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Thermodynamics

Basic Concepts

Session 1

Introduction:

Thermodynamics deals with heat inter-action and work inter-action with the

substances called systems. Work and heat are forms of energy. Transfer of heat or work

to a substance brings about certain changes in the substance and whatever change

happens is called a process. Thermo means heat. Since work is also a form of energy,

thermo is taken to mean heat and work. Dynamics refers to the changes that occur as a

result of heat or work transfer.

Biological systems are capable doing work. For example, micro-organism is

capable swimming in the body fluid of its host. It needs to do the work. Where does

energy for doing this work come from? It is the metabolic activity that converts some

form of energy (Nutrition that it takes form host is a form of chemical energy) into work.

It is important then to understand how this happens so that we can exploit this to our

engineering benefit.

In thermodynamics we have work transfer, heat transfer and then we have a

system for interaction which undergoes a process. Let us look at these basic terms.

System:

We need to fix our focus of attention in order to understand heat and work

interaction. The body or assemblage or the space on which our attention is focused is

called system. The system may be having real or imaginary boundaries across which the

interaction occurs. The boundary may be rigid and sometimes take different shapes at

different times. If the system has imaginary boundary then we must properly formulate

the idea of system in our mind.

1

Surroundings:

Every thing else apart from system constitutes surroundings. The idea of

surroundings gets formulated the moment we define system. System and surroundings

together form what is known as universe.

Closed system:

If the system has a boundary through which mass or material cannot be

transferred, but only energy can be transferred is called closed system. In an actual

system, there may not be energy transfer. What is essential for the system to be closed is

the inability of the boundary to transfer mass only.

Open system:

If the system has a boundary through which both energy and mass can transfer,

then it is called open system.

Properties:

Variables such as pressure, temperature, volume and mass are properties. A

system will have a single set of all these values.

Intensive properties:

The properties that are independent of amount contained in the system are called

extensive properties. For example, take temperature. We can have a substance with

varying amount but still same temperature. Density is another example of intensive

property because density of water is same no matter how much is the water. Other

intensive properties are pressure, viscosity, surface tension.

2

Extensive properties:

The properties that depend upon amount contained in the system are called

extensive properties. Mass depends upon how much substance a system has in it therefore

mass is an extensive property.

State:

It is defined as condition of a system in which there are one set of values for all its

properties. The properties that define the state of a system are called state variables.

There is certain minimum number of intensive properties that requires to be specified in

order to define the state of a system and this number is uniquely related to the kind of

system. This relation is phase rule which we shall discuss little later.

Process:

The changes that occur in the system in moving the system from one state to the other is

called a process. During a process the values of some or all state variables change. The

process may be accompanied by heat or work interaction with the system.

Heat:

It is a form of energy that exists only in transit. This transit occurs between two points

which differ in temperature. Since it exists only in transit, it should be accompanied by

changes that occur in the system. The moment this energy cease to move, it appears as

internal energy. We shall discuss internal energy when we deal with I law of

thermodynamics.

Work:

It is also a form energy that exists only in transit. The work cannot be stored. Work is

defined as the product of force and distance through the force moves. Mathematically,

3

where f is the force and d the displacement. Work is a scalar quantity.

Let us look at the following piston and cylinder arrangement containing some gas. The

system considered is the gas in the cylinder. It is exerting some pressure on the piston in

the upward direction. This is balanced by the atmospheric pressure plus the weight and

therefore piston though it is free to move, does not move. If the weight is increased, then

the piston moves downwards. The pressure of the gas increases and the movement of the

piston stops when the pressures become equal. The additional weight is doing the work

on the gas. The additional weight has to push the force created by the gas inside to move

the piston. So there is force and distance. But as the piston moves, the pressure

continuously changes. Therefore consider small distance (dL) for which work done (dW)

is also small as shown in the figure which results in small volume change (dV). Then by

definition of work, we have, if A is the cross sectional area of the piston

d f W

cos d f

dL

4

Integrating between the two locations of the piston,

2

1

2 1

pdV W

This is the equation we use to determine the work. Please note that in general p cannot

be taken out of the integral sign as p may be continuously changing as above.

If we have a p vs. V curve, we can determine the integral as area under the curve.

The area under the curve a21b is the work done on the gas.

We can carry out a process differently with the same initial and final states given

by the points 1 and 2. Since it is a different process, the curve will be different. In that

case the area under the curve will also be different which means to say the work done is

different though the initial and final states are same. Thus the work depends upon the

process or path or how the state is changing. Such quantities are called path functions.

Since heat is also energy in transit as the work is, heat must also be a path function. No

matter what process, as long we have same initial and final states, it brings about the

same pressure difference. Such properties which depend only on state are called state

properties.

1

2

a b

p

V

5

dL f dW

,

_

A

V

d pA

pdV

Thermodynamics

Basic Concepts

Session 2

Equilibrium state:

A system is said to be in thermodynamic equilibrium if it satisfies the condition

for thermal equilibrium, mechanical equilibrium and also chemical equilibrium. If it is in

equilibrium, there are no changes occurring or there is no process taking place.

Thermal equilibrium:

There should not be any temperature difference between different regions or

locations within the system. If there are, then there is no way a process of heat transfer

does not take place. Uniformity of temperature throughout the system is the requirement

for a system to be in thermal equilibrium.

Surroundings and the system may be at different temperatures and still system

may be in thermal equilibrium.

Mechanical equilibrium:

There should not be any pressure difference between different regions or locations

within the system. If there are, then there is no way a process of work transfer does not

take place. Uniformity of pressure throughout the system is the requirement for a system

to be in mechanical equilibrium.

Surroundings and the system may be at pressures and still system may be in

mechanical equilibrium.

6

Chemical equilibrium:

There should not be any chemical reaction taking place anywhere in the system,

then it is said to be in chemical equilibrium. Uniformity of chemical potential throughout

the system is the requirement for a system to be in chemical equilibrium.

Surroundings and the system may have different chemical potential and still

system may be in chemical equilibrium.

Thermodynamic process:

A system in thermodynamic equilibrium is disturbed by imposing some driving

force; it undergoes changes to attain a state of new equilibrium. Whatever is happening to

the system between these two equilibrium state is called a process. It may be represented

by a path which is the locus all the states in between on a p-V diagram as shown in the

figure below.

For a system of gas in piston and cylinder arrangement which is in equilibrium, altering

pressure on the piston may be driving force which triggers a process shown above in

which the volume decreases and pressure increases. This happens until the increasing

p

V

1

2

7

pressure of the gas equalizes that of the surroundings. If we locate the values of all

intermediate states, we get the path on a p-V diagram.

Phase rule:

The two gas samples below have the same density, viscosity and all other intensive

properties.

1 m3 of nitrogen at a pressure of 2 atmosphere and 300 K

2 m3 of nitrogen at a pressure of 2 atmosphere and 300 K

If a gas behaves ideally, then

RT

p

V

n

nRT pV

RT

pM

V

nM

V

m

RT

pM

Thus the density of an ideal gas depends upon only temperature and pressure as all other

quantities are constants. Since p and T are same for the above nitrogen samples, density is

same. If we take out 1 cc of sample from any of those two, by observing only this 1 cc

sample we can never from where we took the sample. This means to say the samples are

exactly same and indistinguishable. They are said to be in the same state.

In order to define this state of nitrogen, we need only T and p. Thus we need minimum

two variables to specify the state. This number is given by Gibbs phase rule which is

given by

N F + 2

8

where

F : degrees of freedom

: Number of phases

N : Number of components

For the above example, number of phases is one; number of components is one therefore

the degrees of freedom are two. For a system containing liquid water and its vapor in

equilibrium, we get the degrees of freedom to be one.

Following is the phase diagram of water which describes in what phase or phases

it can exist for different temperature and temperature.

9

T

p

Liquid

Solid

Vapor

10

For the system to have two phases, if we mention the temperature alone given by

the vertical line, the pressure has to be the one given by horizontal line. Given the

pressure, its temperature gets fixed. Thus we have a freedom of fixing only one of them

which amounts to say degrees of freedom is one.

