SINGLE-COMPONENT HOMOGENEOUS SYSTEMS

Behaviour of pure substances

Gases: equation of state

 Van der Waals equation

a
[ ] p+
v2
( v −b ) =RT

 Clausius and Berthellot equations

a a
[ p+
T ( v+ c)2
] [
( v−b )=RT c=0 p+ 2 ( v −b ) =RT
→ Tv ]
 Dieterici equation
a
[ p e ] ( v−b )=RT
RTv

 Redlich-Kwong equation
a
[ p+ 1
2
T v (v +b) ] ( v−b )=RT

Reduced variables: law of the corresponding states

- Critical-Point coordinates for a Van der Waals gas

Saddle point:
δp δ2 p
( ) ( )
δv T
=0 ;
δ v2 T
=0

Inserting the Van der Waals equation:

( δpδv ) = ( −RT
T
2a
+ =0
v−b ) v 2
RT
=
( v−b ) v
2a
3 2 3

δ2 p 2 RT 6a 2 RT 6a
( ) 2
=
δ v T ( v−b ) 3
− 4 =0
v 3
( v−b ) v
= 4

2 2a 6a
= 6 a v 4−6 ab v 3=4 a v 4 2 a v 3 ( v−3 b )=0 → v=3 b
(v−b) v 3 v 4
RT 2a 2 a ( 2 b )2 8 a
2
= 3
T= 3
=
( 3 b−b ) (3 b) R (3 b ) 27 Rb
 p=
R ( 278 Rba ) − a
=
a
2 2
3 b−b ( 3 b ) 27 b
1

{
b= v c
3
2
a=3 p c v c
8 pc v c
R=
3 Tc
- Van der Waals equation in reduced variables
3 pc v c 2 8 pc v c 3 p c v c2
[ p+
v
2 ]( 1
v− v c =
3 )
3 Tc
T
1
[
pc v c
p+
v
2 ]( 1
)
v− v c =
3
8 T
3 Tc
2 v r =v / v c
[ p
pc
v
+ 3 c2
v ]( )
v 1 8 T
− = T =T /T c
vc 3 3 T c r
pr = p/ pc{
3 1 8
[ ](pr + 2
vr
vr − = Tr
3 3 )
- Law of the corresponding states
If equal amounts (masses) of two gases are at the same reduced pressure and occupy
the same reduced volume, their reduced temperatures are necessarily also the same.
The law of the corresponding states is “universal” for gases obeying a certain equation
(valid for two-parameter equations of state)

Virial equation of state

Series of expansions as:

B C
pv= A+ + 2 +… pv =A ' + B' p+ C' p 2+ …
v v

Taking that for an ideal gas pv=RT → A= A' =RT

The coefficients of expansions are related by:

A B C
p= + + +…
v v2 v3
2
A B C ' A
pv= A + B '
+ +
v v2 v3
'
(
+C 2 + …
v ) ( )
B' A B ' B +C' A 2

{ pv =A ' +
v
+
B C
v2
pv= A + + 2 + …
v v
+… B=B' A=B' A ' B' =
' '2 ' '2
B
A
C=B B+C A = A B +C ' A ' 2
'
Example: virial expansion for the Van der Waals equation of state

a RT a RTv a RT a
[ ] p+
v 2
( v −b ) =RT p= − 2 pv=
v−b v
− =
v−b v
a−
−
b v
v

b b2 a RTb RT b2 a RTb−a RT b 2
v v [
pv=RT 1+ + 2 +… − =RT +
v ]
v
+ 2 +…− =RT +
v v v
+ 2 +…
v

A=RT

{B=RTb−a the virial coef depend on T an on the gas nature

C=RT b
2

Amagat diagram: Boyle temperature

Representation of pv as function of p for different

temperatures.

Above a certain temperature, there is not any minimum in the

isothermal curves.

Boyle point:

lim
p→0
( δ (δppv ) ) =0
T

Virial expansion

pv= A' + B' p+C ' p2 … ( δ (δppv ) ) =B +2 C p+ … lim ( δ (δppv) ) =B '

T
' '

p →0 T

Boyle temperature B’=0. In this case of a Van der Waals gas:

RTb−a a
B' = =0 → T B=
RT Rb

Compressibility factor

Characterization of the behaviour of a real gas through its deviation from the ideal gas
behaviour.

