THERMODYNAMICS

Course no: CHE F213

Instructor: Dr. Srinivas
Krishnaswamy
2016 - 2017

Contents
Reversibility

and Irreversibility
What is quasi-equilibrium?
Understanding energy
The concept of thermodynamic work
Evaluation of work for common
reversible processes
Work done in an irreversible process
Two inherently irreversible processes
Heat and its comparison with work

Reversibility and
Irreversibility
A process is reversible if it can be completely
reversed, i.e. when carried out in the opposite
direction the system follows the same
succession of states as it followed in the
forward direction (very crude definition)
A process is reversible if after the process
occurs, the system can be restored to its
original state without any effect on its
surroundings
This effect occurs only when the driving force
is infinitesimally small

Reversibility and
Irreversibility
Note The 2nd definition involves the
surroundings
Important to understand that when a process
is reversible, interaction between system and
surroundings are equal and opposite in
direction,i.e. both system and surroundings
are restored to initial conditions
A reversible process leaves no history of the
process after it is reversed
No friction involved
The processes represent idealization and are
never realized in real life

Reversibility and
Irreversibility
A process which is not reversible is
irreversible
Irreversible processes have friction and are
carried out with finite driving forces
If a system in this case is restored to its
original state, surroundings must be altered
Caused by friction, unrestrained expansion,
mixing of substances, combustion, flow of
electricity through a resistor, heat transfer
over a finite temperature difference etc.

Quasi-equilibrium
process
A process in which deviation from
equilibrium is infinitesimal
All states through which a system passes
during such a process can be considered as
a succession of equilibrium states
Takes place very slowly with an infinitesimal
change in properties at each step
Path can be described for such a process
A quasi-equilibrium process without friction
is reversible

Understanding Energy
Difficult

to define in general, but is

defined as capacity of a body to do
work (causes an effect)
Exists in various forms and can be
converted from one form to another
(partial or complete), but can never be
destroyed
Can be classified as energy in
transition and energy in storage
SI units: Joules

Understanding Energy
Energy transferred as a result of potential
difference is energy is transition. Loss of
identity as soon as soon as energy enters
and leaves a system. E.g.: gradient of force,
temperature and potential result in transfer
of mechanical work, heat and electrical
energy respectively
Stored energy possessed by a system as a
result of its position in a force field, its
motion, its atomic or molecular structure etc.
Examples are kinetic, rotational or
vibrational energy, chemical or nuclear
energy etc.

The concept of
thermodynamic work
By

definition it is Force times

displacement, the latter measured in
the direction of the force from the point
of application
But then thermodynamics talk of
system and surroundings. Hence work
needs to be defined in thermodynamic
language

The concept of
thermodynamic work
Work is said to be done by a system if the sole
effect on the surroundings is reduced to
lifting of weight
Note The definition does not call for actual
raising of a weight, but rather the possibility
of a weight being raised
Thermodynamic work is energy in transition
and is manifest at the system boundary only
during system-surrounding interaction.
Before the interaction work is present and
after the interaction no work exists

The concept of
thermodynamic work
MOTOR

WORK
MOTOR

WORK
WORK

Work crosses
system boundary
in both cases
(green and red
boundaries)
Flow of electricity
across a system is
equivalent to
work crossing the
system boundary

The concept of
thermodynamic work
Conventions important when solving
problems
In thermodynamics work done by a system
is positive and work done on a system is
negative
System and surroundings do equal, but
opposite work
Wsystem + Wsurroundings = 0
Net work done by a system is expressed as
Wnet = Wout - Win

Work done in a frictionless

quasi-equilibrium process

Initial conditions
Gas at P, T and volume
V inside frictionless
piston and cylinder
arrangement in thermal
equilibrium
P exerts a force F. Under
equilibrium, this is
balanced by a force
caused by atmospheric
pressure and piston
weights (-F) which
results in Pext

Work done in a frictionless

quasi-equilibrium process

dz

Remove an infinitesimally
small weight. This will
result in reduction of
pressure and slight
expansion will take
place.
Reduced gas pressure will
be balanced by reduced
weights which will be
raised and work will be
done
W = Fdz = (PA)dz = PdV

Work done in a frictionless

quasi-equilibrium process

Final state
after weights
are removed

Let finite weights be removed

ensuring quasi-equilibrium
process 1- 2 in which volume
changes from V1 to V2
During this change system and
surroundings are in
equilibrium
The net work done during the
expansion 1-2 is

1W2

= W = PdV

Work done in a frictionless

quasi-equilibrium process
The

integral represents the area under

the P V diagram
Work done can be found by integration
provided a relationship between P and
V is known
This is displacement work and is valid
only for frictionless process
This expression applies to any
compressible system of any arbitrary
shape