Heat reservoirs:

If the temperature of the system does not change if we remove a finite quantity of

heat from it, then the system is said to be heat reservoir. If the temperature of the system

does not change if we add a finite quantity of heat to it, then the system is said to be heat

sink.

Ocean can be made to act either as heat reservoir or heat sink.

Heat Engine:

Work and heat are forms of energy and are inter-convertible. Any device which

converts continuous supply of heat into useful work continuously is called heat engine.

For any system to undergo continuous process, it should be cyclic. The detailed

mathematical treatment of heat engines will follow in 5

th

chapter on second law of

thermodynamics.

Irreversible process:

If a thermodynamic process takes place in such a way that we can retrace the path

exactly, the process is called reversible. Consider a piston and cylinder arrangement with

piston free to move at some pressure and temperature in equilibrium. The pressure of the

gas is balanced by a pressure equal to sum of atmospheric pressure and the weight on the

piston pan as shown. If the weight on the piston is reduced, then the piston moves up. Let

us just displace the part of the weight horizontally. This involves work. The piston moves

up as it is free to move until the pressures again become equal.

11

Following is the p-V diagram for the process.

State -2

12

State -1

Looking at the sequencing of the events, it is

1. Removal of part of weight on the piston which takes some work.

2. Moving of piston upward following some path on p-V diagram as shown.

Reaching a new steady position called state 2.

Reversal of these events will mean

1. Piston moving downward from state-2 to state-1.

2. Weight moving on to the piston.

Can this reversal be possible? During expansion step, the system does work on the

surroundings. In reverse then, the surroundings should do the work at state 2. This is

not possible as the system and the surroundings have the same pressure. Exact reversing

is not possible. The process of bringing the weight on the piston pan is also not possible

as we need to do only by moving horizontally. The pan level is higher than that of the

weight. This requires extra work to be done. Further, in moving the weight work was

done on the weight. In reverse then, the weight should do the work, go and sit on the pan!

Clearly this is ridiculous which is not possible.

p

2

1

13

V

In order for a process to be reversible, the driving force must be infinitesimally small. If

we remove the weight bit by bit and place it horizontally, every bit would be placed one

above the other and then piston moves upward. At any point, the piston and the bit

removed are at the same level. As a result, at any point, we can move the bit horizontally,

making the piston move a bit down where the next bit of weight is available at the same

level. Reversing is thus possible.

However there is one work that can never be reversed even in this process. That is the

work done on the bit to move it horizontally. But this is less irreversible compared to the

earlier process where large part of the weight was removed. Look at the state-2, in order

to reverse; the weight has to be lifted by some vertical distance which is missing in the bit

by bit process. We can only strive to make a process only closer to reversibility.

Thermodynamics

Session 3

First law is a statement of law of conservation of energy. For a closed system,

since there is no mass exchange with the surroundings, the total energy of the system

must be always a constant. One form of energy may be converted into another. The

system may possess several forms of energy such as kinetic energy, potential energy,

internal energy.

Potential energy:

It is the energy possessed by a body by virtue of its position. An object kept at a

height z, possesses energy to do the work. A spring kept in a compressed state is also

capable of doing work. A body is said to be possessing energy only if it can lift weight by

some mechanical means. If we tie a rope to a body at higher level, pass the rope over a

pulley and tie the other end to another body whose mass is slightly lower, the second

body will be lifted. To one end of the compressed spring in the vertical position, tie a

weight and then release the spring. The weight goes up. Thus a body at higher level or

14

spring in its compressed state possesses energy. The potential energy of a body of mass

m at height of z from some arbitrary level (reference level) is given by

mgz E

P

Arbitrary level may by any level. As long as the same, the changes in energy will also be

same. The changes in potential energy as the level changes will be

z mg z z mg E

i f P

) (

Kinetic energy:

It is defined as the energy possessed by a body by virtue of its velocity. For a

body of mass m which is moving with a velocity u, the kinetic energy is given by,

2

2

1

mu E

K

Change in kinetic energy is

2 2 2

2

1

) (

2

1

u m u u m E

i f K

Internal energy:

When some external work is transferred to a body, its temperature increases

indicating rise in internal energy. Internal energy is due to molecular energy of vibration

and rotation.

First law of thermodynamics for a closed system:

15

If Q is the amount of heat transfer to a system which does W amount of work

(work transfer form the system), then the change in the total energy of the system will be

Q W. This change will have its implications on the kinetic, potential and internal

energy. Since law of conservation is to be valid, the change in internal energy Q W

must be equal to the changes occurring in all forms energy. Mathematically,

K P

E E U W Q + +

Generally, the changes in kinetic and potential energy will be negligible compared to heat

and work interaction,

U W Q

This is first law of thermodynamics. Note that Q is the heat transfer to the system and W

is work done by the system.

Cyclic process:

If the process occurs in such a way that periodically its state repeats then the

process is called cyclic process. The following p V diagram represents a cyclic process.

16

The states 1, 2 and 3 keep repeating in the process in that order. Not only this, all the

states in between also will repeat. Every time process state changes from 1 to 2, 2 to 3

and 3 to 1 following the same paths. During such processes, there will be heat and work

interaction. All the properties will get the same values at state 1 regardless of number of

times cycle repeats. Thus

0

1 3 2 1 1 3 2 1 1 3 2 1 1 3 2 1

T p V U

First law applied to a cyclic process:

Since the change in internal energy is zero,

W Q

W Q

W Q U

0

This means that net heat transfer to the system is the net work done by the system.

p

V

1

2

3

17

Cyclic process consists of several steps. In the cyclic process shown in the diagram, there

are three steps viz., 1-2, 2-3 and 3-1.

Let us have another cyclic process for which heat and work interaction are known as

below.

Step Heat interaction Work interaction

1-2 Q

1-2

is added to the system No work interaction

2-3 Q

2-3

is removed form the system W

2-3

is the work done by the system

3-1 Q

3-1

is added to the system W

3-1

is the work done on the system

Net heat transfer to the system, 1 3 3 2 2 1

+ Q Q Q Q

Net work done by the system, 1 3 3 2

W W W

and

W Q

Flow processes:

So far we considered closed systems only. Let us look at open systems. Mass

exchange can occur. If the process variables do not change with respect to time for the

system, the process is said to be under steady state conditions. Under such conditions the

mass of the system is constant. This is due to the equality of mass entering and leaving.

If the system as a whole is moving undergoing changes, it constitutes steady state flow

process only when the system at a fixed location will have fixed values.

18

This diagram shows an open and steady state flow process. The equipment considered is

between 1 and 2. The gas enters at 1 and leaves at 2. Steady state flow process requires

mass entering at 1 is equal to mass leaving at 2. If certain mass of gas considered to be

the system, such as cylindrical shaped gas at 1, when it reaches a particular location such

as A, it will be at a state (having certain fixed values for all the properties). No matter

what time, the system at A will be in the same state. This is true for all locations.

However, state of the system differs from location to location. There is no variation of the

state with respect to time at a given location.

Heat in, Q

Work output, W

s

1

2

z

1

z

2

A

19

Thermodynamics

Session 4

First law applied to flow process:

Following is the equipment through which the steam is flowing.

Steam enters at 1 and leaves at 2. There is a heat exchanger which adds heat Q to

the steam making it superheated. The superheated steam runs the turbine and shaft work

is obtained. Thus the gas does the work W

s

. The kinetic, potential and internal energy of

the gas changes as it goes from one location to the other. The entrance 1 is at height z

1

and exit is at height z

2

from some reference datum. The velocity of the gas varies as the

flow area varies along the path.

