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Thermodynamic systems
¦ Thermodynamic system
Thermodynamic system is any collection of objects that is
convenient to regard as a unit, and that may have the potential
to exchange energy with its surroundings.
A process in which there are changes in the state of a thermo-
dynamic system is called a thermodynamic process.
¦ Signs for heat and work in thermodynamics
Q W
ÿ is + if heat is added to system
ÿ is ± if heat is lost by system
is + if work is done by the system.
is ± if work is done on the system.
 Work done during volume changes
¦ Work done
Piston in a cylinder moves by r
due to expansion of gas at pressure

Force on piston: 


Incremental work done:

r r 
r 
r p

ë


VV
 VVVV ]

]
r

 Work done during volume changes (cont¶d)
¦ Work and pV diagram
p Work done depends on the path taken.

ppAA ‡ Process A B :
If VB>VA , W > 0

‡ Process B A :
pB If VB>VA , W < 0

‡ Process A B :
If VA=VB , W = 0

M

]

V


V

V 
V  V° 
 Work done during volume changes (cont¶d)
¦ Work and pV diagram (cont¶d)
p Work done depends on the path taken.
D
pA A C :W =0
C B : W = pB(VB-VA)

B C : W = pB(VA-VB)
pB
C
A C B : W = pB(VB-VA)

A D : W = pA(VB-VA)

D B :W=0

A D B : W = pA(VB-VA)
 Internal energy and the first law of thermodynamics

¦ Internal energy
Tentative definition:
The internal energy U of a system is the sum of the kinetic
energies of all of its constituent particles, plus the sum of
all the potential energies of interactions among these
particles.

¦ The first law of thermodynamics

Ñ
m

Ñ
Yow define the change in internal energy using the first law
of thermodynamics.

It is known from experiments that while Q and W depend on

the path, ÚU does not depend on the path.
 Internal energy and the first law of thermodynamics

¦ A cyclic process
A
: is a process in which the initial pA
and final states are the same.
pB

^

G 0



^  G 
^

0



^ 
B

VA VB
^
^   
^
 0



^ 

If the directions of the arrows are reversed, then

^
^   0


^
 

^ 

 Internal energy and the first law of thermodynamics

¦ Infinitesimal changes in state

The first law of thermodynamics:

r  rÿ Ñ r
For the system we will discuss, the work dW is given by pdV

r  rÿ Ñ
r
 üinds of thermodynamics process
¦ Adiabatic process
An adiabatic process is defined as one with no heat transfer into
or out of a system.

ÚU = -W, Q=0
¦ Isobaric process
An isobaric process is a constant-pressure process.

W = p(V2-V1) , p = constant
¦ Isothermal process
An isothermal process is a constant-temperature process.
For a process to be isothermal, any heat flow into or out of the
system must occur slowly enough that thermal equilibrium is
maintained.
T = constant
 üinds of thermodynamics process (cont¶d)

Work done by a gas depends on the path taken in pV space!

¦ Isochoric process
An isochoric process is a
constant-volume process.

^
^ M ^M
 üinds of thermodynamics process (cont¶d)
¦ Isothermal vs. adiabatic process
D
 
  



]

m


G
 




   ]   

m

m


 


   Isothermal expansion (1 ^ 2 on
 diagram)
for ideal gas:
D
D
 
  



 !
"
  



  ! #^ 2 
 
$

D
  

 


3
 


  
 Internal energy of an ideal gas
¦ Free expansion the same final state
the same initial state

Controlled expansion Uncontrolled expansion

(The temperature is kept = Free expansion
constant and the expansion
process is done very slowly)
Work done Yo work done
Heat exchanged Yo heat exchanged
Different paths
 Internal energy of an ideal gas
¦ Another property of an ideal gas
From experiments it was found that the internal energy of
an ideal gas depends only on its temperature, not on its
pressure or volume.

However, for non-ideal gas some temperature change occur.

The internal energy U is the sum of the kinetic and potential
energies for all the particles that make up the system. Yon-ideal
gas have attractive intermolecular forces. So if the internal energy
is constant, the kinetic energies must decrease. Therefore as the
temperature is directly related to molecular kinetic energy, for a
non-ideal gas a free expansion results in a drop in temperature.
 Heat capacities of an ideal gas
¦ Two kinds of heat capacities
‡ CV : molar heat capacity at constant volume easier to measure
‡ Cp : molar heat capacity at constant pressure
But why there is a difference between these two capacities?
‡ For a given temperature increase, the internal energy change
ÚU of an ideal gas has the same value no matter what the process.
constant-volume (no work)
 
 
  
 


T1 and T2 are the same
constant-pressure
 
 
  





  ^

  * 


 
 
   


  For an ideal gas
 Heat capacities of an ideal gas
¦ Ratio of heat capacities





›xample




   


 m
† for an ideal monatomic gas





   

 m
Ë for most diatomic gas


 Adiabatic processes of an ideal gas
¦ p, V, and ü



 ( by definition)




Ñ ( adiabatic process)
 
 Ñ


 
 
 Ñ


( ideal gas)



  

 
 


 
Ñ 
 

  Ñm    Ñ m




   Ñ mY
Y 
°

 Ñm 
Y °  
 Ñm °
 Adiabatic processes of an ideal gas
¦ p, V, and ü (cont¶d)


 Ñm °



 ( ideal gas)



 Ñm

° 

 °


ÿ G  Ñ Ú ( adiabatic process)
Ú    Ñ m 

  m Ñ   For adiabatic process, ideal gas

   ( ideal gas)

 m
 
mm Ñ
   
mm Ñ
 
  Ñm

For adiabatic process, ideal gas

An equation of state is a functional relationship between pressure
volume and temperature of the fluid .The most simple of such equation
is obeyed by ideal gases.For engineering calculation many gases can
be assumed to behave ideally under atmospheric conditions. however
the only state at which real gases follow ideal behaviour in the true
sense of term, is at zero pressure. Several equations of state were
proposed to explain the behavior of real gases.
This chapter discusses the evaluation of thermodynamic properties of
pure fluids using measurable quantities like the pressure- volume-
temperature relationship, the heat capacity data, and the coefficient
of expansion and compressibility. In addition to the internal energy
and enthalpy two more energy properties both involving entropy in
their definitions are discussed i.e. Helmholtz free energy and the
Gibbs free energy.

