Dr. J.

Venkatesan
Professor in Automobile Engineering
Sri Venkateswara College of Engineering
Sriperumbudur, Chennai - 602 117
Ideal gas
A perfect gas or an ideal gas is defined as a gas having no
intermolecular forces. A gas which follows the gas laws at all
ranges of
f pressures and
d temperatures can be considered
d d as an
ideal gas, but no such gas exists in nature.
Boyle’s law
Boyle’s
y law states that if the temperature
p of a g
gas in a closed
system is maintained constant during a process, the volume of
the gas will vary increasingly with absolute pressure during the
change of state.
V α 1/p or pV = Constant
C nst nt when
h n T is constant
nst nt
2
Charle’s law
If the pressure of the gas in a closed system is maintained
constant during a process, the volume of gas will vary directly
with the absolute temperature.
temperature
VαT or V/T = C
A
Avogadro’s
d ’ law
l
A mole of a substance has a mass numerically equal to the
molecular weight of the substance.
Example: 1 kg mole of O2 has a mass of 32 kg
1 kg mole of N2 has a mass of 28 kg
Avogadro’s law states that the volume of a 1 kg mole of all gases
at STP (0oC and 1.01325 bar) is the same and is equal to 22.4 m3.
3
 Example: 1 kg mole of O2 has a mass of 32 kg and volume of
22 4 m3
22.4
1 kg mole of N2 has a mass of 28 kg and volume of
22 4 m3
22.4
At p = 1.01325 bar and T = 273.15 K, for 1 kg mole of gas V
= 22.4 m3
vm = 22.4 m3/kg mole
p vm = Ru T
1.01325 x 105 x 22.4 = Ru x 273.15
Ru = 8314.3 J/kg mol K
Ru Æ Universal gas constant; vm Æ Molar volume
4
 Joule’s law
h s law
This aw stat
statess that th
there
r iss no chang
change of ttemperature
mp ratur wh
when
n
a gas expands without doing external work and without receiving
or rejecting heat.
heat
u = f(T) only for ideal gas
Equation of state
The functional relationship among the properties, pressure p,
molar
l or specific
ifi volume
l v and
d temperature T,
T is
i known
k as an
equation of state, which may be expressed in the form,
f (p, v, T) = 0
If two properties of a gas are known, the third can be
evaluated from the equation of state.
5
pv=RT
Real gas
Most of the real gases obey Boyle
Boyle’ss and Charle
Charle’ss law at low
pressures and temperatures. But the actual behaviour of real
gases at elevated
l d pressures and
d at low
l temperatures deviates
d
considerably.
The ideal gas equation p v = R T can be derived analytically
using
g the kinetic theory
y of g
gases by
y making
g the following
g
assumptions:
• A finite volume of gas contains large number of molecules.
molecules
• The collision of molecules with one another and with the walls
of
f the
th container
nt in is perfectly
p f tl elastic.
l sti
6
• The molecules are separated by large distances compared to
their own dimensions.
dimensions
• The molecules do not exert forces on one another except
when
h n they
th collide.
llid
As long as the above assumptions are valid the behaviour of a
real gas approaches closely that of an ideal gas.
Van der Waals equation

Van der Waals by applying the laws of mechanics to the

individual molecules,
molecules introduced two corrections terms in the
ideal gas equation.

7
The Van der Waals equation for a real gas may be written as

⎛ a ⎞
⎜p+ 2 ⎟ (v − b ) = R T
⎝ v ⎠
aÆ a constant to account for the existence of mutual attraction
between the molecules.
a/v
/ 2 Æ the
th force
f of
f attraction
tt ti
bÆ the coefficient introduced to account for the volumes of molecules,
and is known as co-volume
co volume

27 R 2 Tc2 R Tc
a= b=
64 p c 8 pc
Tc Æ Critical temperature
pc Æ Critical pressure
8
Unique feature
• Van der Waals equation qualitatively accounts for the heating
effect observed at ordinary temperatures.
Limitations
• The values of a and b (which are assumed to be constant) are
found to vary with temperature. Thus the results obtained
from the equation are incorrect when the variation of a and b
is large with respect to temperature.
• The equation
q is not accurate enough
g in the critical region.
g

9
Virial expansions
The virial expansion,
expansion also called the virial equation of state,
state is
the most interesting and versatile of the equations of state
f gases. The
for Th virial
i i l expansion
i isi a power series
i ini powers of
f
the variable, B/V, and has the form,

pv
= Ao + A1 p + A2 p 2 + A3 p 3 + − − − − − −
RT
pv B1 B2 B3
= Bo + + 2 + 3 +−−−−−−
RT v v v
The coefficient, Ao, A1, A2, ……. and Bo, B1, B2, …….. are called
the virial coefficients and are functions of temperature. Ao, Bo
are first virial coefficient and A1, B1 are second virial
coefficients and so on.
10
Law of corresponding states
• For each substance there is a compressibility factor.
factor
• It would be very convenient if one chart could be used for all
s bst
substances.
s
• The general shapes of the vapour dome and of the constant
temperature lines on the p-v plane are similar for all
substances, although the scales may be different.
• This similarity can be exploited by using dimensionless
properties
p p called ‘reduced p
properties’.
p
p
Reduced pressure, p r =
pc
T
Reduced temperature, Tr =
Tc 11
 v
Reduced volume, v r =
vc
Generally for all substances, vr = f(pr, Tr) and Z = f(pr, Tr)
Th relation
The l ti among the
th reduced
d d properties,
ti s pr, Tr and
d vr is
known as the law of corresponding states.