Let us consider unit mass of steam whose volume is the volume of cylinder shown

at location 1. This steam element enters the equipment, goes through it receiving heat Q

in the exchanger, doing work at the turbine and comes out at 2. There are changes

occurring in potential (as the height at which the steam element is present changes),

Heat in, Q

Work output, W

s

1

2

z

1

z

2

20

kinetic energy (as the velocity changes) and internal energy. Let u

1

and u

2

be the

velocities at location 1 and 2. Change in kinetic energy, since m =1, is

) (

2

1

2

1

2

2

u u E

K

Change in potential energy of the steam from 1 to 2 is

) (

1 2

z z mg E

P

Let the change in internal energy be . U We must account for all heat and work

interaction that occur during the process of steam element moving form 1 to 2. The heat

Q is getting transferred in the heat exchanger to the steam element. Apart from work

output of the turbine, there are other fork forms. At location 1, the surrounding has to do

the work on the steam element to push it into the equipment. If the pressure of the steam

is p

1

, and the cross sectional area of the pipe is a

1

, then the distance moved by the steam

element is V

1

/ a1 where V

1

is the specific volume of the steam at 1. The work done at the

entrance on the steam element at 1 is then,

1 1

1

1

1 1 1

) ( V p

a

V

a p W

(Work done on the system)

Similarly work needs to be done by the steam element at section 2 as it has to push the

surrounding which is given by

2 2

2

2

2 2 2

) ( V p

a

V

a p W

(Work done by the system)

The entrance and exit work are also called as flow work. The product of pressure and

volume is the flow work.

21

If the steam element gets into the equipment, it receives work done by the previous steam

element and uses it to push the element next to it. Thus the net work is zero for all the

locations inside the equipment.

Thus the net work done by the element,

1 2

W W W W

S

+

1 1 2 2

V P V P W W

S

+

Substituting in first law of thermodynamics,

) ( ) (

) (

1 1 1 2 2 2

1 1 2 2 1 2

1 1 2 2

V p U V p U E E W Q

V p V p U U E E W Q

E E V p V p W Q

U E E W Q

P K S

P K S

P K S

P K

+ + + +

+ + +

+ + +

+ +

The group

pV U +

occurs frequently in flow processes and is called enthalpy denoted

by the letter H.

pV U H +

Since internal energy, pressure and volume are state functions, enthalpy is also state

function. The above equation becomes,

H E E W Q

H H E E W Q

P K S

P K S

+ +

+ +

1 2

This equation is first law of thermodynamics applied to flow processes. If the changes in

potential and kinetic energy are very small then,

H W Q

S

Heat capacity:

Heat capacity of a substance is defined as the heat transfer necessary to bring

about a change in the temperature of unit amount of substance by one degree centigrade.

Since it is heat transfer which is a path function, it depends upon the way heating is done.

For example gases can be heated to increase the temperature by two different methods.

The unit quantity of gas taken in container with rigid wall, when heated its volume

remains constant. Another method is to have the wall which is flexible. If the piston is

movable in the piston and cylinder arrangement, gas when heated pushes piston and

22

pressure will be constant. Even if we take unit amount of gas in both these heating

methods, it is observed the heat transfer is not the same. Thus we have heat capacity and

constant volume and heat capacity at constant pressure. Mathematically,

dT

dQ

C

p

p

dT

dQ

C

V

V

dT

dQ

C

The heat capacity at constant volume will not be equal to that at constant pressure.

23

Thermodynamics

Session 5

Prepared by Vinod Kallur, RVCE, Bangalore.

PVT Behavior of fluids

Pressure, temperature and volume of gases vary in a definite manner. Based upon the

conditions, matter can exist in solid, liquid and gas phase. This is represented in graphical

form as below. This diagram is for pure water. All pure substances will have more or less

similar diagrams.

Based upon the values of pressure and temperature, if the point lies in a region, the

substance will exist in the corresponding state represented. For example the point a

represents solid state and b represents vapor state. Any point lying on the curve

represents both the phases which are in equilibrium. For example, the point d represents

liquid water and its vapor in equilibrium. Thus there are numerous pair of pressure and

temperature values on the curve and all those points represent liquid and vapor in

equilibrium. Each curve will have always two phases in equilibrium.

T

p

24

Liquid

Solid

Vapor

Critical Point.

Fluid

Gas

a b

d

p T diagram for pure water

The point where all the curves meet is called triple point and at this condition, all the

three phase exist in equilibrium. Critical point is the highest temperature and highest

pressure where the liquid and its vapor can exist in equilibrium.

For all pressures and temperatures higher than those at critical point, the liquid and vapor

properties become similar. This state is called fluid.

Phase is considered liquid if it can be vaporized by reduction in pressure keeping T

constant. This is represented by vertical downward arrow in the figure. The initial point is

in liquid phase region. Phase is considered gas if it can be condensed by reduction in T

keeping p constant. This is shown by horizontal arrow pointing towards left. The point a

represents solid state which on increasing the temperature at constant pressure, only the

temperature of the solid increases until it reaches curve where first drop of liquid appears

and beyond this only vapor exists. This is shown as arrow a b.

The other way is representation using p V diagram for pure substance which is given in

the next figure.

S / V

L / V

L S

C

p

C

p

V

S / L

V

C

T

C

Gas

V

fluid

25

p V diagram for pure substance

There are regions where two phases co-exist in equilibrium. The dashed curve labeled Tc

represents an isotherm at critical temperature.

In thermodynamics, we deal largely with either vapor or gases. The significant portion of

the diagram is given below.

26

The substance at point 1 is in liquid state. If we decrease pressure keeping temperature

constant, the volume decreases along the dashed curve. But this change is very small and

this is why liquids are considered incompressible. Volume change with pressure at

L / V

L

C

p

C

p

V

V

C

T

C

Gas

V

fluid

1

2 3

T

1

4

27

p V diagram for pure substance

constant temperature is negligible for liquids. Decreasing pressure from 1 at constant

temperature (T

1

), a point 2 will be reached where first bubble of vapor appears. Any

further attempt to decrease the pressure fails bringing pressure down, instead more and

more liquid becomes vapor and the pressure and temperature remain constant represented

by dashed horizontal line. Thus point such as 3 represent liquid and vapor in equilibrium.

Further attempt in decreasing the pressure brings the state to the point 4 where all the

liquid becomes vapor. Further decrease in pressure at constant will follow the dashed

curve in the gas region. Thus the dashed line represents an isotherm (T

1

). Given in the

figure there is one more isotherm at a temperature less than T

1

. The dumb bell shaped

curve represents the locus of all points on all isotherms where the points similar to 2 and

3 lie. The isotherms of higher temperature lie on higher and saturated liquid and vapor

volume become closer and closer and finally merge at the critical point. This is point

where liquid and vapor cannot be distinguished. Isotherm T

C

has a point of inflexion at

the critical point.

A point on the curve is called point of inflexion if there is a tangent at that point which

lies on either side of the curve as shown below.

How do we represent this complicated behavior mathematically? This is a challenge

which led to lot of research and we have several mathematical equations. All these

equations do have limitations. We will use simple mathematical equation. This is not a

limitation as no matter what equation all it does is relate pressure, temperature and

volume of gases.

Ideal gas equation: For one mol of any gas,

Internal energy is a function of temperature only.

28

RT pV

2

1

T

T

V

dT C U

2

1

T

T

P

dT C H

No matter what process, the changes in internal energy and enthalpy are given by the

above expression not only for ideal gases even for real gases.

This law is valid for low pressures, large volumes and low temperatures.

At constant pressure

At constant volume

Isochoric Process:

Any process in which volume of the system does not change is called isochoric process.

Work done is zero.

Isobaric process:

pdV dQ dU

29

, dT C dQ

dT

dQ

C

P

p

P

,

_

, dT C dQ

dT

dQ

C

V

V

V

,

_

W Q U

Q U

) (

1 2

2

1

T T C dT C U

V

T

T

V

Q T T C dT C H

P

T

T

P

) (

1 2

2

1

dT C dQ

P

) ( ) (

1 2 1 2

V V p T T C

pdV dT C dU

P

P

) (

1 2

T T C Q H

P

) (

1 2

V V p W

Relation between heat capacities:

Isothermal Process:

Since the temperature is constant there will not be any change in internal energy.

RdT dU dH

RT U H

PV U H

+

+

+

RdT dT C dT C

V P

+

R C C

V P

+

R C C

V P

V P

C C >

30

dW dQ

dW dQ dU

2

1

1

2

ln ln

p

p

RT

V

V

RT W Q

0 U H

Adiabatic Process:

There will not any heat exchange, Q = 0.

dW dU

2

1

V

V

pdV

2

1

V

V

dV

V

RT

2

1

ln

p

p

RT

2

1

ln

p

p

RT

2

1

V

V

pdV W Q

dV

V

RT

dT C

V

dV

V

RT

dT C

V

V

dV

C

R

T

dT

V

31

2

2 2

1

1 1

T

V p

T

V p

V V

P

C

R

C

C

1

V V

P

C

R

C

C

1

1

V

C

R

The temperature and volume change according to the above equation.

