THERMODYNAMICS

 Thermodynamics can be defined as the science

of energy.

 The name thermodynamics stems from the

Greek words therme (heat) and dynamis
(power).

 Thermodynamics is the science which deals

with transformation of energy of all kinds from
one form to another
THE FIRST LAW OF
THERMODYNAMICS
 Anexpression of the conservation of energy principle,
and it asserts that energy is a thermodynamic property

THE SECOND LAW OF THERMODYNAMICS

IT STATES THAT ENERGY HAS A QUALITY AS
WELL AS QUANTITY, AND THE ACTUAL
PROCESSES OCCUR IN THE DIRECTION OF
DECREASING QUALITY OF ENERGY
INTERNAL AND EXTERNAL ENERGY
By internal energy we mean the energy of
a substance associated with the motions,
interactions, and bonding of its
constituent molecules
It is associated with the velocity and

location of its center of mass.

PRACTICE SESSION
 Calculate the potential energy of a rain drop that falls
from a height of 70m, assuming the mass of the rain drop
as 0.15g.

 Calculate the velocity with which the rain drop in the

above problem will hit the ground.

 Convert 212 °F to Kelvin.

 Calculate the absolute pressure in Pascal's if the gauge

pressure is 2.3 atmospheres.
SYSTEM
A thermodynamic system is any
definite quantity of matter or
prescribed region of space enclosed
by a boundary to which
thermodynamic analyses can be
applied.
BOUNDARY AND SURROUNDINGS
 Beyond the system, another part of the universe is the
surroundings.
 Everything outside the boundary is the surroundings.

 Boundary is the surface which separates the system

from its surroundings.

 It may be fixed or moving and real or imaginary.

Surrounding
System s

Boundary
CLOSED SYSTEM
Systems that can exchange energy with the surroundings, but
cannot transfer mass across the boundaries are known as closed
systems.
 In a closed system, matter cannot cross the boundary. Hence

the principle of the conservation of mass is automatically

satisfied whenever we employ a closed system analysis.

Cylinder Piston
OPEN SYSTEMS
 Systems that can exchange both energy and
matter with the surroundings are open systems.
Water in

Control
surface

Water out

 Isolated System
 If a system does not change as a result of changes in its
surroundings, the system is said to be isolated.
ADIABATIC SYSTEM
 Systems may be partially isolated from their
surroundings.
 An adiabatic system is one that is thermally isolated

from its surroundings; a system that is not in thermal

contact but may be in mechanical contact with its
surroundings
TEMPERATURE

 Temperature is a measure of the molecular

activity of a substance.
 The higher the temperature greater is the

movement of molecules.
 It is a relative measure of how “hot” or

“cold” a substance is and can be used to

predict the direction of heat transfer.
PRESSURE
 Pressure is a measure of the force (F) exerted
per unit area (A) on the boundaries of a
substance (or system).
 It is caused by the collisions of the molecules

of the substance with the boundaries of the

system.
 We speak of pressure only when we deal with

a gas or a liquid.
DIFFERENT TYPES OF PRESSURE

Absolute Pressure
The actual pressure at a given position is
called absolute pressure, and it is
measured relative to absolute vacuum
(absolute zero pressure).
  Gauge pressure:
 Most pressure-measuring devices are calibrated to read
zero in the atmosphere, and so they indicate the
difference between the absolute pressure and the local
atmospheric pressure.
 This difference is called the gauge pressure.

VACUUM PRESSURE
 Pressures below atmospheric pressure are called vacuum
pressures and are measured by vacuum gages that indicate the
difference between the atmospheric pressure and the absolute
pressure.
P = Pabs - P atm
gauge

P vac = Patm - P abs

The absolute and gauge pressures in a liquid open to the
atmosphere at a depth h from the free surface are given
as:
P = P atm + ρgh
abs

 P gauge = ρgh

where: ρ = fluid density, kg/m3

g = acceleration due to gravity,
9.807 m/s2
h = height of the liquid, m
PRACTICE SESSION
 Calculate the pressure in atmospheres at the bottom of
the tank which holds water to a height of 15000mm.

