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APPLIED THERMODYNAMICS

TDA-301T 2015
Lecture 10a: Equilibrium and
Stability in One-Component
Systems
By

Prof Alex Sofianos


Bsc Chem Eng, Msc, PhD Ind Chem (Germany), MBL
(UNISA)

Course Contents
1. Introduction
2. Conservation of Mass
3. Conservation of Energy
4. Entropy An additional Balance Equation
5. Liquefaction, Power Cycles, Explosions
6. Thermodynamic Properties of Real Substances
7. Equilibrium and Stability One Component
8. Thermodynamics of Multi-Component Systems
9. Estimation of Gibbs Energy and Fugacity of a
Component in a Mixture
10.
Vapor-Liquid Equilibrium in Mixtures
11.Chemical Equilibrium
2

Course Books
1. Chemical, Biochemical & Engineering
Thermodynamics 4th Edition, Stanley I.
Sandler , John Wiley and Sons (2006)
2. Introduction to Chemical Engineering
Thermodynamics (The McGraw-Hill Series
in Civil and Environmental Engineering) by J.M.
Smith, Hendrik C. Van Ness, and Michael
Abbott (2004)
3. Introduction to Chemical Engineering
Thermodynamics by J.M. Smith (2001)
4. Engineering and Chemical
Thermodynamics 2nd Edition, 3Milo D.
Koretsky (2012)

Assessment TDA 301T


OFFERING TYPE
TOTAL
1. Assignments

NUMBER
2

WEIGHT
10%

20

2. Class Tests

20%

40

3.

10%

10

Practicals

3. Semester Test
1
Predicate
100%
(50)

30%
100
4

30

Objectives
This Chapter should enable the
student :
Identify the Criterion For Equilibrium in
systems subject to different constraints
(Sec. 7.1)
Use the concept of stability to identify
when phase splitting into vapour and liquid
phases will occur
Identify the conditions of phase
equilibrium (Sec. 7.3)
Identify the critical point of a fluid (Sec.
7.3)
5
Calculate the fugacity of a pure

Objectives II
At the end of this Chapter, the student
must:
Be able to calculate the fugacity of a pure
liquid or solid when a volumetric
equation of state is not available (Sec.
7.4)
Use fugacity in the calculation of vapourliquid equilibrium (Sec. 7.5)
Be able to determine the number degrees
of freedom for a pure fluid (Sec. 7.6)

Criteria for Equilibrium


Means of mathematically identifying the
state of equilibrium in a closed, isolated
system.
i.e. system in which M, U, and V are
constant):
Entropy (Ch. 4)
Goal is to develop a means of identification
of the equilibrium state for closed
thermodynamic systems subject to other
constraints, especially those of constant T
and V and and constant T and P !
Starting point: Energy and Entropy
Balances:
7

Criteria for Equilibrium


Further:
From the 2. Law of

Thermodynamics we remember that for


equilibrium or for reversible processes:

gen

the system was chosen in such a way that


the only work term is that of the
deformation of the system boundary
( dV/dt ).
For a constant-volume system, exchanging
no heat with its surroundings,
Equation
reduces to:

= 0 , i.e. U = constant
8

Criteria for Equilibrium


Since
the total number of moles, or mass,

is fixed in a closed, one-component


system,
then: U = constant
= + gen
and equation:

becomes:

gen

entropy function can only increase in value


during the approach to equilibrium!! Why?

Criteria for Equilibrium


gen 0 !
Answer:

Equilibrium criterion for a closed, isolated


system is:

This equilibrium criterion can be used for


identifying the final equilibrium state in a
closed, isolated system
that is initially non-uniform, or
in which several phases or components are
present
10

Example for Equilibrium Criterion


Example:
Single-phase, single-component fluid in an
adiabatic, constant-volume container has
been divided into two subsystems by an
imaginary boundary.
Each of these subsystems is assumed to
contain the same chemical species of
uniform thermodynamic properties.
However, these subsystems are open to
the flow of heat and mass across the
imaginary internal boundary, and
their
11
temperature and pressure are not

