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
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
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.
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
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
L / V
L
C p
C
p
V
V
C
T
C
Gas
V
fluid
1
2 3
T
1
4
p V diagram for pure substance
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.
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.
RT pV =
}
= A
2
1
T
T
V
dT C U
}
= A
2
1
T
T
P
dT C H
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 =
) ( ) (
1 2 1 2
V V p T T C
pdV dT C dU
P
P
=
=
) (
1 2
T T C Q H
P
= = A
) (
1 2
V V p W =
, dT C dQ
dT
dQ
C
P
p
P
=
|
.
|

\
|
=
, dT C dQ
dT
dQ
C
V
V
V
=
|
.
|

\
|
=
W Q U = A
Q U = A
) (
1 2
2
1
T T C dT C U
V
T
T
V
= = A
}
Q T T C dT C H
P
T
T
P
= = = A
}
) (
1 2
2
1
dT C dQ
P
=
Relation between heat capacities:
Isothermal Process:
Since the temperature is constant there will not be any change in internal energy.
2
1
1
2
ln ln
p
p
RT
V
V
RT W Q = = =
0 = A = A U H
}
=
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
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 >
dW dQ
dW dQ dU
=
=
2
2 2
1
1 1
T
V p
T
V p
=
Adiabatic Process:
There will not any heat exchange, Q = 0.
dW dU =
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.
dV
V
RT
dT C
V
=
dV
V
RT
dT C
V
=
V
dV
C
R
T
dT
V
=
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
V V
P
C
R
C
C
= 1
V V
P
C
R
C
C
= 1
1 =
V
C
R
Since the gas is ideal,
) (
1
1 2
T T
R

1
2 2 1 1

V p V p
W
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 =
const pV =

}
= = A
=
2
1
T
T
V
dT C W U
dW dU
) (
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
}
}
= A
= A
2
1
2
1
dT C U
dT C H
V
P
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 .
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

|
|
.
|

\
|

= A

/ 1
1
2 1 1
1
1 p
p V p
U
const pV
n
=