Real Gases - General Observations

Deviations from ideal gas law are particularly important at high

Chapter 20+
pressures and low temperatures
Real gases differ from ideal gases in that there can be interactions
between molecules in the gas state

The Real Gases and

• Repulsive forces important only when molecules are nearly in contact,
i.e. very high pressures

Phase transitions
→
– Gases at high pressures , gases less compressible
• Attractive forces operate at relatively long range (several molecular
diameters)
– Gases at moderate pressures are more compressible since attractive
forces dominate
• At low pressures, neither repulsive or attractive forces dominate →
ideal behavior
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Real Gases - General Observations Real Gases Compression Factor

The Ideal Gas Law ignores both the

volume occupied by the molecules of a Vmreal gas Vmreal gas PVmreal gas
gas and all interactions between Z  
molecules, whether attractive or repulsive Vmperfect gas RT / P RT
In reality, all gases have a volume and the
molecules of real gases interact with one
another. Z = 1 perfect gas

For an ideal gas, a plot of PV/nRT versus P gives a horizontal line Z > 1 repulsive interaction
with an intercept of 1 on the PV/nRT axis.
The reasons for the deviations from ideality are: Z < 1 attractive interaction
•The molecules are very close to one another, thus their
volume is important. Repulsive forces tends to drive the
•The molecular interactions also become important. molecules apart at higher pressures.
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 Real Gases: Deviations from Ideal Behavior Real Gases – van der Waals equation of state
Real gases do not follow PV = nRT perfectly. The van der Waals
equation corrects for the nonideal nature of real gases.
For the ideal gas: For real gases:
 an 2 
1). The size of molecules 1). The molecule itself  P  2  V  nb   nRT
is negligible; occupies a volume;  V 

2). Molecules do not 2). There are interactions Repulsive interaction

interact; among molecules;

V  V-nb
… …
Attractive interaction

pV=nRT (p+p) (V -V ) =nRT P  P+(n/V)2

a corrects for interaction between atoms;
b corrects for volume occupied by atoms.
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The V.d.W Equation The V.d.W Equation

A non-zero volume of molecules =
“nb” (b is a constant depending on the
type of gas, the 'excluded volume'). The
molecules have less free space to move
around in, so replace V in the ideal gas
equation by V - nb
Very roughly, b  4*1/6 d3
where d is the molecular diameter.
The attractive forces between real molecules reduce the pressure:
p  wall collision frequency and
p  change in momentum at each collision.
Both factors are proportional to concentration,
n/V, and p is reduced by an amount a(n/V)2,
where a depends on the type of gas.
[Note: a/V2 is called the internal pressure of
the gas].

In the van der Waals equation, V becomes V-nb P becomes (P  nV 2a )

2
In the van der Waals equation

where “n b” represents the volume occupied by “n” moles of where “n2a/V2” represents the effect on pressure to intermolecular
molecules. attractions or repulsions.
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 Real Gases: Deviations from Ideal Behavior The V.d.W Equation
Simple equation capable of representing both liquid and vapor
nRT n 2a
P  2 behavior.
V  nb V RT a V
P  with V 
___
The V.d. W equation of state:
Corrects for V2 N
V b
___
Corrects for • a and b are positive constants
molecular volume molecular attraction
• General form of the van der Waals equation: • unrealistic behavior in the two-phase region. In reality, two,
 2  within the two-phase region, saturated liquid and saturated vapor
 P  n a V  nb   nRT coexist in varying proportions at the saturation or vapor pressure.
 V 2 
 • Three volume roots, of which two may be complex.
When V or T are very large i.e. at low p or high T, then this van der
Waals equation of state becomes equivalent to the ideal equation. • Physically meaningful values of V are always real, positive, and
a and b are empirical Van der Waals constants. greater than constant b.

It is easy to solve for p given V.

To find V given p you need to solve a cubic equation (with Vm=V/n)
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The V.d.W Equation The vdW Isotherms of Real Gases

Nonideal Conditions when gas PH

gets close to conditions where it
H2O
will liquify
Y
U G
W T S
• Lower Temperature M
J R 400 oC
• Higher Pressure L N 374 oC
V 300 oC
L
L+V 200 oC

K
Isotherms of H2O Vm
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 The vdW Isotherms and Critical point
The vdW Isotherms and Critical point
a ___ RT a
(P  )( V  b )  RT
At fixed P and T, V is the P 
solution of a cubic equation. V b V 2
V2 There may be one or three real-
 P   2P 
valued solutions. at critical point    0 and  2   0
 V T  V T
The set of parameters Pc, RT 2a
  0
Vc, Tc for which the V  b  V3
2

number of solutions 2 RT 6a
 0
changes from one to V  b  V4
3

three, is called the 8a a 8 PV

Vc  3b; Tc  ; Pc  ; R c c
critical point. The van 27bR 27b 2 3Tc
der Waals equation has pcVc 3
an inflection point at Tc. Zc    0.375  const
RTc 8
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Internal Energy of the vdW Gas The Joule Thomson effect

