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Mathematical Theorems

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


Thermodynamics Relations
     
x y z
= 1
Dr. M. Zahurul Haq y z z x x y
           
Professor y x y z z x
= = =1
Department of Mechanical Engineering x z y z z x y x x y z y
Bangladesh University of Engineering & Technology (BUET)
Dhaka-1000, Bangladesh 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/ z z
z = z (x , y) dz = dx + dy = Mdx + Ndy
x y y x
ME 6101: Classical Thermodynamics
   
2 z 2 z M N
For continuous functions, x y = yx = =
y x x y

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 1 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 2 / 22

Maxwell Relationships Cv & Thermodynamics Relationships

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


du = Tds Pdv = u

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

Cv T v s v T v = T T v
Helmholtz Energy, f u Ts df = Pdv sdT  2 
Cv s 2 s
     s  P
Gibbs Energy, g h Ts dg = dh Tds sdT = vdP sdT v T = v T T v = T v T = T T v T = T T 2 v
s P
 
  using Maxwells relation: v T
= + T v
2 z 2 z M N

For continuous functions, x y = yx = y = x y x If P-v-T data or mathematical relationship is available, it is possible to
1 du = +Tds Pdv = T

= P

(A) evaluate 2 P/T 2 , and then (Cv /v )T .
v s s v
Ideal gas: Pv = RT
T v
 
(B)

2 dh = +Tds + vdP = P s =+ s P = T P

= R
& 2 P
= 0 7 Cv 6= f (v )
v v T 2
v
s P
 
3 df = sdT Pdv = v T =+ T v (C) van RT
der Walls gas: P = v b va2
 2 
P R P

s v = = & T 2 = 0 7 Cv 6= f (v )
 
4 dg = sdT + vdP = P T = T P (D) T v v b

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 3 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 4 / 22
CP & Thermodynamics Relationships Tds Relationships

s s
 
s = s(v , T ) ds = T v
dT + v T
dv
s s P
dh = Tds + vdP = h
   
s P = T
Cv = T T v
& v T = + T v , Maxwells Relation (C)
h h s s
     
CP = T = = T P
P s P T P T P Tds = Cv dT + T dv 1st Tds

CP


 s
 
 s   2 
v T v
P T = P T T P = T T P T = T T 2 P
s s
 
using Maxwells relation: P s

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

CP = T T P
& P T = T P , Maxwells Relation (D)
 
2 v
 
v R v

Ideal gas: = T P = P & T 2
= 0 7 CP 6= f (P) Tds = CP dT T dP 2nd Tds
P
v
T P
van der Walls gas: = T P = P a R1 2b

v2
( v) s = s(P, v ) ds = P s

dP + v s

dv
v P
 
 2  R 2 2a3 6ab R P2  2  s
 s

v
= v v4

7 CP = f (P) = T v
dP Cv = T T v & CP = T T P
T 2 P 3 P1 T 2 P
 
a 2b
P 2 (1 v )    
v T T
Tds = Cv dP + CP dv 3rd Tds
P v v P

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 5 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 6 / 22

Internal Energy, u Enthalpy h

u u u
  
u = u (v , T ) du = T v dT + v T dv = Cv dT + v T dv h
 h
 h

h = h(P, T ) dh = T P dT + P T dP = Cp dT + P T dP
P
dv Pdv (- 1st Tds Eq.)

du = Tds Pdv = Cv dT + T v
2nd Tds

T v dh = Tds + dP = CP dT T dP + vdP (- Eqn.)
T P
   
u P    
=T P h v
v T T v
=v T
P T T P
u
  RT 
Ideal gas: v T = v P = 0 h
= v TR

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

du = Cv dT = f (T )
dh = CP dT = f (T )
van der Waals gas:
u
 RT a a van der Waals gas: = h = f (T , P)
v T = v b P = v2
du = Cv dT + v2
dv = f (T , v )

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations 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 v
dT + v dv
h T  i
s s s v s CP s Cv
    
= + - = , =
for isobar: T P T v v T T P T P
 vT  v T T
s v P
 
dhP = CP dTP CP CV = T v T T P = T T v T P
z
  y   x 
for isotherm: f (x , y, x ) = 0 x y z x y z
= 1
v
  
dhT = v T dPT P
 T
 v
 P
 v
 P

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

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

v

T011 1 For liquids & solids, T P
0 CP Cv C
h2 h1 = (h2 h2 ) + (h2 h1 ) + (h1 h1 ) v
 2 P

T P is +ve & v T is -ve for all known substances, CP Cv
2
RP  v
  RT
= P02 v T T P T2
dP + T12 CPo dTP
RP  v
  3 as T 0, Cp Cv , at T = 0, CP = Cv
P01 v T T P T
dP
1