The pressure, temperature and volume all vary in the adiabatic process.

Let us get a relation between the other variables.

Since the gas is ideal,

V

dV

T

dT

) 1 (

V

dV

T

dT

) 1 (

2

1

2

1

) 1 (

V

V

T

T

V

dV

T

dT

1

2

1

2

ln ) 1 ( ln

V

V

T

T

1

2

1

1

2

,

_

V

V

T

T

1

2

1

1

2

ln ln

,

_

V

V

T

T

32

2

2 2

1

1 1

T

V p

T

V p

1 1

2 2

1

2

V p

V p

T

T

1

2

1

2

1

1

2

,

_

V

V

V

V

p

p

2 2 1 1

V p V p

p T

T

V

T V

p

H

,

_

,

_

2

1

T

T

V

dT C W U

dW dU

) (

1

1 2

T T

R

1

2 2 1 1

V p V p

W

2

1

2

1

dT C U

dT C H

V

P

33

) (

1 2

T T C W

V

1

1 2

RT RT

1

1 1 2 2

V p V p

2 2 1 1

V p V p

,

_

1

2

2

1

V

V

p

p

1

2

1

1

2

,

_

p

p

V

V

1

1

1

]

1

,

_

1

2

1

1

2 1 1

1

1 p

p

p

p V p

W

1

1

1

]

1

,

_

1

1

2

1

2 1 1

1

1 p

p

p

p V p

1

1

1

]

1

,

_

1

1

1

2 1 1

1

1 p

p V p

W

( )

; 1

1

/ 1

1

2 1 1

1

1

]

1

,

_

p

p V p

W

( )

1

1

]

1

,

_

/ 1

1

2 1 1

1

1 p

p V p

U

Polytropic Process:

It is a representation of all the processes in a mathematical form as below.

Sl. No n Process

1. 0 Isobaric

2. 1 Isothermal

3.

Isochoric

Generally n lies between 1 and .

34

const pV

n

Thermodynamics

Session 6

Prepared by Vinod Kallur, RVCE, Bangalore.

Guidelines to represent processes on p V diagram:

In the figure above there are two isotherms shown. For these isotherms,

.

1 2

T T >

There

is one isotherm passing through every point on p V diagram. Higher the temperature

higher will be location of the isotherm. As they go downwards they converge as shown.

No two isotherms will ever intersect.

p

V

T

1

T

2

35

Similarly every point has an adiabatic curve passing through it. The adiabatic curve

follows the relation const pV

an adiabatic curve as shown below. The adiabatic curve is steeper.

No two adiabatic curves will ever intersect.

The mathematical relation between pressure, volume and temperature applicable all

ranges of values has not been possible. However, there are equations which are valid over

certain ranges.

Conditions for any equation to be equation of state:

1. The equation should reduce to

RT pV

As p 0.

2. p-V curve should have a point of inflexion for isothermal at critical point C,

0

,

_

C

V

p

and 0

2

2

,

_

C

V

p

Van der Waals equation of state:

( ) RT b V

V

a

p

,

_

+

2

Here a and b are constants that depend upon the gas. If we apply the partial derivative

conditions, we get,

C

C

C

C

p

RT

b

p

T R

a

8

;

64

27

2 2

36

p

V

Isotherm

Adiabatic curve

The Van der Waals equation is cubic in V. Therefore it should have three roots for a

given set of values of pressure and temperature and for a given substance. For any

temperature higher than critical temperature, there is one positive root. For critical

temperature and critical pressure, all the three roots will be equal which gives critical

volume. For temperature and pressure less than critical values, there will be three roots,

least one gives the molar volume of saturated liquid and highest gives that of saturated

vapor which are volumes given by the two ends of horizontal section of the isotherm.

Redlich Kwong Equation:

T b V V

a

b V

RT

p

) ( +

C

C

C

C

p

RT

b

p

T R

a

0867 . 0

;

4278 . 0

2 / 5 2

Note that the above equations reduce to the equation

, RT pV

as p 0.

Other equations of state are Peng Robinson and Virial equations.

Numerical problem:

Air is compressed from an initial state of 1 bar and 298 K to a final state of 5 bar and 298

K through two mechanically reversible processes in a closed system. First heating at

constant volume followed by cooling at constant pressure. Calculate W, Q, change in

enthalpy and internal energy. Use

2

5

,

2

7 R

C

R

C

V P

.

37

a

2

V

p

Isotherm at 298 K

The path is shown in the figure. 1 - a represents heating at constant volume and a - 2

represents cooling at constant pressure. Note that initial and final states lie on a single

isotherm.

Let us do the calculations for one mol of gas.

For the path 1 a, since volume is constant, work done is zero.

dQ dU

dT C dU

V

a

T

T

V a

dT C U

1

1

To use this we need to know temperature at a. Since it is closed system and volume is

same at 1 and a,

1 1

T p T p

a a

Since pressure at a is same as that at 2,

K

p

T p

p

T p

T

a

a

1490

1

) 298 ( 5

2

1 1 1 1

a

T

T

V a

dT C U

1

1

kJ

J

R

dT

R

775 . 24

7 . 24775

) 298 1490 (

2

) 314 . 8 ( 5

) 298 1490 (

2

5

2

5

1490

298

Thus Q

1-a

= U

1-a

= 24.775 kJ.

38

1

kJ J dT C H

P a

686 . 34 34686 ) 298 1490 (

2

) 314 . 8 ( 7

1490

298

1

) ( ) (

1 1 1 1 1 1

V p V p U pV U H

a a a a a a

+ +

to calculate change in enthalpy.

For the step a 2,

dW dQ dU

2

2

T

T

V a

a

dT C U

kJ

J

R

dT

R

775 . 24

7 . 24775

) 1490 298 (

2

5

2

5

298

1490

kJ J dT C H

P a

686 . 34 34686 ) 1490 298 (

2

) 314 . 8 ( 7

298

1490

2

pdV dW

2

2

a

a

pdV W

Along the path a 2, since pressure is constant and equal to 5 bar,

2

2

a

a

pdV W

) ( 10 5

2

5

a

V V x

We should know the volume at a.

From gas law, at the initial condition,

3

5 1

02477 . 0

10 1

) 198 ( 314 . 8

m

x

V

Note that we have taken one mol.

39

1

1 1

2

2 2

T

V p

T

V p

2

1 1

2

p

V p

V

3

004954 . 0

5

) 02477 . 0 ( 1

m

Similarly,

3

5

1245 . 0

10 1

) 1498 ( 314 . 8

m

x p

RT

V

a

a

a

kJ J x V V p W

a a

773 . 59 59773 ) 1245 . 0 004954 . 0 ( 10 5 ) (

5

2 2

kJ Q

Q

W Q U

a

a

a a a

548 . 84

) 773 . 59 ( 775 . 24

2

2

2 2 2

For the entire process,

kJ Q Q Q

a a

773 . 59 ) 548 . 84 ( 775 . 24

2 1 2 1

+ +

0 686 . 34 686 . 34

0 775 . 24 775 . 24

2 1 2 1

2 1 2 1

+

+

a a

a a

H H H

U U U

kJ W W W

a a

773 . 59 ) 773 . 59 ( 0

2 1 2 1

+ +

Since there are no changes in internal energy and enthalpy, work done on the system is

given out as heat.

40

Thermodynamics

Session 7

Determination of changes in internal energy and enthalpy:

No matter what is the process the internal energy and enthalpy are determined using the

following formulae.

dT C dH

dT C dU

P

V

. dQ dT C dU

V

If the process is isobaric, then

. dQ dT C dH

P

Let us recall that

1. For ideal gases internal energy is a function of temperature only.

2. The change in internal energy is a state function.

Let us take an adiabatic process and determine change in internal energy.