  V T dV
 U 
UvdW  Uideal 
Thermal insulation
Let’s start with an ideal gas (the dilute limit, interactions can be
T const
neglected) and compress the gas to the final volume @ T,N =
C F
O O
O

const:
C F
O O
O

5 120

0
4
100
5 120

0 0

  dU  TdS  PdV   T   S

  S   P  
3

 U    P 
80
4
100
0
0 2

  P       T  P
3


60
80
0
0 1
2 0
40

  V T  V T   V  T   T  V    T V
60
0
1
0
20
40
0 1
0
0
0 20
2
1 0 20
0 3
0

2 0

From
40
0 20
4
3

Nk BT aN 2
0

 U 
0 40
5 60

the vdW P   2 N 2a
4 0

 
0

  
5 60

  P  1  N 2a 
0

V Nb V Nk B
equation:     P    V T V 2
 T V V  Nb T  V 2 
T1, P1, Vm,1 T2, P2, Vm,2
Na

 U  f N 2a
U vdW  U ideal  N
U vdW  U ideal    dV  N k BT 
T  const  V T 2 V V
This derivation assumes that the system is homogeneous – it does not work for the

Porous Plug
two-phase (P, V) region (see below).
The same equation for U can be obtained in the model of colliding rigid spheres.
According to the equipartition theorem, K = (1/2) kBT for each degree of freedom
regardless of V. Upot – due to attraction between the molecules (repulsion does not
contribute to Upot in the model of colliding rigid spheres). The attraction forces result
in additional pressure aN2/V2 . The work against these forces at T = const provides
an increase of U in the process of an
 1 
isothermal expansion of the vdW gas:
U vdW T  N
2  1
a
 Vi

 V f 
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 The Joule Thomson effect The Joule Thomson effect

a a
U  W  CV (T2  T1 )  (  )0
V2 V1

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The Joule Thomson effect The Joule Thomson effect

a a a a
U  W  CV (T2  T1 )  (  )0 U  W  CV (T2  T1 )  (  )0
V2 V1 V2 V1

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 The Joule Thomson effect The Joule Thomson effect

a a
U  W  CV (T2  T1 )  (  )0
V2 V1
Ideal gas: U-W~T=0  T1=T2 a 1 1
For real gase: T1  T2  (  )0
CV V1 V2
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The Joule Thomson effect Liquefying gases

PHASE DIAGRAMS

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 Some basic concepts Concepts…...

 Phase  Phase transformation

• A homogeneous region with distinct • Change from one phase to another

structure and physical properties
• E.g. L S, S S etc.
• In principle, can be isolated
• Occurs because energy change is negative/goes
• Can be solid, liquid or gas from high to low energy state

 Phase Diagram  Phase boundary

• Representation of phases present under a set • Boundary between phases in a phase diagram
of conditions (P, T, Composition etc.)
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Gibb’s Phase Rule The Phase Rule

Phase: a state of matter that is uniform throughout

in chemical composition and physical state. (Gibbs)

P+F=C+2 P=number of phases

C=number of components Number of phase (p):
F=number of degrees of freedom Gas or gaseous mixture – single phase
F=C-P+2 (number of independent variables) Liquid – one, two and three phases
two tally miscible liquids – single phase
Modified Gibbs Phase Rule (for incompressible systems)
a slurry of ice and water – two phases
P+F=C+1 Solid – a crystal is a single phase
an alloy of two metals – two phases (immiscible)
F=C-P+1 Pressure is a constant variable - one phase (miscible)

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The Phase Rule The Phase Rule

(a) (b) The difference between (a) constituent and (b)

The difference between (a) a single-phase
solution, in which the composition is uniform
on a microscopic scale, and (b) a dispersion, in
which regions of one component are embedded
in a matrix of a second component.
component
constituent: a chemical species (an ion or a molecule)
that is present in a system
component: a chemically independent constituent of
a system
number of components (c): the minimum number
of independent species necessary to define the
composition of all the phase present in the system

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The Phase Rule The Phase Rule

Degree of freedom or Variance (f): the number of

When no reaction takes place,
intensive variables that can be changed independently
The number of constituent = the number of component without disturbing the number of phases in
equilibrium.
Pure water: a one-component system The phase rule: a general relation among the
variance f, the number of components c and the
water number of phases p at equilibrium for a system of
any composition.
Mixture of
ethanol and a two-component system
water:
f=c–p+2 (7.7)