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 9 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 10 / 22

Example: Liquid Water 1 atm & 20o C


Isothermal compressibility, kT v1 v

P T
Volume expansivity, v1 Tv

P
2 (206.6106 1 )2 105 N2
v 2 2 1
CP Cv = T P
 
v T T P = kT vT
CP Cv = = 45.95106 K1
kT vT kg (293K ) m
1bar
bar 998.21 m 2
1 1 J J
Ideal gas: Pv = RT kT = P, = T = Cp Cv = R CP Cv = 27.29 kg.K , CP = 4188 kg.K 7 CP w Cv
P 1
dT + P
 
for liquid water at 1 bar: P = P(v , T ) dP = T v v T dv = kT dT kT v dv

1
dP = dT dv
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
206.6106 K1
T012
P = 1
45.95106 bar bar (1K ) = 450 kPa
2
= 0.0@4o C for water.
10 kPa

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 11 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 12 / 22
Applications of Tds Relationships Example: 15 cm3 Hg @0o C & 1 bar 1000 bar

at 0o C V = 1.5 105 m 3 CP = 28.6J /K


2nd Tds v = 178 106 K 1 kT = 3.88 106 bar 1

: Tds = CP dT T T P dP
Reversible isothermal change in pressure: isothermal compression: P1 = 1 bar, P2 = 1000 bar.
v

Tds = T T dP Q = mq = T (mv )P = T V P = 78.2 J
R v  P R
q = T T P dP = T vdP = T v P W = mw = V 2kT (P22 P12 ) = 2.91 J
R R v  R P2 v kT 2 2 U = Q + W = 75.29 J
w = Pdv = P T
PdP = P1 vkT PdP = 2 (P2 P1 )
for a liquid & solid, v , & kT are insensitive to change in P 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.
Reversible adiabatic change in pressure:
Tv For a substance with a negative expansivity, heat is absorbed and
dT = CTP T v
dP = Tv

P CP dP = T = CP P the internal energy is increased.
Experiments show that CP hardly changes for a solid & liquid
even for an increase of 10,000 bar. isentropic compression: P1 = 1 bar, P2 = 1000 bar.
= T = TCvP P = 2.55 K

c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 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


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

T v = dT , for mixture of 2 phases, P = f (T )
dP s2 s1 h2 h1 dP h12

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


vfg = (vg vf )sat ,@20  C = 0.035153
o m3 kg
dP P Psat ,@24o C Psat ,@16o C
dT sat ,@20o C = T sat ,@20o C = 240 C 16o C = 17.70 kPa/K
dP
sat ,@20o C
hfg = Tvfg dT = (293.15)(0.035153)(17.70) = 182.40 kJ/kg
o
Tabulated value of hfg @20 C is 182.27 kJ/kg.

hfg
v2 >> v1 v2 = RT P d ln P
d (1/T ) sat = R Clausius-Clapeyron Eq.
   
P2 h 1 1 e789
ln P 1
= R T 1
T 2
sat If the temperature and pressure of a gas can be brought into the region
B between the saturated liquid and saturated vapour lines then the gas
ln Psat =A+ + C ln T + DT , widely used vapour-pressure Eq.
T
will become wet and this wetness will condense giving a liquid.
c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 15 / 22 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 Compress isentropically to 2, where P2 > Pc


2 As T2 > Ta , cool it to Ta using ambient sources, and further cool
to T3 using available cold sources.
e790
3 Expand isentropically form 3 to 4 liquid formation.
c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 17 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 18 / 22

Liquefaction by Cooling 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 e769
A cooling effect cannot be achieved by throttling unless the fluid is

T
 ve : temperature increase
below its maximum inversion temperature. For hydrogen its value
JT = 0 : temperature same
P h is -68o C and hydrogen must be cooled below this temperature if
+ve : temperature drop
further cooling is to be achieved.
c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 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
" #
RT a 1  RT
P= v b v2
= JT = CP
   v e797
P + a2 (v b) 2a3
v v
e796
Maximum inversion temperature = 6.75Tc Two performance parameters:
Minimum inversion temperature = 0.75Tc Yield, z : mass of liquid produced per unit mass of gas compressed.
I If air is compressed to a pressure of 200 bar and a temperature of Sp. work required, wz : work per unit mas of liquid produced.
52o C, after the throttling to 1 bar it will be cooled to 23o C. In case of y h7 h2 Win
z = = wz =
helium, throttling from the came condition will result in 64o C. m h7 h5 z
c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 21 / 22 c Dr. M. Zahurul Haq (BUET) Thermodynamics Relations ME 6101 (2011) 22 / 22