41

p

V

1

2

Consider two states (1) and (2) on an adiabatic path. There is one isotherm for each state

as shown. Adiabatic curve at (1) is steeper than the isotherm. Whether the process

follows adiabatic path or another curve shown in the figure or any arbitrary path, as long

the initial and final state are same, we get the same change in internal energy.

Let us replace adiabatic path by two steps

1. 1 a constant volume process followed by

2. a 2 isothermal process

to accomplish the same change in the state.

2 1 2 1

+

a a

U U U

a

42

p

V

1

2

Since step 1 a is a constant volume process,

dT C dU

V

step a 2 is isothermal and therefore dU = 0.

0

1

2 1

+

a

T

T

V

dT C U

Since

, T T

a 2

2

1

2 1

T

T

V

dT C U

Any process between any two states can be replaced by either an isothermal process

followed by constant volume process or constant volume process followed by an

isothermal process. The total change in internal energy is the change in internal energy

for constant volume step only. Thus no matter what process the change in internal energy

is given by

dT C dU

V

.

Same idea may be extended to change in enthalpy.

Deviations of real gases form ideal behavior:

The deviation from ideal behavior is measured using what is known as

compressibility factor defined as the ratio of volume determined using ideal gas law

to the actual volume at any given temperature and pressure.

For ideal gases, Z = 1. Higher the value Z away from one higher will be the non-ideality.

Following figure gives the value of Z as a function pressure for different gases. All gases

approach ideal gas behavior at low pressures. This figure is called compressibility chart.

There will be as many curves as there are number of gases. The chart that is given here is

for one temperature. Therefore this figure becomes highly cumbersome if applied for all

gases and all temperatures.

43

RT

pV

V

V

Z

ideal

actual

Theory of corresponding states:

It states that all fluids, when compared at the same reduced temperature and reduced

pressure, will have same compressibility factor and all deviate from ideal behavior to the

same extent.

CH

4

N

2

Z

1.0

p

44

The reduced pressure and temperature are defined by

45

C

r

C

r

T

T

T

p

p

p

Here all gases with the same reduced temperature and pressure lie on the same curve.

This chart is called generalized compressibility chart. Different gases are indicated by

different points on the curve. There will be as many curves as there are temperatures.

This is less cumbersome compared to compressibility chart.

Z

p

r

0 1. T

r

5 1. T

r

5 2. T

r

46

The above table gives two gases with the same Z for different T and p. The reason is that

the critical values are different.

T p

T

c

p

c

T

r

p

r

N

2

189.

3

83.7

5

126.

2

33.

5

1.

5

2.

5

CH

4

286.0

5

114.

5

190.

7

45.

8

1.

5

2.

5

47

Thermodynamics

Session 8

Standard Heat of reaction:

It is defined as the enthalpy change accompanying a reaction when both reactants and

products are at their standard states at 298 K and is denoted by

298

0

H

.

) g ( CO ) g ( O ) s ( C 2 2

2

+

kJ . H 2 221 298

0

If the stoichiometry of the above reaction is represented as

Then,

kJ .

kJ .

H 6 110

2

2 221

298

0

The standard heat of combustion of a substance is defined as the enthalpy change

accompanying the reaction when one mol of the substance undergoes combustion when

both reactants and products are at 298K.

The heat of combustion is 1168.12 kJ.

The standard heat of formation:

Standard heat of formation of a substance is defined as the change in enthalpy

accompanying the formation of 1 mol of the substance from the constituent elements

when the reactants and products are at 298K.

) g ( CO ) g ( O ) s ( C 2 2

2

+

kJ . H 2 221 298

0

Standard Heat of Formation of Carbon monoxide is kJ . H f 6 110

0

.

48

) g ( CO ) g ( O ) s ( C +

2

2

2

; O H ) g ( CO ) g ( O ) l ( CHO CH

2 2 2 2

2 2 2 2 + +

. kJ 222222 H 222

2

Hesss Law of constant heat summation:

The net enthalpy involved in a reaction is the same whether the reaction takes place in a

single step or in a series of steps.

C B A +

Let A and B react to form C with heat of reaction H. Let there be one more method of

carrying out this reaction in two steps as given below.

AB B A +

1

H

C AB

2

H

Treating arrow as an equal sign, adding these two reactions gives,

C B A + ,

2 1

H H +

It has been found that

2 1

H H +

is same as . H

This idea is used to determine heat of reaction from heat of formation or heat of

combustion data.

For example if we want to determine heat of formation of sulfuric acid, we must

determine this from the reaction,

No matter what we do, the above reaction cannot be carried out. Let us carry out other

possible reactions such that the over-all reaction is the formation reaction as below.

49

H

2 2 2 2

2 SO H O S H + +

2 2

SO O S +

1

H

----------(1)

3 2 2

2 2 SO O SO +

2

H

----------(2)

4 2 2 3

SO H O H SO +

3

H

-----------(3)

O H O H

2 2 2

2

1

+

4

H ----------(4)

2(1), 2(3) and 2(4) gives,

2 2

2 2 2 SO O S +

1

2 H ----------(1)

3 2 2

2 2 SO O SO +

2

H ----------(2)

4 2 2 3

2 2 2 SO H O H SO +

3

2 H

-----------(3)

O H O H

2 2 2

2 2 +

4

2 H ----------(4)

Adding these equations along with heat of reactions,

and heat of this reaction will be 2 4 3 1

2 H ) H H H ( + + +

Therefore heat of formation of sulfuric acid is

2

2

4 3 1

H

H H H + + +

This is how Hesss law can be used to determine the heat of reaction of a reaction from

heat of reaction of other reactions.

50

2 2 2 2

2 2 2 2 SO H O S H + +

Thermodynamics

Session 9

First deals with law of conservation of energy and defines internal energy.

A stone falls decreasing its potential energy and converting it into kinetic energy. Just

before it strikes the ground, it has maximum kinetic energy. From there why does it not

go up decreasing its kinetic energy and converting it into potential energy?

If we keep two bodies at different temperature in contact, why there is no heat transfer

from a body of low temperature to a body at higher temperature?

When we remove the wall which separates two gases, the two gases mix together without

any external work done on them. Why then the two gases in a mixed state separate

themselves without any external work?

For all the processes mentioned above there is absolutely no violation of I law. In spite of

that, we do not observe these processes. It appears that there is some sense of direction

for spontaneous processes. There is nothing in the first law to indicate any such direction

to any process.

Is there any difference between heat and work though they are both forms of energy? If

they inter-convertible, then any cyclic process should be able to convert all the heat

supplied into work completely as change in internal energy is zero. Does it happen? It has

been found that we cannot have a device whose sole effect is conversion of heat supplied

into work completely. Let us look at why this is so with an example of a process.

In the following figure, there is a heat exchanger where heat is supplied (Q

1

) to the

system which is water in this case and generates steam at high pressure. The steam flows

into a turbine and rotates it producing useful work W

S

. From the turbine, we get steam at

51

relatively lower pressure than with which it entered. The objective here is to convert heat

Q

1

into work. Since this heat is available, can we send the steam from turbine directly

into the heat exchanger in order to make it work continuously so that we get continuous

supply of work? This is shown by a dotted arrow.

The moment we establish this connection, whole process comes to an abrupt stop! We

have lower pressure steam line going into the heat exchanger in which there is higher

pressure steam. If there is connection like this, why does steam preferentially go into the

turbine line? It will enter into both the lines and stop the turbine. Therefore, in order to

have this going on, we must condense the steam bring about a change in its state so that it

can be fed to the heat exchanger. This state must be same as that of feed water to the heat

exchanger.

Thus there is no way Q

2

= 0. We cannot device any process which converts Q

1

completely

into work. The work obtained W

s

is less than Q

1

by an amount equal to Q

2

. By first law,

since for a cycle change in internal energy is zero,

2 1 S

Q Q W

Practically Q

2

cannot be zero.

If we analyze any cyclic process, there will be several heat and work interactions, such

that net work done is equal to net heat supplied. There will be always one step in which

Q

1

Q

2

W

S

Heat Exchanger

Condenser

Turbine

52

there is heat removed which brings down the amount of heat that is getting converted into

work.