The total differential of the four energy properties are used to develop
the maxwell¶s equation. These equation help us to eliminate
unmeasurable quantities like the partial quantities like the partial
derivative of entropy with respect to the pressure or volume
appearing in the thermodynamic relations, in terms of measurable
quantities.
 UYIT 2 SOLUTIOY TH›RMODYYAMICS

A proper understanding of the thermodynamic properties of solution is

essential for analysis of many chemical engineering problems such as
phase equillibria and chemical reaction equillibria.

The partial molar property of substance in solution is an intensive

property strongly depend on concentration. It gives the increase, in the
property of the solution resulting from the addition at constant
temperature and pressure, of one mole of the substance to such large
quantity of the system that its composition remains virtually unchanged.
The method of tangential intercepts was found to be most suitable for
the determination of partial molar properties.
 Ideal solutions

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Lewis Randal rule is applicable for evaluating fugacity of
components in gas mixture.

Lewis Randal rule is valid for

At low pressure when gas behaves ideally.
When Physical properties are nearly same.
At any pressure if component present in excess.
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The Raoult¶s law states that the partial pressure of component in
vapour phase is directly proportional to mole fraction of that
component in the liquid ,which is in equilibrium with the vapour.
›ven for non ideal solutions the partial pressure was found to be
directly proportional to the mole fraction in the liquid as the mole
fraction approaches zero(Henry¶s law). Often the solute portion of
a dilute non ideal liquid solution can be assumed to follow henrys
law and the solvent portion the Raoult¶s law.
The Gibbs- Duhem equations were developed relating the partial molar
properties of the component to one another. They tell us that partial molar
properties of a mixtures cannot change independently; in a binary mixture,
if the partial molar property of one component increases ,that of the other
should decrease. Various forms of Gibbs-Duhem equation applicable for
binary solutions were also developed.
 UYIT 3 TH› PHAS› ›QUILIBRIA

Majority of chemical industries employ transfer of mass between phases

either during the preparation of raw materials or during the purification of
the finished products.

The major thrust of the section was the development of relationship

between the various properties of system such as pressure, temperature
and compositon when a state of equilibrium was attained between the
different phases constituting the system. For a system to be in
mechanical equilibrium the temperature and pressure should be uniform
throughout the system .
For single component systems in thermodynamic equilibrium under
a given temperature and pressure,the molar free energy should be
the same in each phase.

It¶s logical extension of multicomponent multi phase systems reveals

that if a system consisting of several components distributed between
various phases is in thermodynamic equilibrium at a definite
temperature and pressure the chemical potential of each component
will be the same in all the phases.
Vapour- liquid equilibrium involve the calculation of composition of the
liquid and vapour phases such that the fugacity of the components are the
same in both the phases. To evaluate quantitatively the equilibrium
compositions the fugacity be expressed in terms of mole fraction in the
mixture. The fundamental relationship for general VL› problem were
derived . The vapour liquid equilibrium for a system of limited miscibility
and the liquid liquid equilibrium would be helpful of many important
separation processes.
 UYIT 4 CH›MICAL R›ACTIOY ›QUILIBRIA

Thermodynamics of chemical reactions is mainly concerned

with the prediction of equilibrium conversion attainable in a
reaction and the effect of operating conditions on the degree of
completion of reaction.

The criterion chemical equilibrium requires that for a chemical

reaction occurring at equilibrium, there should be no change
in the Gibbs free energy of the system at constant temperature
and pressure. If the system is not in chemical equilibrium, the
reaction occurring must be irreversible and the total Gibbs free
energy must decrease at constant temperature and pressure.
 The equilibrium constant was related to the standard free energy
change. Thus the numerical value of The equilibrium constant
depends on temperature. However it is independent of pressure at
equilibrium.

The effect of temperature on the equilibrium constant was quantitatively

expressed by van¶t Hoff equation. For an exothermic reaction the
equilibrium constant decreases as the reaction temperature increases.
Three methods for the evaluation of The equilibrium constant were
discussed. The one which made use of thermal data in the form of
standard heat of reaction and a standard free energy change of reaction
at a temperature was found to be the most convenient.
If the partial pressure was lowered below this equilibrium value the
solid would decompose and if the pressure on the system was
maintained above the value the formation of solid was favoured.
 UYIT 5 TH›RMODYYAMIC AYALYSIS OF PROC›SS

The refrigeration cycles, the carnot cycle , the vapour compression

cycle, the air refrigeration cycle, and absorption refrigeration cycle
were analyzed for their coefficient performance and merits and
demerits were discussed .

The vapour compression cycle employing an expansion engine

gives higher COP but are not recommended for small scale
applications.An absorption refrigeration system uses for acheving
refrigeration, the heat absorbed from a high temperature source
directly without converting it into work by means of heat engine.
A thermodynamic analysis of linde process employing free expansion
and the claude process employing isentropic expansion was greater
than that in free expansion. However the isentropic expansion
process has practical difficulties that are associated with the
operation of turbine with a two phase mixtures.

The thermodynamic analysis of steam power plants was done by

comparing the performance of the actual cycles.