Compressibility
In thermodynamics
y and fluid mechanics, compressibility
p y is a
measure of the relative volume change of a fluid or solid as a
response to a pressure (or mean stress) change.
change

1 ∂v
K= ----- (1)
v ∂p
where v is specific volume and p is pressure. 12
The isothermal compressibility is defined as
1 ⎛ ∂v ⎞
K T = − ⎜⎜ ⎟⎟ ----- (2)
v ⎝ ∂p ⎠ T
where the subscript T indicates that the partial differential is to be taken
att constant
t t ttemperature.
t

The adiabatic compressibility is defined as

1 ⎛ ∂v ⎞
K S = − ⎜⎜ ⎟⎟ ----- (3)
v ⎝ ∂p ⎠ S
where S is entropy. For a solid, the distinction between the two is usually
negligible.
Coefficient of volume expansion is defined as
1 ⎛ ∂v ⎞
β= ⎜ ⎟ ----- (4)
v ⎝ ∂T ⎠ p
The inverse of the compressibility is called the bulk modulus.
13
We know that, ⎛ ∂p ⎞ ⎛ ∂v ⎞ ⎛ ∂T ⎞
⎜ ⎟ ⎜ ⎟ ⎜⎜ ⎟⎟ = −1 ----- (5)
⎝ ∂v ⎠ T ⎝ ∂T ⎠ p ⎝ ∂p ⎠V

⎛ ∂v ⎞
βv=⎜ ⎟ from (4)
⎝ ∂T ⎠ p
⎛ ∂v ⎞
− K T v = ⎜⎜ ⎟⎟ from (2)
⎝ ∂p ⎠ T

⎛ −1 ⎞ ⎛ ∂T ⎞
Substituting in (5), ⎜⎜ ⎟⎟ (β v )⎜⎜ ⎟⎟ = −1
⎝ K T v ⎠T ⎝ ∂p ⎠V

β ⎛ ∂p ⎞
=⎜ ⎟ ----- (6)
K T ⎝ ∂T ⎠V

14
Compressibility Factor
• The compressibility
p y factor ((Z)) is used to alter the ideal g
gas
equation to account for the real gas behaviour.
• The compressibility factor is usually obtained from the
compressibility chart.
p v v actual
M th
Mathematically,
ti ll it is
i defined
d fi d as, Z= =
R T videal
p Æ the ppressure,
v Æ the spcific volume of the gas,
T Æ the temperature, and
R Æ the gas constant.
Z = 1 for
f ideal
id l gas

pc vc
Critical compressibility
p y factor, Zc =
R Tc
Z can, in general, be either greater or less than unity for a real gas. 15
Compressibility Chart

16
Rules on partial derivatives
Theorem 1 (Exact differential)
If a relation exists among the variables x, y and z, then z may
be expressed as function of x and y.
⎛ ∂z ⎞ ⎛ ∂z ⎞
z = f (x, y) dz = ⎜ ⎟ dx + ⎜⎜ ⎟⎟ dy
⎝ ∂x ⎠ y ⎝ ∂y ⎠ x
Let, M = ⎛⎜ ∂z ⎞⎟ and
⎛ ∂z ⎞
N = ⎜⎜ ⎟⎟
⎝ ∂x ⎠ y ⎝ ∂y ⎠ x
d = M dx
dz d + N dy
d
Differentiating M partially with respect to y, and N with
respect to x,
x
⎛ ∂M ⎞ ∂2z ⎛ ∂N ⎞ ∂ 2
z
⎜⎜ ⎟⎟ = and ⎜ ⎟ =
⎝ ∂y ⎠ x ∂x ∂y ⎝ ∂x ⎠ y ∂y ∂x
17
Therefore, ⎛ ∂M ⎞ ⎛ ∂N ⎞
⎜⎜ ⎟⎟ = ⎜ ⎟
⎝ ∂y ⎠ x ⎝ ∂x ⎠ y
This is the condition of exact or perfect differential.

Theorem 2
If a quantity f is a function of x,
x y and z and a relation
exists among x, y and z, then f is a function of any two of x, y
and
nd z.
If f = f(x, y, z)

⎛ ∂x ⎞ ⎛ ∂y ⎞ ⎛ ∂z ⎞
⎜⎜ ⎟⎟ ⎜ ⎟ ⎜ ⎟ = 1
⎝ ∂y ⎠ f ⎝ ∂z ⎠ f ⎝ ∂x ⎠ f
18
Theorem 3
Among the variables x, y and z, any one variable may be
considered as a function of the other two.
If x = x (y,
(y z),
z) y = y (x,
(x z) & z = z(x,
z(x y)

⎛ ∂x ⎞ ⎛ ∂z ⎞ ⎛ ∂y ⎞
⎜⎜ ⎟⎟ ⎜ ⎟ ⎜ ⎟ = −1
⎝ ∂y ⎠ z ⎝ ∂x ⎠ y ⎝ ∂z ⎠ z
Among the thermodynamics variables, p, v and T, the following
relation
l h ld good.
holds d
⎛ ∂p ⎞ ⎛ ∂v ⎞ ⎛ ∂T ⎞
⎜ ⎟ ⎜ ⎟ ⎜⎜ ⎟⎟ = −1
⎝ ∂v ⎠ T ⎝ ∂T ⎠ p ⎝ ∂p ⎠V