This fact is the basis of statement of II law of thermodynamics. There are several

statements for the II law which are equivalent. In fact we can deduce one from any other.

All the statements are given below.

Second law of thermodynamics:

1. Heat cannot by itself pass from a cold to a hot body.

2. All spontaneous processes are to some extent irreversible and are

accompanied by degradation of energy.

3. It is impossible to construct a heat engine that operates continuously in a cycle

to produce no effect other than conversion of heat supplied completely into

work. This is called Kelvin Planck statement.

4. It is impossible to construct a heat pump (reverse heat engine) that operates

continuously to produce no effect other than transfer of heat from low

temperature body to a high temperature body.

Carnot cycle and Carnot engine:

The Carnot cycle consists of four steps and all the four steps are reversible. The cycle is

shown in the diagram below.

53

There are two isotherms and two adiabatic processes as shown. The isotherms are at TH

and TC.

AB Reversible isothermal expansion

BC Reversible adiabatic expansion

CD Reversible isothermal compression

DA Reversible adiabatic compression

According to first law, it can be shown that

B

A

H AB AB

p

p

ln RT W Q

) T T ( C W

C H V BC

D

C

C CD CD

p

p

ln RT W Q

) T T ( C W

H C V DA

The net work done is given by

p

V

A

B

C

D

T

H

T

C

54

DA CD BC AB net

W W W W W + + +

) T T ( C

p

p

ln RT ) T T ( C

p

p

ln RT

H C V

D

C

C C H V

B

A

H

+ + +

For adiabatic process BC,

/ ) 1 (

C

B

C

H

p

p

T

T

,

_

/ ) 1 (

A

D

H

C

p

p

T

T

,

_

B

A

C

D

p

p

p

p

B

A

C H net

p

p

ln ) T T ( R W

Heat supplied with an objective of converting into work is

B

A

H AB AB

p

p

ln RT W Q

The efficiency is defined as

H

C H

B

A

H

B

A

C H

AB

net

T

T T

p

p

ln RT

p

p

ln ) T T ( R

Q

W

It is clear that efficiency of Carnot engine depends upon only the temperatures between

which it is operating and not on the working substance undergoing the cycle. Since

Carnot engine is reversible, it must have maximum efficiency.

From first law,

55

CD AB net

Q Q W

H

C

AB

CD

AB

CD AB

AB

net

T

T

1

Q

Q

1

Q

Q Q

Q

W

H

C

AB

CD

T

T

1

Q

Q

1

H

C

AB

CD

T

T

Q

Q

Let QCD is heat removed, and be equal to QC; and heat added as Q

H

, with sign convention,

H

C

H

C

T

T

Q

Q

0

T

Q

T

Q

C

C

H

H

+

This equation is applicable to the complete cycle and any quantity that adds to zero for

the cycle is a state property. Thus Q/T is a state property called entropy. Thus second law

of thermodynamics brings in the idea of entropy.

56

Thermodynamics

Session 10

Efficiency of engines:

The efficiency of reversible Carnot Engine is given by

H

C H

H

C H

T

T T

Q

Q Q

The maximum efficiency of any engine operated between two temperatures is always

given by

H

C H

T

T T

Efficiency of real engine is always less than that of reversible engine. If the engine is

irreversible then efficiency is calculated from

H

C H

Q

Q Q

For any irreversible engine,

H

C H

H

C H

T

T T

dQ

dQ dQ

<

H

C

H

C

T

T

dQ

dQ

<

H

H

C

C

T

dQ

T

dQ

<

0

T

dQ

T

dQ

H

H

C

C

< +

57

Thus for irreversible engine,

0

T

dQ

<

0

T

dQ

In general,

0

T

dQ

This is called Clausius inequality. The sum of dQ / T terms over a cycle is less than or

equal to zero depending upon whether the cycle is irreversible or reversible.

The changes in entropy are always determined using,

58

T

dQ

dS

v Re

Let A1B Represent irreversible process and A2B represent reversible process between

the same states.

To determine entropy change we must have only reversible path. However the entropy

change between the states 1 and 2 is same regardless of the path as it is a state function.

What the above equation says is entropy is not equal to dQ/T along an irreversible path.

A

B

1

2

p

V

59

T

dQ

dS

v Re

B 2 A

B A

T

dQ

S d p

T

V

T V d T C d H

p

P

1

1

]

1

,

_

+

To determine entropy change for any irreversible path between two states, replace the

path by a reversible path with the same states, and find the entropy of the reversible path.

Entropy and irreversibility:

Let us look at a cyclic process given below.

Let A1B Represent reversible process and B2A represent irreversible process between

the same states. Therefore A2B is also irreversible. Since A1B is reversible,

B 1 A

B 1 A

T

dQ

S

Since cycle as a whole is irreversible and as per Clausius inequality,

A

B

1

2

p

V

60

0

T

dQ

T

dQ

A 2 B B 1 A

< +

RHS is independent of the path which will be equal to

B 1 A

S .

LHS is dQ / T term and it is along an irreversible path and therefore it does not represent

entropy change.

Mathematical Statement of II law:

For a process involving transfer of heat Q from heat source at T

1

to a heat sink at T

2

,

The process can be made less and less irreversible by lowering the temperature T

1

closer

and closer to T

2

.

As the temperatures become closer and closer, irreversibility decreases and

For any heat transfer there has to be some temperature difference. Therefore T

1

> T

2

and

hence,

61

2

T

dQ

<

2

T

dQ

S

A 2 B

B 2 A

< +

2

T

dQ

S

A 2 B

A 2 B

< +

A 2 B

A 2 B

S

T

dQ

<

2 2

total

T

Q

T

Q

) S ( +

,

_

2 2

2 2

total

T T

T T

Q ) S (

. 2 S

total

. 2 S

total

This is the mathematical statement of II law of thermodynamics. Thus the entropy of the

universe always increases and the energy is conserved.

Because of irreversibility, there will be some dissipation and degradation of energy which

will not be available as work. This is called lost work which is given by

total 0 lost

S T W

Where T

0

refers to the temperature of the sink to which heat is rejected.

Determination of entropy changes:

This is the basic equation. The heat transfer term may replaced by any term using first

law or any equation applicable to the process for which entropy change is to be

determined. This is applicable only the process is reversible. For example, for an ideal

gas undergoing isothermal reversible process,

pdV dW dQ

T

pdV

dS

V

RdV

dS

1

2

V

V

ln R S

This is how entropy changes may be determined

62

T

dQ

dS

R

Thermodynamics

Session 11

Fundamental Property Relations:

Apart from enthalpy, internal energy and entropy, there are other thermodynamic

properties which are necessary to apply to phase equilibria and reaction equilibria. So far

we have treated only closed systems which consist of single phase without any reaction.

In order treat the systems we need to know other energy terms involved with reaction and

phase equilibria. The use these properties will get clearer when we do the chapters on

these areas.

Let us derive the fundamental property relations from basics.

Enthalpy:

From I law,

dW dQ dU

Vdp TdS dH

Vdp pdV pdV TdS

Vdp pdV dU

d(pV) dU dH

pV U H

pdV TdS dU

+

+ +

+ +

+

+

Helmholtz free energy:

It is defined as

A = U TS

63

Differentiating,

dA = dU-d(TS)

= TdS pdV TdS SdT

dA= - pdV SdT

Gibbs Free energy:

It is defined as G = H TS

Differentiating, dG= dH TdS SdT

= TdS +Vdp TdS SdT

dG = Vdp - SdT

These four equations are called fundamental property relations as many equations are

derived from these equations.

Maxwells relations

As some of the thermodynamic properties are not directly measurable, we must write the

equations in terms of measurable properties. The measurable and determinable (by

experiment) properties are temperature, pressure, volume, heat capacities and in some

cases even enthalpies. These relations are derived from fundamental property relations.

The derivations are based upon a mathematical relation applied to exact differential

equations.