 Calculate the specific heat at constant pressure if the

specific heat at constant volume is 0.023 kJ/mole.k

 Draw the isothermal line in a P V graph.

 Calculate the change in internal energy, change in

enthalpy, work done and heat supplied for a system
which was initially at 1 atm, 20 ºC and 2500 lit, heated at
constant pressure to 5 m3.
EQUATIONS OF STATE
P,V,T, and n are not independent.
Any three will determine the fourth.
An equation of state is an equation that
relates P,V,T, and n for a given substance.
Gases have the simplest equations of
state.
The simplest equation of state is the ideal
gas law, pV = nRT
 IDEAL GAS LAW
pV nRT
p = pressure
 V = volume

 n = moles

 T = temperature

 R = universal gas constant

Table 1.1 The values of the molar gas constant R in various

units
__________________________________________
R = 8.3145 J . mol-1 . K-1
= 0.083145 dm3 . bar . mol-1 . K-1
= 83.145 cm3 . bar . mol-1 . K-1
= 0.082058 L . atm . mol-1 . K-1
= 82.058 cm3 . atm . mol-1 . K-1
__________________________________________
IDEAL GAS MODEL
 Molecules may be treated as point masses relative to the
volume of the system.
 Molecular collisions are elastic, i.e. kinetic energy is

conserved.
 Intermolecular forces of attraction and repulsion have

negligible on the molecular motion.

 The internal energy of an ideal gas depends only on

temperature. It is independent of pressure and volume.

 U   U 
   0  
 V  T  P  T
PROPERTY RELATION OF AN IDEAL GAS
 The definition of heat capacity at constant volume leads
for an ideal gas to the conclusion that Cv is a function of
temperature only.  U   dU 
   
Cv  T  v  dT  = Cv (T)

The defining equation for enthalpy, applied to an ideal gas leads to the conclusion that enthalpy H also is a function
of temperature only.
H= U+PV
= U(T)+RT= H(T)

The heat capacity at constant pressure C p is a function of temperature only:

 H  dHT 
Cp    = Cp (T)
 T  p dT
A useful relation between Cp and Cv for an ideal gas is obtained from above.

dH dU
Cp    R= Cv + R
dT dT
EQUATIONS FOR PROCESS INVOLVING
IDEAL GAS
PV
Diagram
CONSTANT VOLUME PROCESS ,

 An isochoric process is one in which the volume is held constant

(V=constant), meaning that the work done by the system will be zero.
 It follows that, for the simple system of two dimensions, any heat energy
transferred to the system externally will be absorbed as internal energy.
 An isochoric process is also known as an isometric process or an iso
volumetric process.
 An example would be to place a closed tin can containing only air into a
fire. To a first approximation, the can will not expand, and the only change
will be that the gas gains internal energy, as evidenced by its increase in
temperature and pressure. Mathematically, δQ = dU.

U m CV dT

H m C P dT
W  PdV 0
By 1st law ,

Q U m Cv dT
CONSTANT PRESSURE PROCESS
 An isobaric process occurs at constant pressure (P=constant).
An example would be to have a movable piston in a cylinder,
so that the pressure inside the cylinder is always at atmospheric
pressure, although it is isolated from the atmosphere. In other
words, the system is dynamically connected, by a movable
boundary, to a constant-pressure reservoir.

U  CV dT By 1st law,

H Q  C P dT Q H C p dT
Q  C p dT
W  R(T2  T1 )
CONSTANT TEMPERATURE PROCESS
 An isothermal process occurs at a constant temperature
(T=constant). An example would be to have a system
immersed in a large constant-temperature bath. Any
work energy performed by the system will be lost to the
bath, but its temperature will remain constant. In other
words, the system is thermally connected, by a thermally
conductive boundary to a constant-temperature reservoir.
U H 0
For ideal gas: P
Q  RT ln 2
 V
  RT ln 2