19
Maxwell’s equations

• A pure substance existing in a single phase has only two

independent variables.
• Of the eight quantities,
quantities p,
p v,
v T,
T s,
s u,
u h,
h F (Helmholts function)
and G (Gibbs function), any one may be expressed as a function
of any two others.
(i) Consider a non flow process.
q = w + Δu
dq
q = dw + du
du = dq – dw
= T ds – p dv ----- (1)
Therefore, u = f (s, v) 20
 ⎛ ∂u ⎞ ⎛ ∂u ⎞
du = ⎜ ⎟ ds + ⎜ ⎟ dv ----- (2)
⎝ ∂s ⎠V ⎝ ∂v ⎠ S
Comparing (1) and (2)
⎛ ∂u ⎞ ⎛ ∂u ⎞
T =⎜ ⎟ and − p=⎜ ⎟
⎝ ∂s ⎠V ⎝ ∂v ⎠ S
⎛ ∂T ⎞ ∂ 2u ⎛ ∂p ⎞ ∂ 2u
⎜ ⎟ = and ⎜− ⎟ =
⎝ ∂v ⎠ S ∂v ∂s ⎝ ∂S ⎠ S ∂s ∂v

But, ⎛ ∂ 2u ⎞ ⎛ ∂ 2u ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
⎝ ∂v ∂s ⎠ ⎝ ∂s ∂v ⎠
⎛ ∂T ⎞ ⎛ ∂p ⎞
Therefore, ⎜ ⎟ = −⎜ ⎟ Æ I – Maxwell equation
⎝ ∂v ⎠ S ⎝ ∂s ⎠V
The rate of
Th f increase
i i temperature with
in i h respect to volume
l d i
during
isentropic process is equal to the rate of decrease in pressure with
21
respect to entropy during constant volume process.
 (ii) Consider a flow process.
q = w + Δh
dq = dw + dh
dh = dq – dw
= T ds + v dp ----- (1)
Therefore, h = f (s, p)
⎛ ∂h ⎞ ⎛ ∂h ⎞
dh = ⎜ ⎟ ds + ⎜⎜ ⎟⎟ dp ----- (2)
⎝ ∂s ⎠ p ⎝ ∂p ⎠ S
Comparing (1) and (2)
⎛ ∂h ⎞ ⎛ ∂h ⎞
T =⎜ ⎟ and v = ⎜⎜ ⎟⎟
⎝ ∂s ⎠ p ⎝ ∂p ⎠ S
⎛ ∂T ⎞ ∂ 2h ⎛ ∂v ⎞ ∂ 2h
⎜⎜ ⎟⎟ = and ⎜ ⎟ =
⎝ ∂p ⎠ S ∂p ∂s ⎝ ∂s ⎠ p ∂s ∂p 22
But, ⎛ ∂2h ⎞ ⎛ ∂2h ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
⎝ ∂p ∂s ⎠ ⎝ ∂s ∂p ⎠
⎛ ∂T ⎞ ⎛ ∂v ⎞
⎜
Therefore, ⎜ ⎟
⎟ = ⎜ ⎟ Æ II – Maxwell equation
⎝ ∂p ⎠ S ⎝ ∂s ⎠ p
The rate of increase in temperature with respect to pressure during
isentropic process is equal to the rate of increase in volume with respect
to entropy during constant pressure process.

((iii)) F = u – Ts
dF = du – (T ds + s dT)
= du – T ds – s dT
But, du = T ds – p dv
Therefore,
h f dF = T ds
d – p dv
d – T ds
d – s dT
d
= - p dv – s dT ----- (1)
23
Therefore, F = f (v, T)
⎛ ∂F ⎞ ⎛ ∂F ⎞ ----- ((2))
dF = ⎜ ⎟ dT + ⎜ ⎟ dv
⎝ ∂T ⎠V ⎝ ∂v ⎠ T
Comparing (1) and (2)
⎛ ∂F ⎞ ⎛ ∂F ⎞
−s =⎜ ⎟ and − p=⎜ ⎟
⎝ ∂T ⎠V ⎝ ∂v ⎠ T
∂
⎛ ⎞s ∂ 2
F ⎛ ∂p ⎞ ∂ 2
F
−⎜ ⎟ = and − ⎜ ⎟ =
⎝ ∂v ⎠ T ∂v ∂T ⎝ ∂T ⎠V ∂T ∂v

