Mathematical Theorems

If there exists a relation among x , y & z ; f (x , y, z ) = 0

Thermodynamics Relations

Dr. M. Zahurul Haq



Professor
Department of Mechanical Engineering
Bangladesh University of Engineering & Technology (BUET)
Dhaka-1000, Bangladesh

y
x

 
z

x
y

x
y

 

y
z

z = z (x , y) dz =

ME 6101: Classical Thermodynamics

For continuous functions,

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Thermodynamics Relations

ME 6101 (2011)

1 / 22

Maxwell Relationships

Enthalpy, h u + Pv dh = du + Pdv + vdP = Tds + vdP

Helmholtz Energy, f u Ts df = Pdv sdT

Gibbs Energy, g h Ts dg = dh Tds sdT = vdP sdT

 


2 z
N
M
2 z
For continuous functions, x
=
=
=
y
yx
y
x y
x

du = +Tds Pdv =

T

=
x

z
x

c Dr. M. Zahurul Haq

(BUET)

z
x

2 z
x y

dx +
y

2 z
yx

z
y

 
y

x
z

=1
y

dy = Mdx + Ndy
x

M
y

Thermodynamics Relations

=
x

N
x

ME 6101 (2011)

y
2 / 22

v
s P

(B)

=+

P
T v

(C)

Ideal gas: Pv = RT




2 P
R
P
&
=
= 0 7 Cv 6= f (v )
= T
2
v
T
v

v

(D)

T
P s

df = sdT Pdv =

s
v T

dg = sdT + vdP =

s

P T

If P-v-T data or mathematical relationship is available, it is possible to

evaluate 2 P/T 2 , and then (Cv /v )T .

=+

dh = +Tds + vdP =

P

du = Tds Pdv = u
s v = T



s



u
s
Cv T
= u
s v T v = T T v
v
 2 





 s 
Cv

s
2 s
P

v T = v T T v = T v T = T T v T = T T 2 v




P
s
= + T
using Maxwells relation: v
T
v

(A)

(BUET)

z
y

= 1

c Dr. M. Zahurul Haq

 

Cv & Thermodynamics Relationships

Internal Energy, du = q + w = Tds Pdv (for rev. process)

z
x

f (x , y, z ) = 0 7 z = z (x , y), y = y(z , x ), x = x (y, z )

zahurul@me.buet.ac.bd
http://teacher.buet.ac.bd/zahurul/

c Dr. M. Zahurul Haq

 

y
z

T P

Thermodynamics Relations

ME 6101 (2011)

van

3 / 22

v
RT
der Walls gas: P = v b va2
 2 


P
P
R
&
=
T v
v b
T 2 = 0 7

c Dr. M. Zahurul Haq

(BUET)

Cv 6= f (v )

Thermodynamics Relations

ME 6101 (2011)

4 / 22

CP & Thermodynamics Relationships

Tds Relationships

dh = Tds + vdP = h
s P = T








s
h
s
h
=
=
T
CP = T
s
T
T
P
P
P
P

 2 




 s 
CP

v
P T = P T T P = T T P T = T T 2 P




v
s
= T
using Maxwells relation: P
T
P
Ideal gas: =

v
T P

R
P

&


v

2 v
T 2

= 0 7 CP 6= f (P)

van der Walls gas: = T P = P a R1 2b

( v)
v2


 2 
 2 
R P2
R 2 2a3 6ab
v
v4
v
v



C
=
f
(P)
=
T
=

dP
P
3
P1
T 2 P
T 2 P
2b
a
P 2 (1 v )
v

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

5 / 22

Internal Energy, u
u
T v

u
v

 RT

u
v T

dT +

du = Tds Pdv = Cv dT + T

P

T v

=T
T

dv = Cv dT +

u
v T

dv

dv Pdv (- 1st Tds Eq.)

P
T

Thermodynamics Relations

van der Waals gas:

u
RT
v T = v b P =

a
v2

du = Cv dT +

a
dv
v2

h
T P

h
P

h
P T

dT +

dh = Tds + dP = CP dT T

Thermodynamics Relations

h = h(P, T ) dh =

ME 6101 (2011)

6 / 22

v
T P

=v T
T

dP = Cp dT +

dP + vdP (

v
T

h
P T

2nd Tds

dP

Eqn.)

h
= 0 h 6= f (P)
= v TR
Ideal gas: P
T




P




v
h
h
h
=
0
=
=
Pv h
P
T
v T P T
v
T v T = 0
h
h
P T = 0 h 6= f (P) :
v T = 0 h 6= f (v )

du = Cv dT = f (T )