Def: ratio of the specific volume and the specific volume of an ideal gas at the same pressure
and temperature.

v pv
Z= =
RT / p RT
 B C B C A B C
pv= A+ + 2 +… ZRT = A+ + 2 + … Z= + + 2 +…
v v v v RT vRT v RT

~ B

{
B=
RT ~ ~
B C
~ C Z=1+ + 2 + … Z=1+ ~
B' p+ ~
C' p2 + …
C= v v
RT
…

pv pr v r p c v c
Z= = Z=Z ( p r ,T r )
RT Tr RTc
Thermal coefficients

pv

( δ δTln Z ) =( )
δ ln
RT 1 δv 1 1
p δT p
= ( ) − =α −
v δT p T T

( δ δpln Z ) = 1v ( δpδv ) + 1p = 1p − χ
T T
T

( δ δTln Z ) = 1v ( δTδp ) − T1 =β− T1

p v

Joule-Kelvin coefficient

Cooling or heating associated with the isenthalpic expansion of a gas in a throttling device:
 h1 =h2

Slope of the isenthalpic lines:

μJK = ( δTδp ) ( δTδp ) ( δpδh ) ( δTδh ) =−1

h h T p

δh
−( )
δT δp −1 δh
μ =( ) =
C ( δp )
T
JK =
δp δh
h
( δT )
p
p T

δh δs
dh=Tds+ vdp → ( ) =T ( ) + v
δp T δp T

( δpδs ) =−( δTδv ) Maxwell

T p

1 δv
μJK =
Cp
T
[( ) ]
δT p
−v

Ideal gas:

μJK =0

Intersection between the inversion curve and the vertical axis (max inversion temperature)

In the case of a Van der Waals gas:

3
1 RT v b−2 av ( v−b )
2
2 a ( v i−b )2 2a
μJK = =0T i= T i ,max =
C p RT v −2 a ( v−b )
3 2
R vi b2
Rb
SINGLE COMPONENT- MULTIPHASE SYSTEMS: PHASE EQUILIBRIUM
Multiphase systems: the concept of phase

Phase: amount of matter homogeneous in both chemical composition and physical structure,
bounded by a surface through which the physical properties change abruptly.

Phase equilibrium

Single component system, two phases ( p1= p2 ; T 1=T 2 ¿

p ,T =cte
G=m1 g 1+ m 2 g2

Equilibrium condition :dG=m 1 d g1 + g1 d m 1 +m 2 d g2 + g2 d m 2=0

cte T , p → d g 1=0 ; d g 2=0

{m1 +m 2=cte d m 1+ d m 2=0
dG=( g 1−g2 ) d m1=0 g 1 ( T , p )=g 2(T , p)

The equilibrium condition is the equality g1 ( T , p )=g2 (T , p)

V , T =cte
F=m 1 f 1 +m 2 f 2

Equilibrium condition :d F=m 1 d f 1+ f 1 d m 1 +m 2 d f 2+ f 2 d m2=0

V =m 1 v 1 +m2 v 2=cte

{ m1 d v1 + v 1 d m1+ m2 d v 2 +v 2 d m2=0
p m1 d v 1+ p v 1 d m1+ p m2 d v 2+ p v 2 d m2=0
( f 1 + p v 1 ) d m1+ ( f 2 + p v 2 ) d m2 +m 1 ( d f 1 + p v 1 ) +m2 ( d f 2+ p d v2 ) =0
df =−sdT − pdv T =cte df + pdv =0 d m1 +d m2=0

( f 1+ p v 1 )=( f 2 + p v 2 ) g 1=g2
→

The equilibrium condition remains independent of the system constraints.

Two phases of a pure substance cannot coexist at any T and p: if one is fixed, the other
is determined.

Clausius-Clapeyron equation

Starting state of equilibrium g1 ( T , p )=g2 (T , p) , if the system remains in equilibrium after an

infinitesimal deviation, then:

g1 +d g 1=g2 +d g 2 d g1=d g2−s 1 dT +v 1 dp=−s 2 dT + v 2 dp

 dp ( s2−s 1) ∆ s
( v 1−v 2 ) dp=( s1−s 2) dT dT = =
( v 2−v 1 ) ∆ v
Latent heat associated with the phase change: l=T ∆ s

dp ∆ s l
= =
dT ∆ v T ∆ v

Vaporization and sublimation lines

dp
l>0 ∆ v> 0 >0
dT
Fusion line:

dp
l>0 ∆ v ≈ 0 (slope) depends on the sign of ∆ v
dT

Integration of the Clauisus-Clapeyron equation for vaporization and sublimation lines

Hypothesis:

- l does not depend on T , p

- The volume condensed phase is negligible compared to the volume of the vapour
∆ v=v 2−v 1 ≈ v 2
RT
- The vapour phase behaves as an ideal gas v 2=
p
l
dp l lp dp l dT
−
R ( )
= =
dT T ∆ v R T 2
→ =
p R T 2
→ ln p=
T [ ]
+C
− ( l /R )

p=C ' e
[ T ]

August and Antoine equations

B
log p= A− August equation
T
B
log p= A− A ntoine equation
C+T

Thermodynamic properties of biphasic systems

Quality:

mv
x=
mv + ml
The states below the saturation dome are determined by the values of the saturation line and
the quality of the mixture.

v−v l u−u l h−hl s−sl

x= = = =
v g−vl u g−ul h g−hl sg −s l

Tables and charts

Refrigeration systems with phase change