But, ⎛ ∂ 2
F ⎞ ⎛ ∂ 2
F ⎞
⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
⎝ ∂v ∂T ⎠ ⎝ ∂T ∂v ⎠
Therefore, ⎛⎜ ∂s ⎞⎟ = ⎛⎜ ∂p ⎞⎟ Æ III – Maxwell equation
⎝ ∂v ⎠ T ⎝ ∂T ⎠V
The rate of increase in entropy with respect to volume during isothermal
process is equal to the rate of increase in pressure with respect24to
temperature during constant volume process.
 (iv) g = h – Ts
dg = dh – (T ds + s dT)
= dh – T ds – s dT
B t dh = T ds + v d
But, dp
Therefore, dg = T ds + v dp – T ds – s dT
= v dp – s dT ----- (1)
Therefore, g = f (p, T)
⎛ ∂g ⎞ ⎛ ∂g ⎞
dg = ⎜ ⎟ dT + ⎜⎜ ⎟⎟ dp ----- (2)
⎝ ∂T ⎠ p ⎝ ∂p ⎠ T
⎛ ∂g ⎞ ⎛ ∂g ⎞
Comparing (1) and (2) − s = ⎜ ⎟ and v = ⎜⎜ ⎟⎟
⎝ ∂T ⎠ p ⎝ ∂p ⎠ T
⎛ ∂s ⎞ ∂2g ⎛ ∂v ⎞ ∂2g
− ⎜⎜ ⎟⎟ = and ⎜ ⎟ =
⎝ ∂p ⎠ T ∂p ∂T ⎝ ∂T ⎠ p ∂T ∂p 25
 ⎛ ∂2g ⎞ ⎛ ∂2g ⎞
But, ⎜⎜ ⎟⎟ = ⎜⎜ ⎟⎟
⎝ ∂p ∂T ⎠ ⎝ ∂T ∂p ⎠
⎛ ∂s ⎞ ⎛ ∂v ⎞
Therefore
Therefore, ⎜⎜ ⎟⎟ = −⎜ ⎟ Æ IV – Maxwell equation
⎝ ∂p ⎠ T ⎝ ∂T ⎠ p
The rate of increase in entropy with respect to pressure during isothermal
process is equal to the rate of decrease in volume with respect to
temperature during constant pressure process.

26
TdS equations
(i) Let s = f (T, v) Æ T and v independent variables

⎛ ∂s ⎞ ⎛ ∂s ⎞
ds = ⎜ ⎟ dT + ⎜ ⎟ dv ------ (1)
⎝ ∂T ⎠V ⎝ ∂v ⎠ T
Let u = f (T, v)
⎛ ∂u ⎞ ⎛ ∂u ⎞
du = ⎜ ⎟ dT + ⎜ ⎟ dv
⎝ ∂T ⎠V ⎝ ∂v ⎠ T
⎛ ∂u ⎞
= CV dT + ⎜ ⎟ dv d ------ (2)
∂
⎝ ⎠T
v
Also, du = T ds – p dv ------ (3)
Equating (2) and (3),
⎛ ∂u ⎞
T ds − p dv = CV dT + ⎜ ⎟ dv
⎝ ∂v ⎠ T 27
 CV 1 ⎡⎛ ∂u ⎞ ⎤
ds = dT + ⎢⎜ ⎟ + p ⎥ dv ------ (4)
T T ⎣⎝ ∂v ⎠ T ⎦
Comparing (1) and (4), ⎛⎜ ∂s ⎞⎟ = CV ------ (5)
⎝ ∂T ⎠V T

From Maxwell III-equation, ⎛⎜ ∂s ⎞⎟ = ⎛⎜ ∂p ⎞⎟ ------ (6)

⎝ ∂v ⎠ T ⎝ ∂T ⎠V
S b i i (5) and
Substituting d (6) in
i (1)
(1),
CV ⎛ ∂p ⎞
ds = dT + ⎜ ⎟ dv
T ⎝ ∂T ⎠V
⎛ ∂p ⎞
T ds = CV dT + T ⎜ ⎟ dv Æ First T ds equation
⎝ ∂T ⎠V
β ⎛ ∂p ⎞
We know that, =⎜ ⎟
K T ⎝ ∂T ⎠V
⎛ β ⎞
T ds = CV dT + T ⎜⎜ ⎟⎟ dv Æ First T ds equation 28
⎝ KT ⎠
(ii) Let s = f (T, p) Æ T and p are independent variables
⎛ ∂s ⎞ ⎛ ∂s ⎞
ds = ⎜ ⎟ dT + ⎜⎜ ⎟⎟ dp ------ (1)
⎝ ∂T ⎠ p ⎝ ∂p ⎠ T
Let h = f (T, p)
⎛ ∂h ⎞ ⎛ ∂h ⎞
dh = ⎜ ⎟ dT + ⎜⎜ ⎟⎟ dp
⎝ ∂T ⎠ p ⎝ ∂p ⎠ T
⎛ ∂h ⎞
= C p dT + ⎜⎜ ⎟⎟ dp ------ (2)
⎝ ∂p ⎠ T
Also, dh = T ds + v dp ------ (3)

⎛ ∂h ⎞
E
Equating
tin (2) and
nd (3),
(3) T ds d = C p dT + ⎜⎜ ⎟⎟ dp
d + v dp d
⎝ ∂p ⎠ T

Cp 1 ⎡⎛ ∂h ⎞ ⎤
ds = dT + ⎢⎜⎜ ⎟⎟ − v ⎥ dp ------ (4)
T T ⎣⎢⎝ ∂p ⎠ T ⎥⎦ 29
 ⎛ ∂s ⎞ Cp
Comparing (1) and (4), ⎜ ⎟ = ------ (5)
⎝ ∂T ⎠ p T
⎛ ∂s ⎞ ⎛ ∂v ⎞
From Maxwell IV-equation, ⎜⎜ ⎟⎟ = −⎜ ⎟ ------ (6)
⎝ ∂p ⎠ T ⎝ ∂T ⎠ p