If z = f(x,y) then

dy

y

f

dx

x

f

df

x y

,

_

+

,

_

This equation is also written as

df = Mdx + Ndy

For this differential equation to be exact,

y x

x

N

y

M

,

_

,

_

64

Applying these conditions to all the property relations, we get,

Ndy Mdx df +

y x

x

N

y

M

,

_

,

_

pdV TdS dU

V S

S

p

V

T

,

_

,

_

Vdp TdS dH +

p

S

S

V

p

T

,

_

,

_

SdT pdV dA

T V

V

S

T

p

,

_

,

_

SdT Vdp dG

T p

p

S

T

V

,

_

,

_

Generating function:

Consider

2 2

T R

) RT ( Gd RTdG

RT

G

d

,

_

dT

RT

G

dG

RT

1

2

dT

RT

TS H

) SdT Vdp (

RT

1

2

,

_

RT

SdT

RT

HdT

RT

SdT

RT

Vdp

2

+

dT

RT

H

dp

RT

V

2

65

dT

RT

H

dp

RT

V

RT

G

d

2

,

_

From this equation, at constant temperature and at constant pressure we can write,

2 p

T

RT

H

T

) RT / G (

;

RT

V

p

) RT / G (

1

]

1

1

]

1

thermodynamic properties and hence it is called generating function.

Entropy changes:

We know that

V

V

p

P

T

Q

C ;

T

Q

C

,

_

,

_

Since

TdS dQ

,

T

C

T

S

T

S

T C

P

p

p

P

,

_

,

_

And

T

C

T

S

T

S

T C

V

V

V

V

,

_

,

_

Using these,

,

_

1

2

P

T

T

P

p

T

T

ln C

T

dT

C S

2

1

and

66

,

_

1

2

V

T

T

V

V

T

T

ln C

T

dT

C S

2

1

If S is considered as

S = f (T,p) then

dp

p

S

dT

T

S

dS

T p

,

_

+

,

_

P

/T which is derived and

second by a Maxwells relation, we get,

dp

T

V

dT

T

C

dS

p

P

,

_

Similarly by taking S as function of V and T, we get,

dV

T

p

dT

T

C

dS

V

V

,

_

+

If there is any relation between three variables, from mathematics we have, a relation

between p, V and T as

1

V

T

T

p

p

V

p V T

,

_

,

_

,

_

dV

) p / V (

) T / V (

dT

T

C

dS

T

p

V

dV p

) p / V (

) T / V (

T dT C dU

T

p

V 1

]

1

+

Internal energy may also be written as

1

1

]

1

+

,

_

pdV dp

T

V

T dT C dU

p

P

67

Using

, Vdp TdS dH +

we get

dp

T

V

T V dT C dH

p

P

1

1

]

1

,

_

+

68

Thermodynamics

Session 12

Internal energy changes:

The internal energy changes can be expressed in terms measurable quantities such as heat

capacities, pressure, volume and temperature. We can use Maxwells relations to get

these expressions.

The following are fundamental property relations.

We have derived the following relations.

Let us derive the expression for internal energy in terms C

P

and C

V

.

Replace dS in terms of C

V

,

dp

T

V

dT

T

C

dS

p

P

,

_

dV

T

p

dT

T

C

dS

V

V

,

_

+

dV

) p / V (

) T / V (

dT

T

C

dS

T

p

V

69

2

V

T

T

p

p

V

p V T

,

_

,

_

,

_

pdV TdS dU

pdV dV

) p / V (

) T / V (

dT

T

C

T dU

T

p

V

1

]

1

dV p

) p / V (

) T / V (

T dT C dU

T

p

V 1

]

1

+

pdV TdS dU

Vdp TdS dH +

SdT pdV dA

SdT Vdp dG

Internal energy change in terms of C

p

:

Replace dS in terms of C

p

,

Enthalpy changes:

Starting from

in the same way we can get,

We can use these expressions and find the changes in enthalpy. These equations are

applicable for any gas. P-V-T relations used should be for the gas for which you are

determining the changes.

Use these relations and derive the expressions for dH and dU for ideal gas.

Effect of p, V and T on U, H and S:

This is one of the Maxwells relations which gives the effect of pressure on entropy at

constant temperature.

This equation derived earlier gives the effect of temperature on entropy at constant

pressure.

70

pdV TdS dU

pdV dp

T

V

dT

T

C

T dU

p

P

1

1

]

1

,

_

1

1

]

1

+

,

_

pdV dp

T

V

T dT C dU

p

P

Vdp TdS dH +

dp

T

V

T V dT C dH

p

P

1

1

]

1

,

_

+

p T

T

V

p

S

,

_

,

_

T

C

T

S

P

p

,

_

At constant volume,

Or

This gives the effect of temperature on internal energy at constant volume.

At constant temperature, since dT is zero,

This gives the effect of volume of internal energy at constant temperature.

Similarly from

we can get,

At constant pressure,

At constant temperature,

These expressions give the effect of temperature and pressure on enthalpy.

Relationship between the heat capacities:

The heat capacities are related by the following expression.

which can also be written as

using the cyclic relation of partial derivatives of p, V and T.

71

dV

) p / V (

) T / V (

T Vdp dT C dU

T

p

V 1

]

1

+

V

C

dT

dU

V

V

C

T

U

,

_

1

]

1

+

,

_

p

) p / V (

) T / V (

T

V

U

T

p

T

dp

T

V

T V dT C dH

p

P

1

1

]

1

,

_

+

P

p

C

T

H

,

_

p T

T

V

T V

p

H

,

_

,

_

V p

V P

T

p

T

V

T C C

,

_

,

_

T

2

p

V P

V

p

T

V

T C C

,

_

,

_

are called Volume expansivity and isothermal Compressibility. The difference between

heat capacities is written in terms of these as

Effect of pressure and volume on heat capacities:

These are given by the following equations.

72

T

p

V

V

2

,

_

;

T

V

V

2

p

,

_

VT

C C

2

V P

p

2

2

T

P

T

V

T

p

C

,

_

,

_

2

R

V

p T

S

U

T

,

_

V

2

2

T

V

T

p

T

V

C

,

_

,

_

T

p

2

2

T

V

p

V

T

p

T

p

C

,

_

,

_

,

_

Thermodynamics

Session - 13

The equation of state of a gas

is given by

and the specific heat is given by

Derive the expressions for changes in internal energy, enthalpy and entropy for an

isobaric process.

As pressure is constant, dp = 0,

Internal energy:

Enthalpy:

Entropy:

73

2

T

c

p

RT

V

bT a C

p

+

) V V ( p ) T T (

2

b

) T T ( a U

2 2

2

2

2

2 2 2 2 2

+

pdV dT ) bT a ( dU +

pdV dT C dU

P

1

1

]

1

+

,

_

pdV dp

T

V

T dT C dU

p

P

dp

T

V

T V dT C dH

p

P

1

1

]

1

,

_

+

dT C dH

P

) T T (

2

b

) T T ( a H

2

2

2

2 2 2 2 2

+

dT

T

bT a

dS

,

_

) T T ( b

T

T

ln a S

2 2

2

2

2 2

+

dp

T

V

dT

T

C

dS

p

P

,

_

dT

T

C

dS

P

o

C at a constant pressure of 4 bar. The gas is then

cooled to 60

o

C at constant volume. The mass of the gas is 5 kg. Determine total entropy

change. C

P

and C

V

are 1.0 and 0.72 kJ/kg.K

p

r

e

s

s

u

r

e

volume

1

1

T

2

T

2

3

74

2

2

T

T

2 2

T

dQ

S

2

2

T

T

p

T

dT C

Total entropy change = 5(0.2161)=1.0805 kJ / K

Prove that

dp ) T p ( V dT ) pV C ( dU

p

+

Where

p T

T

V

V

1

,

p

V

V

1

,

_

,

_

dp

p

U

dT

T

U

dU

T p

,

_

+

,

_

p p p

T

V

p

T

S

T

T

U

,

_

,

_

,

_

3

2

T

T

3 2

T

dQ

S

3

2

T

T

V

T

dT C

75

K . kg / kJ 2222 . 2

222

222

ln

222

222

ln 22 . 2 K . kg / kJ 2222 . 2

2 2 2 2 2 2

S S S

+

K . kg / kJ 2222 . 2

2222 . 2 2222 . 2 S

2 2

) p , T ( U U

pdV TdS dU

T

dQ

dS

T

dT C

dS

p

T

C

T

S p

p

,

_

p

p

p

T

V

p

T

C

T

T

U

,

_

,

_

,

_

pdV TdS dU

T p

p

S

T

V

,

_

,

_

T T T

p

V

p

p

S

T

p

U

,

_

,

_

,

_

0

S

U

V

U

p

U

T T T

,

_

,

_

,

_

76

T p T

p

V

p

T

V

T

p

U

,

_

,

_

,

_

dp

p

V

p

T

V

T dT

T

V

p

T

C

T dU

T p p

p

1

1

]