Example for Equilibrium Criterion


For the composite system consisting of the
two subsystems, the total mass (or number
of moles), internal energy, volume, and
entropy, all of which are extensive
variables,
are the sums of the respective quantities
for the two subsystems, i.e.:

In addition:
We know that S = S ( U, V, N)

12

Example for Equilibrium Criterion


From
S = S ( U, V, N) we can calculate the

change in the entropy of system 1 due to


changes in N1, U1, and V1 as follows:

Then:
dS1 =
In the same way:
dS2 = dU2 + dV2 - dN2
Entropy change for the whole system is
dS = dS1 + dS2
13

Example for Equilibrium Criterion


Therefore
Entropy change is :

dS = dU1 + dV1 - dN1 + dU2 + dV2- dN2

Total number of moles, total volume and


total internal energy were set to be
constant
Hence under the condition that:

dS =

[ - ] dU1 + [ - ] dV1 - [ - ]dN1


14

Example for Equilibrium Criterion


Since
S = maximum or dS = 0

for all system variations at constant N, U,


and V we
conclude by comparison of
equations below :
dS =

[ - ] dU1 + [ - ] dV1 - [ - ]dN1

That:

15

Example for Equilibrium Criterion


And since T1 = T2

In other words, the equilibrium condition


for the system illustrated above is satisfied
if both subsystems have the same
temperature, the same pressure, and the
same molar Gibbs energy.
For a single-component, single-phase
system, this implies that the composite
system should be uniform.
16

Example for Equilibrium Criterion


Conclusion:

The condition dS = 0 may be used to
identify a possible equilibrium state of the
closed, isolated system, that is, a state for
which S is at a maximum
However: dS = 0 necessary but not
sufficient condition for a maximum; it
could also describe a minimum!
Therefore, an additional condition is
required:
The condition d2 S 0, together with dS = 0,
assures us that a maximum value of the
entropy, and hence a true equilibrium
17
state, has been identified rather than a

Example for Equilibrium Criterion


Conclusion:
Thus, the sign of d 2S determines the
stability of the state found from the
condition that dS = 0.
Stability condition for equilibrium d2S < 0
New Example
Possible to develop the equiIibrium and
stability conditions for systems subject to
other constraints.
For a closed system at constant
temperature and volume, the energy and
entropy balances are:
18

Example for Equilibrium Criterion


Eliminating
Q between these two

equations, and using the fact that: T dS =


d(TS), since T is constant we obtain:

This last part stems from the fact that T =


constant and positive: T and gen
- T gen
0
Therefore:
and as we saw with entropy we get for the
Helmholtz free energy

19

Example for Equilibrium Criterion


New Example
For a closed system at constant
temperature and constant pressure , the
energy and entropy balances are:

and
Combining the two above equations over Q,
we obtain:

20

Example for Equilibrium Criterion


This
last part stems from the fact that T =

constant and positive: T and gen


- T gen
0
Therefore again:
and as we saw with entropy we get for the
Gibs free energy

This is the most important of the


equilibrium criteria and also shows the
equality of the molar Gibbs energies as a
condition for equilibrium.
21

Example for Equilibrium Criterion


Equality of Gibbs Free Energy as
condition for equilibrium:

22

Equilibrium Condition
in Problem Solving
EXAMPLE: Two identical metal blocks of
mass M with initial temperatures T1, i and T2,
i , respectively, are in contact with each other
in a well-insulated (adiabatic), constantvolume enclosure. Find the final equilibrium
temperature of the blocks.