 P1   V1 

. Q=−W
ADIABATIC PROCESS
 An adiabatic process is a process in which there is no energy
added or subtracted from the system by heating or cooling
(δQ=0). For a reversible process, this is identical to an
isentropic process. We may say that the system is thermally
insulated from its environment and that its boundary is a
thermal insulator. If a system has an entropy which has not yet
reached its maximum equilibrium value, the entropy will
increase even though the system is thermally insulated.
PV  cons tan t
 P1V1  P2V2 cons tan t
 1  1

T2  V1   P2 
Hence,    
T1  V2   P1 
Work of an adiabatic process is given by
 1  1
     
P1V1   P2    RT1 1   P2  
W  1    
  1 P
 1     1 P
 1  
   
POLYTROPIC PROCESS
 The pressure volume relationship is given by
PVn = constant
 If n = 0 , the process is constant pressure
 If n = 1 , the process is isothermal

 If n= ∞, the process is constant volume

 If n = γ, the process is adiabatic.

 Generally n varies from 1 to γ, meaning the process varies

between isothermal and adiabatic .

EXERCISE - 1
 Air is compressed from an initial condition of 1 bar and 25 0C to a
final state of 5 bar and 250C by heating at constant volume followed
by cooling at constant pressure. Calculate the work required (W),
heat transferred(Q), and the changes in internal energy(∆U) and the
enthalpy of air(∆H) for each process.
Air may be considered an ideal gas with the constant heat capacities
CV=20.785 or (5/2) R; CP=29.099 or (7/2) R
where R=8.314J/mol K
sol:
Basis : 1 mole of air
For constant volume process,
For constant volume process, P1  P2 P2T1
 T2  (5)(298) 1490 K
T1 T2 P1

Q nU nCV T (sin ce, W 0)

=(20.785)(1490-298)= 24788 J.
H C P T ( 29.099)(1490  298) 34703 J / mole

W=0
 EX 1 CONT..

 For the second step at constant pressure,

Q H C P T (29.099)(298  1490)  34703 J
U CV T (20.785)(298  1490)  24788 J / mole
W U  Q  24788  ( 34703) 9915 J

Hence for the entire process,

U 24788  24788 0
H 34703  34703 0
Q 24788  34703  9915 J
W 0  9915 9915 J
EXERCISE 2
 Carbon dioxide is compressed from an initial condition of 1 bar and
250C to a final state of 5 bar and 250C by an isothermal compression.
Calculate the work required (W), heat transferred (Q), and the
changes in internal energy (∆U) and the enthalpy of air(∆H) for each
process.
 Air may be considered an ideal gas with the constant heat capacities
CV=20.785 or (5/2) R CP=29.099 or (7/2) R
 where R=8.314J/mol K

Sol :
Basis : 1 mole of carbon di oxide
For the isothermal compression of an ideal gas,
U H 0
P 
 
Hence, Q  W  nRT ln 2   (8.314)(298.15) ln 5  3990 J
1
 P1 
EXERCISE 3
Calculate the change in internal energy, change in enthalpy, work done and the heat supplied in the following processes

•An ideal gas is expanded from 5 bar to 4 bar isothermally at 600 K.

•Anideal gas contained in a vessel of 0.1m 3 capacity is initially at 1 bar and 298 K. It is heated at constant volume to 400 K.
Given Cp = 30J/mol K
 EXERCISE 4
An ideal gas undergoes the following sequence of mechanically
reversible processes in a closed system. From an initial state of 70º C and
1 bar, it is compressed adiabatically to 150ºC.Calculate W, Q, ΔU and
ΔH for process.
PVT BEHAVIOR OF PURE
SUBSTANCES
 The heat and work flows on to a system depend on the thermodynamic
properties such as enthalpy and internal energy.
 For example, the heat required to change the temperature of 1 kg water by
10 degrees will be different from that needed to change the temperature of
one kg of air by 10 degrees.
 For fluids these properties are evaluated from measurements of molar
volume as a function of temperature and pressure.
 The relationship between pressure (P), molar volume (V) and temperature
(T) may be expressed mathematically as equations of state.
 E.g. PV=nRT gives a simple realistic model of fluid behavior
PHASE DIAGRAM AN INTRODUCTION
 Equations of state are useful in metering of fluids, sizing
of vessels and pipelines. The behavior of a pure
substance can be expressed in terms of PVT diagrams.
 Understanding of phase diagrams is essential to