ethanol water no reactions

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 The Phase Rule
Two assumptions:
(1) no chemical reactions occur
(2) every chemical species is present in every phase
Counting the total number of intensive variables
(properties that do not depend on the size of the
system). The pressure P and temperature T count as 2.
Specify the composition of a phase by giving the mole
fractions of c-1 components (because x1+x2+…+xc=1,
and all mole fractions are known if all except one are
specified.)
There are p phases, the total number of composition
variables is p(c-1). At this stage, the total number of
intensive variables is p(c-1)+2.
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One-component phase equilibrium
For a one-component system (pure water)
f＝1－p＋2＝3－p，(C＝1）
f ≥0, p ≥1, 3≥p≥1
p＝1，f＝2
p＝2，f＝1
p＝3，f＝0
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The Phase Rule
At equilibrium, the chemical potential of a
component j must be the same in every phase:
j, = j, =… for p phase
That is, there are p-1 equations to be satisfied for each
component j. as there are c components, the total
number of equations is c(p-1).
Each equation reduces the freedom to vary one of the
p(c-1)+2 intensive variables. It follows that the total
variance is
f = p(c-1) + 2 - c(p-1) = c – p + 2
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The Phase Rule
Phase diagram: shows the regions of pressure and
temperature at which its various phases are
thermodynamically stable.
Phase boundary: a boundary between regions,
shows the values of P and T at which two phases
coexist in equilibrium.
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 The Phase Rule The Phase Rule

 Tf Tb P P
solid Critical solid Critical
liquid liquid
point point
Triple Triple
point point

Solid Liquid Gas vapor vapor

stable stable stable T3 Tc T3 Tc
T T T
Solid-liquid phase boundary: a plot of the freezing point at various P. Triple point: at which three different phases (s, l, g) all simultaneously
coexist in equilibrium. It occurs at a single definite pressure and
Liquid-vapor phase boundary: a plot of the vapor P of liquid against T.
temperature characteristic of the substance (outside our control).
Solid-vapor phase boundary: a plot of the sublimation vapor P against T. Critical point: at which (critical P and critical T) the surface disappears.

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Chemical Potentials in an Ideal Gas Mixture

H2O phase diagram: P — T

Chemical Potential of a Pure Ideal Gas D
dG  SdT  VdP 218 atm C
(4.36)
dGm  d   S m dT  Vm dP I Y

 G  solid liquid Line

i     Gm ,i one-phase pure S

P / 10 5 Pa
(4.86)*
 ni T , P substance 1 atm
Point
 RT  R
Region
d  Vm dP   dP
 P  isothermal, pure ideal gas gas
1 P1 P
0.00611
P2 1 A
d   RT dP
2

P O
 (T , P2 )   (T , P1 )  RT ln 2 isothermal, pure ideal gas (6.1)
P P1
0.0024 0.01 99.974 374.2
   o (T )  RT ln o pure ideal gas, Po1 bar (6.2) Tf T3 Tb
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t/℃

10
 Physical Chemistry Chapter 7
Difference between triple point and freezing point
Difference between triple point and freezing point
vapor Air and vapor

P=611Pa P=101..325 kPa

Why the freezing point is lower than the triple point?

ice t=0.01℃ t=0℃

The higher pressure lowers the freezing point
compared with that of pure water
冰

The dissolved air (i.e. N2 and O2) lowers the

Pure water Air-saturated water
freezing point compared with that of pure water

Triple point Freezing point

In a sealed vessel In an open vessel

(a) Triple point of H2O (b) Freezing point of H2O

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The Clapeyron Equation

H2O phase diagram: P — T
Region (s, l, g): Phase equilibrium: P  +
D
 
C
218 atm f=2, one phase  
Y Phase 
I
Line (OA, AD, For a pure substance dP 2
solid liquid 1 Phase 
AC):
P / 10 5 Pa

Gm  Gm
S
1 atm
f=1, two phases
At point 1, Gm ,1  Gm ,1
R  
in equilibrium T
gas dT
At point 2, Gm, 2  Gm , 2
0.00611  
A
Point (A): Fig. 7.5 two neighboring points on a
Gm ,1  dGm  Gm ,1  dGm
O two-phase line of a one-component
f=0, three phases system.
0.0024 0.01 99.974 374.2
Tf T3 Tb Tc in equilibrium
t/℃
dGm  dGm (7.13)
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 The Clapeyron Equation ThePhysical
Clapeyron
ChemistryEquation Chapter 7

For a single phase
dG   SdT  VdP  i i dni
dG   SdT  VdP  dn
Gm  G / n, G  nGm
dG  ndGm  Gm dn
ndGm  Gm dn   SdT  VdP  dn
ndGm   SdT  VdP
For any point on the - equilibrium line
dGm  dGm (7.13)
pure phase (7.14) dGm   S m dT  Vm dP (7.15)
 S m dT  Vm dP   S m dT  Vm dP (7.16)
(Vm  Vm ) dP  ( S m  S m )dT
dP S m  S m S m S
   (7.17)*
dT Vm  Vm Vm V

dGm   S m dT  Vm dP one-phase, one-component (7.15)

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The Clapeyron Equation The Clapeyron Equation

For a reversible (equilibrium) phase change P  +

dP S m

S  H / T dT Vm Phase 
dP 2
dP S m  S m S m S

   (7.17)* dP H m H 1 Phase 
dT Vm  Vm Vm V  
dT TVm TV
dP H m H
  (7.18)* The slope of the T
dT TVm TV dT
phase boundaries
Fig. 7.5: two neighboring points on a
one component two-phase equilibrium two-phase line of a one-component
Any phase equilibrium of system.
Clapeyron Equation (Clausius-Clapeyron equation) any pure substance

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