Choose the two metal blocks as the system


for writing the balance equations.
23

Equilibrium Condition
in Problem Solving
Balance equations:
There is no exchange of mass between the
blocks, so the mass balance does not
provide any useful information
The energy balance for the system is:

or by introducing of heat capacity:

24

Equilibrium Condition
in Problem Solving
Equation below can be simplified

to:
And by using the entropy balance for the
system in which M, U, and V are constant,
at equilibrium the entropy is a maximum.
The final entropy of the system is

25

Equilibrium Condition
in Problem Solving
To calculate this final equilibrium
temperature, we use the energy balance:

The equilibrium equation can be satisfied


if
T1,f = T2,f = Tfinal ;
that is, the final temperature of the two
blocks must be equal:

And

26

Proving the Equality of Gibbs Energies


for Vapour-Liquid Equilibrium
ILLUSTRATION 7.1-2
Use the information in the steam tables of
Appendix A to show that Eq. 7.1-9c is
satisfied at 100C and 0.10135 MPa. The
equilibrium equation can be satisfied if

SOLUTION
From the saturated steam temperature
.table, we have at 100C and 0.101 35 MPa

27

Proving the Equality of Gibbs Energies


for Vapour-Liquid Equilibrium
ILLUSTRATION 7.1-2
Given:
100C and 0.101 35 Mpa

We know that: = - T
Then we have:
L = L - T L = 419.04 373.15 X 1.3069
= - 68.6 kJ/kg
V = V - T V = 2676.1 373.15 X 7.3549
= - 68.4 kJ/kg
28

Proving the Equality of Gibbs Energies


for Vapour-Liquid Equilibrium
L = L - T L = 419.04 373.15 X 1.3069 =
- 68.6 kJ/kg
V = V - T V = 2676.1 373.15 X 7.3549 =
- 68.4 kJ/kg
L
=
These are closeenough
to justify L = V
V

at this vapor-liquid phase equilibrium state


and therefore:

29

Stability of Thermodynamic
Systems
The
result dS = 0 used to identify the
equilibrium state of an initially non-uniform
system constrained to remain at constant
mass, internal energy, and volume.
In this section we explore the information
content of the stability criterion:
d2S 0 , at constant M, U, and V
By studying the sign of the second
differential of the entropy, we are really
considering the following question:

30

Stability of Thermodynamic
Systems

Suppose that a small fluctuation in a


fluid property, say temperature or
pressure, occurs in some region of a fluid
that was initially at equilibrium;
is the character of the equilibrium state
such that
d2S < 0, and the fluctuation will dissipate,
or such
d2S > 0 , in which case the fluctuation
grows until the system evolves to a new
equilibrium state of higher entropy
Since we know that fluids exist in
thermodynamically stable state, we will
31
2
accept that d S < 0 for all real fluids at

Stability of Thermodynamic
Systems

Problem of the intrinsic stability of the


equilibrium state in a pure single-phase
fluid, and then
Problem of the mutual stability of two
interacting systems or phases
Previous example of Figure 7.1-1 of the
last section, equilibrium in a pure fluid at
constant mass (actually, we will use
number of moles), internal energy, and
volume.
Using the subdivision of the system into
two subsystems, and writing the extensive
properties N, U, V, and S as sums of these
32
properties for each subsystem, we: were

Stability of Thermodynamic
Systems

Using the subdivision of the system into


two subsystems, and writing the extensive
properties N, U, V, and S as sums of these
properties for each subsystem, we were
able to show that the condition:

for all system variations consistent with the


constraints led to the requirements that at
equilibrium:

33

Stability of Thermodynamic
Systems

Now we write an expression for the


stability requirement d2S < 0 for this
system and obtain:

It now remains to evaluate the various


entropy derivatives, so that the stability
restrictions of Equation above and its
derivatives can be put into a more usable
form.
34

Stability of Thermodynamic
Systems

Starting with equation below:

Which for an open system becomes:

And:

35

Thermal Stability Criterion


Finally, since T is absolute temperature and
positive, one condition for the existence of
a stable equilibrium state of a fluid is that:
Cv > 0
This is the First or Thermal Stability
Criterion
Which says that for an open system the
constant-volume heat capacity must be
positive, so that internal energy
increases as the fluid temperature
increases
36

Stability of Thermodynamic
Systems

Similarly we can derive

And with quite a lot of Algebra we obtain:

Which can be reduced to

37

Mechanical Stability Criterion


Finally we have the Second or
mechanical stability criterion:

Or as
where kT : the isothermal
compressibility of the fluid.
This result indicates that if a fluid is to
be stable, its volumetric equation of
state must be such that the fluid
volume decreases as the pressure
38
increases at constant temperature.