1

,

_

,

_

+

1

1

]

1

,

_

,

_

dp

p

V

p

T

V

T dT

T

V

p C

T p p

p

1

1

]

1

,

_

+

,

_

1

1

]

1

,

_

dp ) pV V T ( dT ) pV C (

p

dp ) T p ( V dT ) pV C ( dU

p

+

pdV TdS dU

T T

S

V

p T

S

U

,

_

,

_

V T

p

T

p T

S

U

,

_

,

_

R

pV

T

R

V

p

T

V

,

_

2

R

V

p T

S

U

T

,

_

pdV TdS dU

p

V

S

T

V

U

T T

,

_

,

_

T V

V

S

T

p

,

_

,

_

p

T

p

T

V

U

V T

,

_

,

_

2 p

V

R

T

V

U

T

,

_

And hence

77

pV H U

pV U H

+

1

1

]

1

,

_

,

_

,

_

V

p

V

p

p

H

p

U

T T T

p T

T

V

T V

p

H

,

_

,

_

1

1

]

1

,

_

1

1

]

1

,

_

,

_

V

p

V

p

T

V

T V

p

U

T p T

T p T

p

V

p

T

V

T

p

U

,

_

,

_

,

_

2

p

RT

p

p

R

T

p

U

2

T

,

_

2

S

U

V

U

p

U

T T T

,

_

,

_

,

_

Thermodynamics

Session 14

Fugacity:

This is a concept used to determine Gibbs free energy for real gases. Recall that Gibbs

free energy is an important thermodynamic property used in phase and reaction

equilibria. We have one fundamental property relation,

At constant temperature,

If the gas is ideal,

Obviously this equation is not valid for real gases. To make it valid for real gases, let us

replace actual pressure by a fictitious term f, so that the equation becomes valid even for

real gases as

Here f is called fugacity and it will have the units of pressure.

Integrating,

For ideal gases,

Therefore

The fugacity is proportional to pressure.

78

SdT Vdp dG

Vdp dG

( ) p ln RTd dp

p

RT

dG

( ) p ln RTd dG

( ) f ln RTd dG

2

2

2 2

f

f

ln RT G G G

2

2

2 2

p

p

ln RT G G G

p f ., e . i

p

p

f

f

2

2

2

2

As pressure is decreased, we know real gases will increasingly behave like ideal gases.

Mathematically,

Fugacity coefficient is defined as the ratio of fugacity to the pressure. The fugacity is

to be determined with reference to some standard state. The standard state is chosen such

that, the pressure is equal to fugacity. This means that, the gas is at a very low pressure.

This state is designated as f

0

corresponding to a low pressure p

0

.

Effect of temperature on fugacity:

Gibbs free energy change between any state and standard state is given by

Partial differential w. r. t. T at constant pressure,

Since f

0

is at low pressure, its variation with temperature will be negligible. Using Gibbs

Helmholtz equation,

This equation gives the effect of temperature on fugacity.

79

2

p

f

lim

2 p

2

2

f

f

ln RT G G

T

G

T

G

f

f

ln R

2

2

T

G

T

G

) f ln f (ln R

2

2

2 2

p

2

p p

2

p

T

) T / G (

T

) T / G (

T

f ln

T

f ln

R

,

_

,

_

1

1

]

1

,

_

,

_

2

2

p

RT

H H

T

f ln

,

_

At constant temperature,

Writing it as partial differential equation with respect to pressure at constant T,

This equation gives the effect of pressure on fugacity.

Determination of fugacity: Under isothermal condtions,

We need to integrate this between p = 0 to the pressure at which we want to determine

fugacity.

As p 0, f p , also note that

is not defined.

This can be avoided by certain simplification as below:

80

( ) f ln RTd Vdp dG

RT

V

p

f ln

T

,

_

( ) f ln RTd Vdp dG

( ) dp

p

Z

dp

RT

V

f ln d

2 p

p ln

dp

p

Z

dp

p

2

dp

p

2

+

( ) dp

p

2 Z

p ln d

+

dp

p

2 Z

p

f

ln d

,

_

( ) dp

p

Z

f ln d

( ) dp

p

2 Z

ln d

Method of residual volumes:

Residual volume is defined by

Using this in the relation,

af

Using equation of state:

81

( ) dp

p

2 Z

ln d

( )

p

2

p

2

dp

p

2 Z

ln d

p

RT

V

( ) dp

RT

V

f ln d

dp

RT

2

p

RT

,

_

+

dp

p

2

RT

,

_

+

( )

,

_

+ p ln d dp

RT

dp

RT p

f

ln d

,

_

( ) p d

RT

ln d

p

o

p

2

p d

RT

ln

p

o

( ) f ln RTd Vdp dG

( ) Vdp

RT

2

f ln d

( )

p

p

p

p

2 2

Vdp

RT

2

f ln d

p

p 2

2

Vdp

RT

2

f

f

ln

We need to apply the above result to the equation of state of your choice.

Application to Van der Waals equation:

Equation of state is

Substituting this in

We get,

Consider the integral,

Put

82

p

p 2

2

Vdp

RT

2

f

f

ln

2

2

V

a

b V

RT

p

RT ) b V (

V

a

p

,

_

+

dV

V

a 2

) b V (

RT

dp

2 2

,

_

p

p 2

2

Vdp

RT

2

f

f

ln

dV

V

a 2

) b V (

RT

V

RT

2

f

f

ln

2 2

V

V 2

2

,

_

V

V

2

V

V

2

2 2

RTV

aVdV 2

) b V (

VdV

V

V

2

V

V 2

2 2

) b V (

VdV

RTV

a 2

f

f

ln

+

V

V

2

2 2

2

) b V (

VdV

RTV

a 2

RTV

a 2

f

f

ln

V

V

2

2

2

) b V (

VdV

RTV

a 2

f

f

ln

2

) b V (

VdV

du dV

u b V

Since V

0

is at a very low pressure, it is very large. As an approximation which is valid,

0 0

V b V

This equation gives the expression for fugacity of a gas that follows Van der Waals

equation.

83

,

_

+ du

u

b

u

2

2

2

u

du ) b u (

u

b

u ln

b V

b

) b V ln(

b V

b

b V

b

b V

b V

ln

) b V (

VdV

2 2

V

V

2

2

,

_

b V

b

b V

b V

ln

2

,

_

2

) b V (

VdV

V

V

2

2

2

) b V (

VdV

RTV

a 2

f

f

ln

b V

b

b V

b V

ln

) b V (

VdV

2

V

V

2

2

,

_

b V

b

b V

b V

ln

RTV

a 2

f

f

ln

2 2

+

,

_

b V

b

V

b V

ln

RTV

a 2

p

f

ln

2 2

+

,

_

b V

b

V ln ) b V ln(

RTV

a 2

p ln f ln

2 2

+ +

b V

b

p

RT

ln ) b V ln(

RTV

a 2

2

+

,

_

+

b V

b

p ln ) RT ln( ) b V ln(

RTV

a 2

p ln f ln

2 2

+ +

RTV

a 2

b V

b

b V

RT

ln f ln

+

,

_

Based on residual volume,

For low to moderate pressures,

And we know that

Assuming as an approximation, the residual volume may be assumed to be independent

of temperature, the above integral may be written as,

The above equation may be used for quick estimation of fugacity.

84

p d

RT p

f

ln

p

o

,

_

2

p

f

( ) 2 x x ln Lim

2 x

RT

p

2

p

f

RT

p

2

p

f

+

,

_

+

p

RT

V

RT

p

2

p

f

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