Work done in a frictionless

quasi-equilibrium process
Specific work = Work per unit mass of the system
W = mw = PdV = m Pd
The integral can be evaluated by graphical or
numerical methods (if path known from
experimental data) or by curve fitting
experimental data to obtain a relationship
between P and V and then using direct
integration

Evaluating work for some

common processes
CONSTANT PRESSURE PROCESS
P = CONSTANT
1W2 = W = PdV = P dV
WORK DONE = P (V2 V1)
P

1 W2

Evaluating work for some

common processes
CONSTANT VOLUME PROCESS
V = CONSTANT, dV = 0
WORK DONE = 0
P

Evaluating work for some

common processes

HYPERBOLIC PROCESS
PV = CONSTANT = P1V1 = P2V2
1W2 = W = P1V1 (dV / V)
WORK DONE = P1V1 ln(V2 / V1) =
P2V2 ln(V2 / V1)
1
1W2

NOTE HYPERBOLIC
PROCESS BECOMES
ISOTHERMAL IF T IS
CONSTANT, PV = RT = C

Evaluating work for some

common processes
POLYTROPIC PROCESS
PVn = P1V1n = P2V2n = C
The index n is the polytropic index. It can be
evaluated if P and V at initial and final states
are known, thus
n = ln (P1 / P2) / ln (V2 / V1)
The polytropic relation represents the most
convenient curve fitting of actual
experimental data between P and V with the
value of the index n evaluated with the help
of any two points on the curve

Evaluating work for some

common processes
For integration purposes
P = C / Vn = P1V1n / Vn = P2V2n / Vn
n)
W
=

W
=
C
(dV
/
V
1 2
1n- V 1n) / 1 n
W
=
C
(V
1 2
2
1
Substituting C = P1V1n = P2V2n
from V /V =
(P /P )
1W2 = (P2V2 - P1V1) / 1 n
){(n 1) / n} 1]
W
=
(P
V
/
1

n)
[
(P
/
P
1 2
1 1
2
1
2

1
1/n

Evaluating work for some

common processes
n,

the polytropic index can have many

values. note that when n = 0, the
process is constant pressure (isobaric)
and when n = , it is a process at
constant volume
Integration valid when n 1
For hyperbolic process n = 1

Evaluating work for some

common processes
If the gas is ideal, then
P1V1 / T1 = P2V2/T2
A relationship between T P and V T can
be obtained thus
T2 / T1 = (P2 / P1)(n 1 / n) = (V1 / V2)(n 1)
Putting P2V2 = mRT2 and P1V1 = mRT1
1W2 = m R (T2 - T1) / 1 n
(Polytropic work for an ideal gas)

Evaluating work for some

common processes
A gas is contained in a cylinder fitted with a
piston loaded with a small number of
weights. The initial pressure of the gas is
1.3 bar and the initial volume is 0.03 m3.
The gas is now heated until the volume
increases to 0.1 m3. Calculate the work
done by the gas for the a constant pressure,
constant temperature process and PV1.3 = C
process

Evaluating work for some

common processes
CONSTANT PRESSURE PROCESS
(CAUSED BY MOVING PISTON AS GAS IS
HEATED)
WORK DONE = P (V2 V1) = 9.1 kJ
CONSTANT TEMPERATURE PROCESS
(REMOVE WEIGHTS AT A RATE THAT
THE TEMPERATURE REMAINS
CONSTANT WHILE HEAT IS ADDED TO
THE GAS)
WORK DONE = P1V1 ln(V2 / V1) = 4.695 kJ

Evaluating work for some

common processes
POLYTROPIC PROCESS (ACHIEVED
BY REMOVING WEIGHTS AT A
RATE SUCH THAT P1V11.3 = P2V21.3
DESCRIBES P V RELATIONSHIP
WORK DONE = (P2V2 - P1V1) / 1 n = 3.933 kJ
STATE 1 2 CAN BE ACHIEVED THROUGH
DIFFERENT ROUTES. WORK DONE IS
DIFFERENT FOR EACH PATH. WORK IS THUS
A PATH FUNCTION (REMEMBER QUASIEQUILIBRIUM)

Evaluating work for some

common processes
Work

done in a process is not only a

function of the two end states, but it
also depends on the path followed in
going from one state to another
Work is a path function and an inexact
differential
Thus 1W2 = W W2 W1. Hence
never speak of work in state 1 or state
2. There is only Win and Wout which is
work in transition

Work done in an
irreversible process
Not

all processes confirm to idealized

quasi-equilibrium conditions. Actual
process are inherently irreversible, i.e.
surroundings are altered even when
system returns to original state
A process maybe irreversible
essentially in two ways, i.e. nonequilibrium irreversible or due to
friction