Mechanical Stability Criterion


The main conclusion from this exercise
is that if a fluid is to exist in a stable
equilibrium state, that is, an
equilibrium state in which all small
internal fluctuations will dissipate rather
than grow, theC fluid
> 0 must be such that:
v

and
or
39

Mechanical Stability Criterion


Since all real fluids exist in
thermodynamically stable states, these
equations must be satisfied for real fluids.
In fact, no real fluid state for which either

> 0 or Cv < 0 has yet been


found!
Hence, for real fluids the criteria as set out
below are valid:
Cv > 0
40

Stability Criteria
Next we consider the problems of
identifying
the equilibrium state for two
interacting phases of the same molecular
species but in different states of
aggregation,

Determination of requirements for the


stability of
this state.

An example of this is a vapor and a liquid


in equilibrium. To be general, we again
consider u
composite system isolated
from its environment,
except that here
the boundary between the two
subsystems is the real interface between
41
the phases.

Stability Criteria

For this system we have:

Since N, U , and V are fixed, the equilibrium


condition is that the entropy should attain a
maximum value.
However. we allow for the fact that the states of
aggregation in regions I and II are different, so
that the fluids in these regions may follow
different equations of state.

Using the same analysis we find that at


equilibrium (i.e., when dS = O),
TI = TII , P I
42
= P II and G I = G II

Stability Criteria

Using the same analysis we find that at


equilibrium (i.e., when dS = O),
TI = TII and P I = P II are obvious conditions,
but
G I = G II Not so obvious condition for
equilibrium!

Again, from the stability condition d2 S < 0, we


obtain: (following the same analysis as before:

43

Stability Criteria More


Phases

Here, however, the two partial derivatives in


each of the bracketed terms need not be equal,
since the two phases are in different states of
aggregation and thus obey different
equations of state, or different roots of
the
same equation of state.

It is clear from a comparison with Eq. 7.2-2b


that a
sufficient condition for Eq. 7.2-16 to be
satisfied is that each phase to be intrinsically
stable; that is, Eq. 7.2-16 is satisfied if, for each
of the coexisting phases, the equations:

44
need to be satisfied!! Therefore, a condition
for

Stability Criteria More


Phases

Therefore, a condition for the mutual


stability of two interacting subsystems is
that each subsystem be intrinsically stable.

45

Phase Equilibria: Application of


Equilibrium And Stability Criteria
to an Equation Of State
Isotherms computed using a the van der
Waals equation of state (as an example of an
EOS).

46

Application of Equilibrium And


Stability Criteria to an Equation
Of State
Isotherms
are labeled so that T5 > T4 > T3 >
T2 > T 1
The isotherm T3 has a single point, C, for
which ()T = 0;
at all other points on this
isotherm ()T < 0.
On the isotherms T4 and T5,
()T < 0 everywhere, whereas
for the isotherms T1 and T2,
()T < 0 in some regions and
()T > 0 in other regions
47

Application of Equilibrium And


Stability Criteria to an Equation
Of State
The criterion
for fluid stability requires that
()T < 0;
This is satisfied for the isotherms T 4 and T5,
but not in the aforementioned regions of the
T1 and T2 isotherms.
Thus we conclude that the regions A to B
and A' to B' of the isotherms T 1 and T2 ,
respectively, are not physically realizable;
that is,
they will not be observed in any experiment
since a fluid in these states is not stable,
and instead would go to an appropriate
48
stable state

Equilibrium And Stability Criteria in


EOS

Take any constant-pressure line between PA


and PB in this figure, such as Pa
We see that it intersects the equation of
state three times, corresponding to the fluid
49
volumes V a V a , and V a:.