thermodynamics because there will be many occasions

in which reference to a phase diagram
PROPERTY DIAGRAMS-PRESSURE
TEMPERATURE DIAGRAM (PHASE
DIAGRAM)
COMPONENTS OF PHASE DIAGRAM
 This diagram is often called phase diagram
since all phases are separated from each other
by three lines.
 The sublimation line separates the solid and

vapor regions, the vaporization line separates

the liquid and vapor regions, and the melting (or
fusion) line separates the solid and liquid
regions.
 These three lines meet at the triple point, where

all three phases coexist in equilibrium.

CRITICAL POINT

 Itis defined as the point at which the

saturated liquid and saturated vapor states
are identical.
 The temperature, pressure, and specific

volume of a substance at the critical point

are called the critical temperature (Tc),
critical pressure (Pc), and critical specific
volume (vc), respectively.
PV DIAGRAM

On the PV diagram, we consider only the liquid and vapor state at different
temperatures. Since the liquid state is almost incompressible, it can be seen
that the reduction in pressure at constant temperature produces only negligible
change in volume. There is a rapid increase in volume from the point where
vaporization begins. During the phase change, which takes place at constant
temperature and pressure, the two phases liquid and vapor will be in
equilibrium. The vapor and the liquid coexisting at equilibrium are called
saturated phases.
 Understanding P V diagram

 The pressure at which the liquid and vapor phases

coexist in equilibrium is called the saturation pressure
and the temperature corresponding to this pressure is
called saturation temperature. When the pressure is
lowered to a value less than the saturation pressure at
constant temperature or when the temperature is
increased above the saturation temperature at constant
pressure, the vapor gets superheated.
 If the temperature is less than the critical temperature,

the substance to the right of the saturated vapor line is

called vapor. If the temperature is above the critical
temperature, the substance is called a gas. A vapor can
be condensed to a liquid at compression at constant
temperature or by cooling at constant pressure. A gas can
be condensed by cooling at constant pressure only.
MATHEMATICAL REPRESENTATION OF PVT
BEHAVIOR

 The thermodynamic state of a single homogeneous

fluid may be specified by properties such as pressure,
temperature and volume. The mathematical
expression called PVT equation of state is a
functional relationship between these variables and
may be represented as
f ( P, V , T ) 0

 An equation of state may be solved for any one of the

three quantities P, V or T as a function of the other
two.
 The simplest equation of state is the one applicable for
ideal gases.
VIRIAL EQUATIONS OF STATE
,

 Isotherms for gases and vapours lying are simple curves for which V
increases as P decreases. The product PV can be expressed as a
power series in P: 2
PV a  bP  cP  ......
 If, b aB ' , c aC '
PV a (1  B ' P  C ' P 2  D ' P 3  ......)
' '
where a , B , C , etc are constants for a given temperature and
chemical species.
 It has been shown experimentally that a is the same function of
temperature for all species and can be taken as a=RT
 The above equation can be written as
PV  RT (1  B ' P  C ' P 2  D ' P 3  ......)
Defining PV
Z called compressibility factor. With this definition and with a=RT, the above equation reduces to
RT

Z 1  B ' P  C ' P 2  ........

VIRIAL EQUATIONS OF STATE CONT…
 An alternate expression for Z is also in common use:
B C
Z 1   2  ......
V V
Both the above equations are known as virial expansions and the parameters B’,C’,D’ and B,C,D are
called virial coefficients.

It can be shown that B C  B2

B'  , C' 
RT RT 2
The accuracy required determines the number of terms that are
kept -- more terms make the equation more accurate, but also more
complicated to work with.
APPLICATIONS OF VIRIAL EQUATION
 At temperatures below critical temperatures and low to
moderate pressures, the ideal gas equation ceases to apply.
Under these conditions, you must deal with "real" gases.
 Real gases require more complex equations of state than do

ideal gases, one of some of them being virial equations of

state.
 The two forms of the virial equations are infinite series.