Substituting (5) and (6) in (1), ds =

Cp ⎛ ∂v ⎞
dT − ⎜ ⎟ dp
T ⎝ ∂T ⎠ p
⎛ ∂v ⎞
T ds = C p dT − T ⎜ ⎟ dp Æ Second-T ds equation
⎝ ∂T ⎠ p
1 ⎛ ∂v ⎞
We know that, β = ⎜ ⎟
v ⎝ ∂T ⎠ p
⎛ ∂v ⎞
βv=⎜ ⎟
⎝ ∂T ⎠ p
T ds = C p dT − T β v dp Æ Second-T ds equation
30
(iii) Let u = f (p, v) Æ p and v are independent variables
⎛ ∂u ⎞ ⎛ ∂u ⎞
du = ⎜⎜ ⎟⎟ dp + ⎜ ⎟ dv ------ (1)
⎝ ∂p ⎠V ⎝ ∂v ⎠ p
⎛ ∂u ⎞ ⎛ ∂u ⎞ ⎛ ∂T ⎞ KT
⎜⎜ ⎟⎟ = ⎜ ⎟ ⎜⎜ ⎟⎟ = C v ------ (2)
⎝ ∂p ⎠ v ⎝ ∂T ⎠V ⎝ ∂p ⎠V β
Also
Also, u = h – pv
⎛ ∂u ⎞ ⎛ ∂h ⎞
⎜ ⎟ =⎜ ⎟ − p
⎝ ∂v ⎠ p ⎝ ∂v ⎠ p
⎛ ∂h ⎞ ⎛ ∂T ⎞
=⎜ ⎟ ⎜ ⎟ −p
⎝ ∂T ⎠ p ⎝ ∂v ⎠ p
1
= Cp −p ------ ((3))
vβ
31
Substituting (2) and (3) in (1),
KT ⎡Cp ⎤
du = C v dp + ⎢ − p ⎥ dv ------ (4)
β ⎣v β ⎦
We know that T ds = du + p dv

KT ⎡Cp ⎤
T ds = C v dp + ⎢ − p ⎥ dv + p dv
β ⎣v β ⎦
KT Cp
= Cv dp + dv ------ (5)
β vβ
KT 1
T ds = CV dp + C p dv Æ Third T ds equation
q
β βv

32
Change in internal energy
du = T ds – p dv ------ (1)
⎛ ∂p ⎞
T ds = CV dT + T ⎜ ⎟ dv Æ First T ds equation
⎝ ∂T ⎠V
Substituting in (1)
⎛ ∂p ⎞
du = CV dT + T ⎜ ⎟ dv − p dv
⎝ ∂T ⎠V
⎡ ⎛ ∂p ⎞ ⎤
du = CV dT + ⎢T ⎜ ⎟ − p ⎥ dv
⎣ ⎝ ∂T ⎠V ⎦
Internal energy of an ideal gas is function of temperature
only
nl
⎡ ⎛ ∂p ⎞ ⎤
du = CV dT + ⎢T ⎜ ⎟ − p ⎥ dv
⎣ ⎝ ∂T ⎠V ⎦
For an ideal gas, pv=RT 33
 RT
p=
v
⎛ ∂p ⎞ R p
⎜ ⎟ = =
⎝ ∂T ⎠ v v T
⎡ ⎛ p⎞ ⎤
du = CV dT + ⎢T ⎜ ⎟ − p ⎥ dV = C v dT
⎣ ⎝ T ⎠V ⎦
Therefore the internal energy is depending only on
temperature.
Change in internal energy when a gas obeys Van der Waals
equation
⎡ ⎛ ∂p ⎞ ⎤
We know
k that,
h du = CV dT + ⎢T ⎜ ⎟ − p ⎥ dv
⎣ ⎝ ∂T ⎠V ⎦

Van der Waals equation is, ⎛ p + a ⎞ (v − b) = R T

⎜ 2 ⎟
⎝ v ⎠ 34
 RT a
p= − 2
v−b v
⎛ ∂p ⎞ R
⎜ ⎟ =
⎝ ∂T ⎠ v v − b
⎡ ⎛ R ⎞ RT a⎤
Therefore, du = CV dT + ⎢T ⎜ ⎟− + 2 ⎥ dv
⎣ ⎝v−b⎠ v−b v ⎦
⎡a⎤
du = CV dT + ⎢ 2 ⎥ dv
⎣v ⎦
2 2 2
dv
∫1 du = CV ∫1 dT + a ∫1 v 2
⎡1 1 ⎤
u 2 − u1 = CV (T2 − T1 ) + a ⎢ − ⎥
⎣ v1 v 2 ⎦
35
Change in entropy when a gas obeys Van der Waals
equation
⎛ ∂p ⎞
T ds = CV dT + T ⎜ ⎟ dv Æ First T ds equation
⎝ ∂T ⎠V
dT ⎛ ∂p ⎞
ds = CV +⎜ ⎟ dv
T ⎝ ∂T ⎠V
V der
Van d Waals
W l equation
i is,
i ⎛ a ⎞
⎜ p + ⎟ (v − b ) = R T
⎝ v2 ⎠
RT a
p= − 2
v−b v
⎛ ∂p ⎞ R
⎜ ⎟ =
⎝ ∂T ⎠ v v − b
dT ⎛ R ⎞
Therefore, ds = CV +⎜ ⎟ dv
T ⎝v−b⎠ 36
 2 2 2
dT dv
∫1 ds = CV ∫1 T + R ∫1 v − b
⎛ T2 ⎞ ⎛ v2 − b ⎞
s 2 − s1 = C v ln⎜⎜ ⎟⎟ + R ln⎜⎜ ⎟⎟
⎝ T1 ⎠ ⎝ v1 − b ⎠
Change in enthalpy
dh = T ds + v dp
⎛ ∂v ⎞
T ds = C p dT − T ⎜ ⎟ dp Æ Second T ds equation
⎝ ∂T ⎠ p
⎛ ∂v ⎞
dh = C p dT − T ⎜ ⎟ dp + v dp
⎝ ∂T ⎠ p
⎡ ⎛ ∂v ⎞ ⎤
= C p dT − ⎢T ⎜ ⎟ − v ⎥ dp
⎢⎣ ⎝ ∂T ⎠ p ⎥⎦
⎡ ⎛ ∂v ⎞ ⎤
dh = C p dT + ⎢v − T ⎜ ⎟ ⎥ dp 37
⎢⎣ ⎝ ∂T ⎠ p ⎥⎦
Enthalpy of an ideal gas is function of temperature only
⎡ ⎛ ∂v ⎞ ⎤
dh = C p dT + ⎢v − T ⎜ ⎟ ⎥ dp
d
⎢⎣ ⎝ ∂T ⎠p ⎦⎥