Equilibrium And Stability Criteria in


EOS

We see that it intersects the equation of


state three times, corresponding to the fluid
volumes V a ; V a , and V a
One of these, V a, is on the part of the
isotherm that is not possible by the stability
criterion.
However. the other two intersections, at V a
and V a , are physically possible.
This suggests that at a given pressure and
temperature the system can have two
different volumes;
But:
This contradicts the axiom that two
state
50

Equilibrium And Stability Criteria in


EOS

This can only happen if equilibrium can


exist between two phases of the same
species that are in different states of
aggregation (and hence density).
The equilibrium between liquid water and
steam at 100C and 101.325 kPa (I atm) is
one such example.
Hence, there is a portion of the isotherm
where the specific volume varies continuous
at fixed temperature and pressure;
Two-phase coexistence region, here the
vapour-liquid coexistence region.
51

Equilibrium And Stability Criteria in


EOS

The variation of the overall (or two-phase)


specific volume in this region arises from the
fact that although the specific volumes of
the vapour and liquid phases are fixed (since
the temperature and pressure are fixed in
each of the one-phase equilibrium
subsystems),
the fraction of the mixture that is vapour,
V
, can vary continuously from 0 to 1.
In the two-phase region the specific volume
of the two-phase mixture is given by:
where

and

are fractions 52
of vapour

Equilibrium And Stability Criteria in


EOS
where V and L are fractions of vapour
and liquid, on a molar basis and

=1

And

53

Maxwell or Lever Rule

where V and L are fractions of vapour


and liquid, on a molar basis and

=1

And

54

Maxwell or Lever Rule

where V and L are fractions of vapour


and liquid, on a molar basis and

=1

And

55

Computing the Properties of a


Two-Phase Mixture
Compute the total volume, total
enthalpy, and total entropy of 1 kg of
water at 100C, half by weight of which
is steam and the remainder liquid water.

SOLUTION
From the saturated steam temperature
table at 100C, the equilibrium pressure is
0.101 35 MPa and

Using equation:

56

Computing the Properties of a


Two-Phase Mixture
SOLUTION
We obtain by substitution into :

Using corresponding equation we get


the enthalpy as well :

57

Computing the Properties of a


Two-Phase Mixture
SOLUTION
We obtain by substitution into :

Using corresponding equation we get


the enthalpy as well :

And the entropy:


58

Two-Phase Mixture

as the pressure is lowered along an


isotherm on which a liquid-vapour
phase transition occurs, the actual
volume-pressure behaviour is as shown
below (there is no sigmoid curve!):

59

Two-Phase Mixture

We can improve the representation of the


two-phase region when using the van der
Waals or other EOS by recognizing that
all van der Waals loops, such as those
in Fig. 7.3-2. should be replaced by
horizontal lines (isobars), as shown in
Fig. 7.3-3.
This construction ensures that the
equilibrium phases will have the same
temperature and pressure
Question: at which pressure should the
isobar be drawn, since any pressure such
that
60
Pa < P < P b

Two-Phase Mixture

To find out the equilibrium pressure we


start from:

We integrate between any two points


along an isotherm of the equation of
state,

Then we have:

61

Two-Phase Mixture

To calculate the specific volume in each of


the integrations we use the equation of
state for the appropriate part of the van
der Waals loop.
Alternatively, we can find the equilibrium
pressure graphically by noting that Eq.
7.3-2 requires that
Areas I and II between the van der Waals
loop and the constant pressure line in Fig.
7.3-2 be equal at the pressure at which
the vapour and liquid exist in equilibrium.
This vapour-liquid coexistence pressure,
(a function of temperature!), is called the
62
vapor pressure of the liquid and
will be

Two-Phase Mixture

of temperature!), is called the vapor


pressure of the liquid and will be
denoted by Pvap(T).