Reasonably close values are realized when two or three terms

are used for gases and vapours at low to moderate pressures.
CUBIC EQUATIONS OF STATE
Virial equations cannot represent thermodynamic
systems where both liquid and vapor are present.
 A "cubic" equation of state is needed to do this. One

such is the Vander Waals equation and the Redlich

Kwong equation.
VAN DER WAALS EQUATION
 In real gases, the molecules occupy some space and so the
actual volume available for the movement of the molecules is
(V-b) where b is the correction for the volume occupied by the
molecules.
 Similarly the velocity of a molecule about to strike the wall of

the container is reduced due to attractive forces of the

neighboring molecules. Since pressure is a direct consequence
of the velocity with molecules strike the container walls,
attractive forces decreases pressure.
 a
 This reduction in pressure is equal to v2
 a 
P 2  V  b  =RT
 V 

 Imposing mathematical conditions at the critical point,

parameters a and b can be determined.

 Pc = 3  RT c 
 
8  Vc 
27R 2 Tc2
 a 
64Pc
RTc
b =8P
c


Pc Vc
Zc 
RTc
REDLICH / KWONG EQUATION
Another two parameter real gas equation is the Redlich-Kwong
equation. It is almost always more accurate than the van der
Waals equation and often more accurate than some equations
with more than two parameters. The Redlich-Kwong equation
is RT a
 
P V  b   T V V  b 

0.42748R 2Tc2 0.08664RTc

a b
Pc Pc
PRINCIPLES OF CORRESPONDING STATES
 These dimensionless thermodynamic co-ordinates provide the
basis for the simplest form of the theorem of corresponding
states:

 All fluids, when compared at the same reduced temperature

and the reduced pressure, have approximately the same
compressibility factor (Z) , and all deviate from ideal gas
behavior to about the same degree.
A-CENTRIC FACTOR
 Corresponding-states correlations of Z based on this
theorem are called two-parameter correlations, because
they require use of the two reducing parameters T c and
Pc. Although these correlations are very nearly exact for
the simple fluids (argon, krypton and xenon) systematic
deviations are observed for more complex fluids.
Appreciable improvement results from introduction of a
third corresponding states parameter (in addition to T c
and Pc), characteristic of molecular structure; the most
popular such parameter is the acentric factor ω,
THREE PARAMETER THEOREM
 All fluids, having the same value of ω, when compared
at the same reduced temperature and the reduced
pressure, have approximately the same compressibility
factor (Z) , and all deviate from ideal gas behavior to
about the same degree.
GENERALIZED CORRELATION FOR
GASES/COMPRESSIBILITY CHARTS:

 Equations of state that express Z in terms of T r and Pr are

said to be generalized because of their general
applicability to all gases and liquids. Generalized
correlations find widespread use. Most popular are the
correlations developed by Pitzer and co-workers for the
compressibility factor Z and for the second and third
virial coefficients B, C.
 The generalized compressibility chart is constructed

based on the principle of corresponding states. The

compressibility factor Z is plotted as a function of
reduced temperature and pressure.
EX 1.6
A CYLINDER IS FILLED WITH CARBON DIOXIDE TO A PRESSURE OF
12X106PA AT 300 K. USING THE GENERALIZED COMPRESSIBILITY
CHARTS, DETERMINE THE MASS OF CARBON DIOXIDE IN THE CYLINDER,
GIVEN THAT THE CYLINDER COULD HAVE HELD 40 KG OF ETHYLENE AT
10 MPA AND 350 K. TC OF ETHYLENE IS 282.3 K. P C OF ETYLENE IS 50.4 X
105 PASCALS. TC OF CO2 = 304.2 K; PC OF CO2 = 73.83 X 105 PA.

Sol
Ethylene :
T = 350 K, Tc = 282.3 K
Tr= 1.24 ; Pr = 1.98
From the Lee Kesler chart, Z = 0.66
CO2
T = 300 K, Tc=304.2 K
Tr= 0.986 ; Pr = 1.63

From the Lee Kesler chart, Z = 0.26

n= 40/28 = 1.4
Moles of CO2= 4.98=5

= 5 x 44 = 220 kg