(BUET)

(BUET)

Ideal gas: v T = v P = 0



P





u
u
P u
u
v
T = 0 = P T v T = v P
T P T = 0
u
u
v T = 0 u 6= f (v ) :
P T = 0 u 6= f (P)

c Dr. M. Zahurul Haq

c Dr. M. Zahurul Haq

Enthalpy h

u = u (v , T ) du =

u

s
s
s = s(v , T ) ds = T
dT
+
dv
v
v
T






s
P
s
&
=
+
,
Maxwells
Relation (C)
Cv = T T
v T
T v
v


P
dv
1st Tds
Tds = Cv dT + T
T v




s
s
s = s(P, T ) ds = T
dT + P
dP
P
T






s
v
s
&
=

,
Maxwells
Relation (D)
CP = T T
P T
T P
P


v
2nd Tds
Tds = CP dT T
dP
T P




s
s
dP + v
dv
s = s(P, v ) ds = P
v
P




s
s
Cv = T T v & CP = T T P




T
T
Tds = Cv
dP + CP
dv
3rd Tds
P v
v P

dh = CP dT = f (T )

van der Waals gas: = h = f (T , P)

= f (T , v )
ME 6101 (2011)

7 / 22

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

8 / 22

CP Cv




s
s
s = s(v , T ) ds = T
dT + v
dv
v
h T











CP
s
v
s
s
s
s
,
=
+
=
=
T P
T v
v T T P
T P





vT
v T
s
v
P
CP CV = T v T T P = T T v T P

 y   x 
z
f (x , y, x ) = 0 x
= 1
y z x y z












T
v
v
P
P
P
v T P v T P = 1 v T T P = T v

v





v 2
P
= T P
CP Cv = T T
v T T P
v T P

for isobar:
dhP = CP dTP
for isotherm:

dhT = v T

v
T P



dPT

T011

h2 h1

= (h2 h2 ) + (h2 h1 ) + (h1 h1 )

RP 
RT


v
= P02 v T T
dP + T12 CPo dTP
P T2
RP 


v
P01 v T T
dP
P T

2
3

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

Isothermal compressibility, kT v1


v
Volume expansivity, v1 T
P


CP Cv = T P
v T
Ideal gas: Pv = RT kT =

1
P,

ME 6101 (2011)

9 / 22

1
T

v
0 CP Cv C
For liquids & solids, T
P




2
P
v
T P is +ve & v T is -ve for all known substances, CP Cv
as T 0, Cp Cv , at T = 0, CP = Cv

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

10 / 22

Example: Liquid Water 1 atm & 20o C

v
P T

v 2
T P

Cv
T

 105 N2 
(206.6106 1 )2
1
 m 
= 45.95106 K1
CP Cv =
(293K
)
kg
 1bar 
bar 998.21 m 2
J
J
CP Cv = 27.29 kg.K , CP = 4188 kg.K 7 CP w Cv

P
1
P = P(v , T ) dP = T
dT + P
v T dv = kT dT kT v dv
v
2
kT vT

2
kT vT

= Cp Cv = R

for liquid water at 1 bar:

dP =

dv
dT
kT
kT v

If liquid water temperature is raised form 19.5 to 20.5o C at

constant volume: dP = kT dT 7 P = kT T

P =

T012

= 0.0@4o C for water.

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

206.6106 K1
bar
1
45.95106 bar
2

(1K ) = 450 kPa

10 kPa

ME 6101 (2011)

11 / 22

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

12 / 22

Example: 15 cm3 Hg @0o C & 1 bar 1000 bar

Applications of Tds Relationships

at 0o C

2nd Tds

Tds = CP dT T

v

T P

dP

Reversible isothermal change in pressure:

v
Tds = T T
dP
R
R v
P
q = T
T P dP = T vdP = T v P
R P2
R
R v

v kT
2
2
PdP
=
w = Pdv = P
P1 vkT PdP = 2 (P2 P1 )
T
for a liquid & solid, v , & kT are insensitive to change in P

(BUET)

Thermodynamics Relations

ME 6101 (2011)

= 1.5 105 m 3
= 178 106 K 1

CP
kT

= 28.6J /K
= 3.88 106 bar 1

isothermal compression: P1 = 1 bar, P2 = 1000 bar.

Q = mq = T (mv )P = T V P = 78.2 J
W = mw = V 2kT (P22 P12 ) = 2.91 J
U = Q + W = 75.29 J

78.2 J heat is liberated but only 2.91 J work is done. The extra
amount of heat comes from the store of the internal energy.
For a substance with a negative expansivity, heat is absorbed and
the internal energy is increased.