For an ideal gas,

gas p v = R T
RT
v=
p
⎛ ∂v ⎞ R v
⎜ ⎟ = =
⎝ ∂T ⎠ v p T
⎡ ⎛v⎞⎤
dh = C p d
dT + ⎢v − T ⎜ ⎟ ⎥ dp = C p d
dT
⎣ ⎝T ⎠ ⎦

Therefore the enthalpy is depending only on temperature.

38
Difference in heat capacities (Cp – Cv)
To derive
⎛ ∂v ⎞ ⎛ ∂p ⎞ β
2 2
C p − C v = −T ⎜ or (Cp – Cv) = R or C p − C v =
T v
⎟ ⎜ ⎟
⎝ ∂T ⎠ p ⎝ ∂v ⎠ T KT
N t Derive
Note: D i First
Fi t and
d Second
S d T ds
d equations
ti and
d proceed
d as follows:
f ll

⎛ ∂p ⎞
T ds = CV dT + T ⎜ ⎟ dv ÆF
First
r T ds equation
qu n
⎝ ∂T ⎠V
⎛ ∂v ⎞
T ds = C p dT − T ⎜ ⎟ dp Æ Second T ds equation
q
⎝ ∂T ⎠ p
Equating the above equations,
⎛ ∂p ⎞ ⎛ ∂v ⎞
CV dT + T ⎜ ⎟ dv = C dT − T ⎜ ⎟ dp
⎝ ∂T ⎠V ⎝ ∂T ⎠ p
p

(C p − Cv )dT = T ⎛⎜ ∂p ⎞⎟ dv + T ⎛⎜ ∂v ⎞⎟ dp
⎝ ∂T ⎠ v ⎝ ∂T ⎠ p
39
 ⎛ T ⎞ ⎛ ⎞
dT = ⎜ ⎟⎛⎜ ∂p ⎞⎟ dv + ⎜ T ⎟⎛⎜ ∂v ⎞⎟ dp ----- (1)
⎜C −C ⎟⎝ ∂T ⎠ ⎜C −C ⎟⎝ ∂T ⎠
⎝ p v ⎠ v ⎝ p v ⎠ p

We can write, T = f (p, v)

⎛ ∂T ⎞ ⎛ ∂T ⎞
dT = ⎜⎜ ⎟⎟ dp + ⎜ ⎟ dv ----- (2)
⎝ ∂p ⎠V ⎝ ∂v ⎠ p

C
Comparing
i (1) and
d (2),
(2)
⎛ ∂T ⎞ T ⎛ ∂p ⎞
⎜ ⎟ = ⎜ ⎟ ----- (3)
⎝ ∂v ⎠ p C p − C v ⎝ ∂T ⎠ v

⎛ ∂p ⎞ ⎛ ∂v ⎞
From (3), C p − Cv = T ⎜ ⎟ ⎜ ⎟ ----- (4)
⎝ ∂T ⎠ v ⎝ ∂T ⎠ p

⎛ ∂p ⎞ ⎛ ∂T ⎞ ⎛ ∂v ⎞
But
But, ⎜ ⎟ ⎜ ⎟ ⎜⎜ ⎟⎟ = −1
⎝ ∂T ⎠ v ⎝ ∂v ⎠ p ⎝ ∂p ⎠ T
40
 ⎛ ∂p ⎞ ⎛ ∂v ⎞ ⎛ ∂p ⎞
⎜ ⎟ = −⎜ ⎟ ⎜ ⎟ ----- (5)
⎝ ∂T ⎠ v ⎝ ∂T ⎠ p ⎝ ∂v ⎠ T

Substituting (5) in (4),

⎛ ∂v ⎞ ⎛ ∂p ⎞
2

C p − C v = −T ⎜ ⎟ ⎜ ⎟ ----- (6)
⎝ ∂T ⎠ p ⎝ ∂v ⎠ T
RT
pv=RT v=
p
⎛ ∂v ⎞ R
⎜ ⎟ = ----- (7)
⎝ ∂T ⎠ p p
RT
p=
v
⎛ ∂p ⎞ − RT
⎜ ⎟ = 2 ----- (8)
⎝ ∂v ⎠ T v 41
Substituting (7) and (8) in (6),
R2 ⎛ − R T ⎞ R 3
T 2
C p − C v = −T 2 ⎜ 2 ⎟= 2 2
p ⎝ v ⎠ p v
pv=RT