Work done in an
irreversible process
In a non-equilibrium process, there is a finite
change. Path of the process is not known.
Only end states are known
In a process where friction is present quasistatic conditions can exist, i.e.
Pext F/A = P
Local temperature changes due to friction
near piston cylinder contacts.
Thermodynamic equilibrium is thus absent.
Work is dissipated as heat and cannot be
recovered

Work done in a nonequilibrium process

Actual

case where finite weights are

removed. Only initial and final states
are known. The system and
surroundings are not in equilibrium at
each step
Pext = P2
P

Pext = P1

1
1W2

Work done in a nonequilibrium process

PdV does not represent work
But some work has been done because
volume has changed and this is finite
change, i.e. V
W = Pext V (work done in a non-equilibrium
process)
Note pressure Pext here is external pressure
and during the process never equal to P, the
pressure of the gas.

Work done in a process

with friction
In

this case Pext + F/A = P or Pext - F/A =

P is possible depending on whether
expansion or compression takes place
For compression Pext > P and for
expansion Pext < P (P is the gas
pressure)
Thus in a process with friction
W = PextdV (Pext = P F/A)
Less work obtained during expansion and
more work required during compression

Work done in an
irreversible process
Lost work = PdV - PextdV
It is seen that for a reversible process, for a
given change of state, work output during
expansion is maximum and work input
during compression is minimum. In an
irreversible process during expansion work
output is less than maximum and during
compression more than minimum
An irreversible process is always inferior

Two inherently
irreversible process
expansion where PdV is finite,
but work done is zero. Finite means
can be evaluated
Pext = 0

Free

Fluid, state
1, P1, V1

Vacuum,
Pext = 0

Q=0
W=0

Not quasiequilibrium

PextdV = 0
Q=0
Fluid, state
2, P2, V2

W=0

No work done
during free
expansion

Two inherently
irreversible process
MOTOR

A situation where
PdV is zero, but
work is still done

Paddle wheel
work

Volume does not

change and
friction not
involved
System boundary
does not move

Problem

a.
b.
c.

An insulated vertical cylinder fitted with a piston held in

position by a pin contains 0.0135 m3 of Freon-12
saturated vapour at 30 oC. The diameter of the cylinder
is 9 cm. The mass of the piston is 90 kg. The
atmospheric pressure is 1 bar. The pin is now suddenly
moved. The piston oscillates and comes to equilibrium
after a period of time when final and initial temperatures
become equal.
Determine the final pressure and volume of the system
Determine the work done by Freon during this process
Calculate the work done by Freon for a reversible
process undergoing the same state change

Solution
Area of piston = ( / 4) * D * D = 63.584e-4 m2
Initial pressure and specific volume of
saturated vapour P1 = 0.7449 MPa and 1=
g = 0.023 m3 / kg ( at 30 oC)
Final pressure P2 = Pext = Patm + mg / A =
2.388e5 Pa
At 0.2388 MPa and 30 oC Freon is
superheated. So final specific volume
from superheat table =
2= 0.084022 m3 / kg
Mass of Freon = V1 / 1 = 0.52535 kg
Final volume = m 2 = 0.04414 m3

Solution
Work done = PextdV = Pext (V2 V1) =
7.32 kJ
For reversible isothermal process
WORK DONE = P1V1 ln(V2 / V1) = 11.91 kJ

Note Reversible work > Irreversible work

Other modes of work

transfer
Shaft

work W = 2NT / 60 where, N

denotes revolutions per minute and T
is the torque
Stretched wire
Magnetic work
Electrical work
Surface film
Chemical work

The State Postulate

Simple system: A system which involves only
one work mode
State Postulate: The number of independent
intrinsic properties required to define the
state of a system is equal to one plus the
number of possible work modes
Thus for a simple system, the number of
independent intrinsic properties required is 2

The concept of heat

In

the case of paddle wheel work,

temperature rises, i.e. a change of
state occurs
The same state can be brought about
if heat entered the system instead of
work
Effect of heat on a system could be
same as the effect of work
Heat is energy as work is and has
units of work

The concept of heat

Heat is thus defined as energy in
transition flowing by a virtue of a
temperature difference between two
systems or between a system and it s
surroundings
It manifests only at the system boundary
and cannot be contained

The concept of heat

Sign convention of heat is just opposite to
that of work
Heat entering a system is positive (added
to) and leaving a system is negative
A process in which no heat transfer takes
place is an adiabatic process
In a closed system an application of work or
heat can cause a change of state

The concept of heat

When heat is added to a pure substance it
is seen that either the phase changes with
temperature remaining constant (saturation
state) or temperature changes with
substance remaining in the same phase
In the former case it is called latent heat and
in the latter sensible heat
Heat transfer by 3 modes: conduction,
convection or radiation