Reversible adiabatic change in pressure:

Tv

v
dT = CTP T
dP = Tv
CP dP = T = CP P
P
Experiments show that CP hardly changes for a solid & liquid
even for an increase of 10,000 bar.

c Dr. M. Zahurul Haq

isentropic compression: P1 = 1 bar, P2 = 1000 bar.

= T = TCvP P = 2.55 K
13 / 22

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

14 / 22

Low Temperature Refrigeration

Clausius-Clapeyron Equation (for Phase Change)

Tc & Pc of Common Substances

s2 s1
s
P
T v = v T = v2 v1 : phase change T = Tsat = const.


P
dP
T v = dT , for mixture of 2 phases, P = f (T )


s2 s1
h2 h1
h12
dP
dP
dT = v2 v1 = T (v2 v1 ) dT sat = Tv12 Clapeyron Eqn.

Example: using only P-v-T data, estimate hfg of R-134a at 20o C

o
vfg
= (vg vf )sat ,@20
m3 kg

C = 0.035153
Psat ,@24o C Psat ,@16o C
dP
P
= 17.70 kPa/K
dT sat ,@20o C =
240 C 16o C

T sat ,@20o C =
dP
=
(293.15)(0.035153)(17.70)
= 182.40 kJ/kg
hfg = Tvfg dT
sat ,@20o C
o
Tabulated value of hfg @20 C is 182.27 kJ/kg.

hfg
d ln P

v2 >> v1 v2 = RT
P
d (1/T ) sat = R Clausius-Clapeyron Eq.


 
P2
h
1
1
=

ln P
R
T
T
1
1
2

sat

ln Psat

B
+ C ln T + DT , widely used vapour-pressure Eq.
=A+
T

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

15 / 22

e789

If the temperature and pressure of a gas can be brought into the region
between the saturated liquid and saturated vapour lines then the gas
will become wet and this wetness will condense giving a liquid.

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

16 / 22

Liquefaction by Cooling

Liquefaction by Cooling

Liquefaction by Cooling

Liquefaction by Expansion

This method is satisfactory if the liquefaction process does not require

very low temperatures. Example butane, propane, Examples of these
are the hydrocarbons butane and propane, which can both exist as
liquids at room temperature if they are contained at elevated pressures.
Mixtures of hydrocarbons can also be obtained as liquids and these
include liquefied petroleum gas (LPG) and liquefied natural gas (LNG).

e792
1
2

e790

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

17 / 22

Compress isentropically to 2, where P2 > Pc

As T2 > Ta , cool it to Ta using ambient sources, and further cool
to T3 using available cold sources.
Expand isentropically form 3 to 4 liquid formation.

c Dr. M. Zahurul Haq

Liquefaction by Cooling

(BUET)

Thermodynamics Relations

ME 6101 (2011)

18 / 22

Liquefaction by Cooling

Gas Expansion & Joule-Thomson coefficient

The temperature behaviour of a fluid during a throttling process is
described by Joule-Thomson coefficient, JT .

e772
e773

JT



ve
T
=

0
P h
+ve

c Dr. M. Zahurul Haq

(BUET)

: temperature increase
: temperature same
: temperature drop

Thermodynamics Relations

ME 6101 (2011)

e769

A cooling effect cannot be achieved by throttling unless the fluid is

below its maximum inversion temperature. For hydrogen its value
is -68o C and hydrogen must be cooled below this temperature if
further cooling is to be achieved.

19 / 22

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

20 / 22

Liquefaction by Cooling

Liquefaction by Cooling

Simplified Linde Liquefaction Plant

e793

P=

RT
v b

a
v2

= JT =

1
CP

"

 RT
 
P + a2 (v b) 2a3
v

e797

Maximum inversion temperature = 6.75Tc

Minimum inversion temperature = 0.75Tc
I If air is compressed to a pressure of 200 bar and a temperature of
52o C, after the throttling to 1 bar it will be cooled to 23o C. In case of
helium, throttling from the came condition will result in 64o C.

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

21 / 22

e796

Two performance parameters:

Yield, z : mass of liquid produced per unit mass of gas compressed.
Sp. work required, wz : work per unit mas of liquid produced.
y
h7 h2
Win
z =
=
wz =
m
h7 h5
z

c Dr. M. Zahurul Haq

(BUET)

Thermodynamics Relations

ME 6101 (2011)

22 / 22