R3 T 2
C p − Cv = 2 2 = R
R T
Cp – Cv = R ----- (9)

1 ⎛ ∂v ⎞ ⎛ ∂v ⎞
We know that, β = ⎜ ⎟ Æ ⎜ ⎟ =βv
v ⎝ ∂T ⎠ p ⎝ ∂T ⎠ p

1 ⎛ ∂v ⎞ ⎛ ∂v ⎞
K T = − ⎜⎜ ⎟⎟ Æ ⎜⎜ ⎟⎟ = −v K T
v ⎝ ∂p ⎠ T ⎝ ∂p ⎠ T
42
Therefore equation (6) can be written as,
−1
C p − C v = −Tβ 2 v 2
v KT
T vβ2
C p − Cv = ----- ((10))
KT
Ratio of heat capacities
Note: Derive First and Second T ds equations and proceed as follows:

⎛ ∂p ⎞
T ds = CV dT + T ⎜ ⎟ dv Æ First T ds equation
⎝ ∂T ⎠V
⎛ ∂v ⎞
T ds = C p dT − T ⎜ ⎟ dpp Æ Second T ds equat
equation
on
⎝ ∂T ⎠ p
Consider isentropic process, ds = 0
⎛ ∂v ⎞
C p dT = T ⎜ ⎟ dp
⎝ ∂T ⎠ p 43
 ⎛ ∂v ⎞ dp
Cp = T⎜ ⎟
⎝ ∂T ⎠ p dT

⎛ ∂p ⎞
CV dT = −T ⎜ ⎟ dv
⎝ ∂T ⎠V
⎛ ∂p ⎞ dv
CV = −T ⎜ ⎟
⎝ ∂T ⎠V dT
Cp ⎛ ∂v ⎞ ⎛ ∂T ⎞ dp dT
= −⎜ ⎟ ⎜⎜ ⎟⎟
Cv ⎝ ∂T ⎠ p ⎝ ∂p ⎠ v dT dv
Cp ⎛ ∂v ⎞ ⎛ ∂T ⎞ dp
= −⎜ ⎟ ⎜⎜ ⎟⎟
Cv ⎝ ∂T ⎠ p ⎝ ∂p ⎠ v dv

But, dp = ⎛⎜ ∂p ⎟⎞ for isentropic process

dv ⎝ ∂v ⎠ s
Therefore, Cp ⎛ ∂v ⎞ ⎛ ∂T ⎞ ⎛ ∂p ⎞
= −⎜ ⎟ ⎜⎜ ⎟⎟ ⎜ ⎟ ----- (1)
Cv ⎝ ∂T ⎠ p ⎝ ∂p ⎠ v ⎝ ∂v ⎠ s 44
 ⎛ ∂p ⎞ ⎛ ∂T ⎞ ⎛ ∂v ⎞
We can write, ⎜ ⎟ ⎜ ⎟ ⎜⎜ ⎟⎟ = −1
⎝ ∂T ⎠ v ⎝ ∂v ⎠ p ⎝ ∂p ⎠ T

⎛ ∂p ⎞ ⎛ ∂T ⎞ ⎛ ∂v ⎞
⎜ ⎟ ⎜ ⎟ = −⎜⎜ ⎟⎟
⎝ ∂T ⎠ v ⎝ ∂v ⎠ p ⎝ ∂p ⎠ T
Cp ⎛ ∂v ⎞ ⎛ ∂p ⎞
Substituting
g in (1),
( ), = ⎜⎜ ⎟⎟ ⎜ ⎟ ----- (2)
C v ⎝ ∂p ⎠ T ⎝ ∂v ⎠ s

1 ⎛ ∂v ⎞ ⎛ ∂v ⎞
K T = − ⎜⎜ ⎟⎟ ⎜⎜ ⎟⎟ = −v K T
v ⎝ ∂p ⎠ T Æ
⎝ ∂p ⎠ T
1 ⎛ ∂v ⎞ ⎛ ∂v ⎞
K S = − ⎜⎜ ⎟⎟ Æ ⎜⎜ ⎟⎟ = −v K S
v ⎝ ∂p ⎠ S
⎝ ∂p ⎠ S
Cp KT
Substituting in (2), =
Cv K S 45
Joule-Thomson coefficient
-Ag
gas is made to undergo
g continuous throttling
gpprocess by
ya
valve, as shown.
- The pressures and temperatures of the gas in the insulated
pipe upstream and downstream of the valve are measured with
suitable
it bl manometers
t and
d thermometers.
th t

⎛ ∂T ⎞
μ J = ⎜⎜ ⎟⎟
⎝ ∂p ⎠ h

J l Th
Joule-Thomson expansion
i
46
• Let p1 and T1 be the arbitrarily chosen pressure and
temperature before throttling and let them be kept constant.
constant
• By operating the valve manually the gas is throttled
successively to different pressures and temperatures.
temperatures
• These are then plotted on the T-p coordinates.
• The curve passing through all these points is an isenthalpic
curve.

