
surroundings. What type of walldoes
the system have?
(ifi) wamount of work is done by the Fig. 6.5(a) Work done on an ideal gas in a
System and q amount of heat is cylinder when it is compressed by a
supplied tothe system. What type of constant external pressure, Pex
system wouldit be? (in sigle step) is equal to the shaded
area.
 Basic Concepts of Thermodynamics
Every science has its own unique vocabulary associated with it. Precise definition of basic
concepts forms a sound foundation for development of a science and prevents possitble
misunderstandings. Careful study of these concepts is essential for a good understanding
of topics in thermodynamics.

Thermodynamics and Energy

Thermodynamics can be defined as the study of energy, energy transformations and its
relation to matter. The analysis of thermal systems is achieved through the application of
the governing conservation equations, namely Conservation of Mass, Conservation of
Energy (1st law of thermodynamics), the 2nd law of thermodynamics and the property
relations. Energy can be viewed as the ability to cause changes.
First law of thermodynamics: one of the most fundamental laws of nature is the
conservation of energy principle. It simplystates that during an interaction, energy can
change from one form to another but the total amount of energy remains constant.
Second law of thermodynamics: energy has quality as well as quantity, and actual
processes occur in the direction of decreasing quality of energy.
Whenever there is an interaction between energy and matter, thermodynamics is
involved. Some examples include heating and air-conditioning systems, refrigerators,
water heaters, etc.

Dimensions and Units

Any physical quantity can be characterized by dimensions. The arbitrary magnitudes

assigned to the dimensions are called units. There are two types of dimensions, primary or
fundamental and secondary or derived dimensions.
Primary dimensions are: mass, m; length, L; time, t; temperature, T
Secondary dimensions are the ones that can be derivedfrom primary dimensions such as:
velocity (m/s), pressure (Pa = kg/m.s).
There are twounit systems currently available SI (International System) and USCs (United
States Customary System) or English system. We, however, will use Sl units exclusively in
this course. The Sl units are based on decimal relationship between units. The prefixes
used toexpress the multiples of the various units are listed in Table 1-1.
Table 1: Standard prefixes in Sl units.
MULTIPLE 10" 10 10 10 10 10 10° 10 10

PREFIX tetra, T Biga, G mega, M kilo, k centi, c mili, m micro, H nano, n pico, p

SFUM. Bahrami ENSC388 (F 09) Intro and Basic Concepts 1

 Important note: in engineering all equations must be dimensionally homogenous. This
means that every term in an equation must have the same units. It can be used as a sanity
check for your solution.
Example 1:Unit Conversion
The heat dissipation rate density of an electronic device is reported as 10.72 mw/mm by
the manufacturer. Convert this to W/m.
2

10.72
mW 1000mm = 10720
W
2
mm Im 1000mW m

Closed and Open Systems

Asystem is defined as a quantity of matter or a region in space chosen for study. The
mass or region outside the system is called the surroundings.

BOUNDARY
SURROUNDINGS
SYSTEM

Fig. 1: System, surroundings, and boundary

Boundary: the real or imaginary surface that separates the system from its surroundings.
The boundaries of a system can be fixed or movable. Mathematically, the boundary has
zero thickness, no mass, and no volume.
Closed system or control mass: consists of a fixed amount of mass, and no mass can cross
its boundary. But, energy in the form of heat or work, can cross the boundary, and the
volume of a closed system does not have to be fixed.
Open system or control volume: is a properly selected region in [Link] usually encloses
adevice that involves mass floW such as acompressor. Both mass and energy can cross
the boundary of a control volume.
Important note: some thermodynamics relations that are applicable toclosed and open
systems are different. Thus, it is extremely important to recognize the type of system we
have before start analyzing it.
Isolated system: Aclosed system that does not communicate with the surroundings by
any means.

Rigid system: Aclosed system that communicates with the surroundings by heat only.

SFUM. Bahrami ENSC388 (F 09) Intro and Basic Concepts 2

 Adiabatic system: Aclosed or open system that does not exchange energy with
the
surroundings by heat.

X
CLOSED
SYSTEM
m =const.

energy

Fig. 2: Closed system, mass cannot cross the boundaries, but

energy can.

mass

CONTROL
VOLUME

energy

Fig. 3: Control volume, both mass and energy can cross the boundaries.

Energy
In thermodynamics, we deal with change of the total energy only. Thus, the total
energy
of a system can be assigned a value of zero at some reference point. Total energy of a
system has two groups: macroscopic and microscopic.
Macroscopic forms of energy: forms of energy that a system posses as a whole with
respect to some outside reference frame, such as kinetic and potential energy. The
macroscopic energy of a system is related to motion and the influence of some external
effectssuch as gravity, magnetism, electricity, and surface tension.

SFUM. Bahrami ENSC 388 (F 09) Intro and Basic Concepts

 Kinetic energy: energy that a system posses as a result of its relative motion
relative to some reference frame, KE
my?
KE =
2
(kJ)
where Vis the velocity of the system in (m/s).
Potential energy: is the energy that a system posses as a result of its elevation in a
gravitational field, PE
PE = ngz (kJ)
where g is the gravitational acceleration and z is the elevation of the center of gravity
of the system relative to some arbitraryreference plane.
Microscopic forms of energy: are those related to molecular structure of asystem. They
are independent of outside reference frames. The sum of microscopic energy is called the
internal energy, U.
The total energy of a system consistsof the kinetic, potential, and internal energies:
my2
E=U+ KE + PE =U+
2
+ mgz (k/)
where the contributions of magnetic, electric, nuclear energy are neglected. Internal
energy is related to the molecular structure and the degree of molecular activity and it
may be viewed as the sum of the kineticand potential energies of molecules.
The sum of translational, vibrational, and rotational energies of molecules is the
kinetic energy of molecules, and it is also called the sensible energy. At higher
temperatures,system will have higher sensible energy.
Internal energy associated with the phase of a system is called latent heat. The
intermolecular forces are strongest in solids and weakest in gases.
The internal energy associated with the atomic bonds in a molecule is called
chemical or bond energy. The tremendous amount of energy associated with the
bonds within the nucleolus of atom itself is called atomic energy.
Energy interactions with a closed system can occur via heat transfer and work.