Isenthalpic state of a gas 47

 Isenthalpic curves and the inversion curve

The initial ppressure and temperature

p of the g
gas (before
throttling) are then set to new values, and by throttling to
different states, a family of isenthalpes is obtained for the
gas The curve passing through the maxima of these
gas.
isenthalpes is called the inversion curve.
48
 The numerical value of the slope of an isenthalpe on a T-p
diagram at any point is called the ‘Joule-Thomson
Joule Thomson coefficient
coefficient’
and is denoted by μJ.
At inversion
i i curve, μJ = 0
At right side of the inversion curve, dT is positive, dp is
negative.
μJ = - ve (Heating region)
At left side of the inversion curve, dT is negative, dp is
negative.
g
μJ = + ve (Cooling region)
dh = T ds
d + v dp
d ----- (1)
49
Second T ds equation is given by,
⎛ ∂v ⎞
d = C p dT − T ⎜
T ds ⎟ dpd
⎝ ∂T ⎠ p
⎛ ∂v ⎞
Substituting in (1),
(1) dh = C p dT − T ⎜ ⎟ dpd + v dp
d
⎝ ∂T ⎠ p
⎡ ⎛ ∂v ⎞ ⎤
= C p dT − ⎢T ⎜ ⎟ − v ⎥ dp
d
⎣⎢ ⎝ ∂T ⎠ p ⎥⎦
The second term in the above equation stands only for a real
gas, because for an ideal gas,
dh = Cp dT
dh = 0 for isenthalpic process
⎡ ⎛ ∂∂vv ⎞ ⎤
Th
Therefore,
f C p dT − ⎢T ⎜ ⎟ − v ⎥ dp = 0
⎢⎣ ⎝ ∂T ⎠ p ⎥⎦ 50
 ⎡ ⎛ ∂v ⎞ ⎤
C p dT = ⎢T ⎜ ⎟ − v ⎥ dp
⎢⎣ ⎝ ∂T ⎠ p ⎥⎦
dT 1 ⎡ ⎛ ∂v ⎞ ⎤
= ⎢T ⎜ ⎟ −v⎥
dp C p ⎢⎣ ⎝ ∂T ⎠ p ⎥⎦
⎛ ∂T ⎞ 1 ⎡ ⎛ ∂v ⎞ ⎤
⎜⎜ ⎟⎟ = ⎢T ⎜ ⎟ −v⎥
⎝ ∂p ⎠ h C p ⎢⎣ ⎝ ∂T ⎠ p ⎥⎦

⎛ ∂T ⎞ 1 ⎡ ⎛ ∂v ⎞ ⎤
Therefore, μ J = ⎜⎜ ⎟⎟ = ⎢T ⎜ ⎟ −v⎥
⎝ ∂p ⎠ h C p ⎢⎣ ⎝ ∂T ⎠ p ⎥⎦
For an ideal gas pv=RT
RT
v=
v 51
 ⎛ ∂v ⎞ R v
⎜ ⎟ = =
⎝ ∂T ⎠ p p T

⎛ ∂T ⎞ 1 ⎡ ⎛v⎞ ⎤
μJ =⎜ ⎟ =
⎜ ⎟ ⎢T ⎜ ⎟−v ⎥= 0
⎝ ∂p ⎠ h C p ⎣ ⎝ T ⎠ ⎦
There is no change
g in temperature
p when an ideal g
gas is made to
undergo a throttling.
Another form
⎛ ∂T ⎞ 1 ⎡ ⎛ ∂v ⎞ ⎤
μ J = ⎜⎜ ⎟⎟ = ⎢T ⎜ ⎟ −v⎥
⎝ ∂p ⎠ h C p ⎢⎣ ⎝ ∂T ⎠ p ⎥⎦
1 ⎛ ∂V ⎞
But, β = ⎜ ⎟
V ⎝ ∂T ⎠ p
μJ =
1
[T β v − v ]= [T β − 1]
v
Cp Cp
1
β= for an ideal gas since μJ = 0 52
T
Clausius-Clapeyron equation

• Clausius-Clapeyron
u u p y equation
qu is a relationship
p between
w the
saturation pressure, temperature, the enthalpy of evaporation
and the specific volume of the two phases involved.
involved
• This equation provides a basis for calculations of properties
in a two phase
h region.
• It gives the slope of a curve separating the two phases in the
p-T diagram.

⎛ ∂p ⎞ ⎛ ∂s ⎞
III-Maxwell
ll equation, ⎜ ⎟ =⎜ ⎟
⎝ ∂T ⎠ v ⎝ ∂v ⎠ T

⎛ dp ⎞ ⎛ ds ⎞ s g − s f s fg
⎜ ⎟=⎜ ⎟= =
⎝ dT ⎠ ⎝ dv ⎠ v g − v f v fg 53
 sg = specific entropy of saturated vapour
sf = specific entropy of saturated liquid
vg = specific volume of saturated vapour
vf = specific volume of saturated liquid
hfg = increase in specific entropy
vfg = increase in specific volume

h fg
Also, sg − s f =
T
⎛ dp ⎞ s g − s f h fg h fg
⎜ ⎟= = =
⎝ dT ⎠ v g − v f v fg T v fg
This equation is known as Clausius-Clapeyron equation for evaporation of
liquids. The derivative dp/dT is the slope of vapour pressure versus
temperature curve. Knowing this slope and the specific volume vg and vf
from experimental data, we can determine the enthalpy of evaporation, 54
hfg.
55
56