63

Two-Phase Mixture

We can continue in the manner described


here to determine the phase behaviour of
the fluid for all temperatures and
pressures.
For the van der Waals fluid, this result
is the temperature!), is called the vapour
pressure of the liquid and will be
denoted by Pvap(T). An important
feature of this figure is the domeshaped. [two-phase co-existence
region].
The inflection point C of Fig. 7.3-1 is the
peak of this dome, and therefore is the
64
highest temperature at which the

Two-Phase Mixture

It is worthwhile retracing the steps


followed in identifying the existence and
location of the two-phase region in
the P-V plane:
1. The stability condition () T < 0 was used
to identify the unstable region of an
isotherm and thereby establish the
existence of a two-phase region.
2. The conditions T' = T" and P' = P" were
then used to establish the shape (but not
the location) of the horizontal
coexistence line in the P-V plane.
3. Finally. the equilibrium condition, G I =
65
G II was used to locate the position
of

Two-Phase Mixture

Three-dimensional PVT phase diagram is


shown in Fig. 7.3-5.

66

Two-Phase Mixture

The P, V, T phase diagram for a substance


with a single solid phase diagram

67

Two-Phase Mixture
If we assume that it were possible to
compute the Gibbs
energy as a function
of temperature and pressure for any
phase,
either from an equation of state,
experimental data,
or statistical mechanics.
Then, at fixed pressure,
we could plot G as a function
of T for each phase, see Fig.
for the vapor and liquid phases.
equilibrium condition is G
is a minimum! At phase transition
temperature Tp.
68

the liquid is the equilibrium phase at

Two-Phase Mixture
The angle of intersection between the
liquid and vapor Gibbs energy curves
decreases as the pressure (and
temperature) at which the intersection occurs
increases (provided P < Pc).
At the critical pressure, the two Gibbs
energy curves
intersect, with = 0: i.e., the two curves
are collinear
for some range of T around
the critical temperature T.
Thus, at the critical point,

Since:

we find at the critical69point:

Two-Phase Mixture

Since the molar Gibbs energy, molar


entropy,
temperature, and pressure
each have the same value in the vapor and
the liquid phases, the values of all other
state variables must be identical in the
two equilibrium phases at the critical
point.
Therefore, the vapor and liquid phases
become indistinguishable at the critical
point.
This is exactly what is experimentally
observed.
At all temperatures higher than the
70
critical temperature, regardless
of the

Two-Phase Mixture

This is the reason for the abrupt termination


of the vapor-liquid coexistence line in
the pressure-temperature plane at the
critical point.
The triple point, this is the intersection of
the solid-liquid, liquid-vapor, and solidvapor coexistence curves.
It is the only point on the phase diagram
where the solid, liquid, and vapor coexist at
equilibrium.
Since the solid-liquid coexistence
curve generally has a steep slope
the triple-point temperature for
most fluids is close to the normal
71
melting temperature, i.e. the melting

The Molar Gibbs Energy and


Fugacity of a Pure Component

We need to consider how one uses an


equation of state to identify the states of
vapor-liquid
equilibrium in a pure fluid.

The starting point is the equality of molar


Gibbs energies in the coexisting phases:

Then using equation:


We obtain

and
72

The Molar Gibbs Energy and


Fugacity of a Pure Component
To compute V as a function of T and P, only
Eq. below will be considered further:

Integration of equation above between


any two
pressures P1 and P2 (at constant
temperature) yields:

If the fluid under consideration were an


ideal gas,
following equation would be
valid:
73
We obtain then by substitution:

The Molar Gibbs Energy and


Fugacity of a Pure Component

If we subtract the ideal gas equation from


that of the real gas we obtain:

Further,
i. setting P1 equal to zero,
ii. recognizing that at P = 0 all fluids are
ideal gases so that G(T1, P = 0 ) = G IG
(T1 , P = 0), and
iii. omitting all subscripts yields equation:
74

Definition of Fugacity of a Pure


Component

If we define a new thermodynamic


function, the fugacity, denoted by the
symbol f .

and the related fugacity coefficient


by division
with the pressure as:

Fugacity is a well-defined function


related to the exponential of the
difference
75

Definition of Fugacity

In chemical thermodynamics, the fugacity


(f) of a real gas is an effective pressure
which replaces the true mechanical pressure
in equilibrium calculations.
It is equal to the pressure of an ideal gas
which has the same chemical potential as
the real gas.
EXAMPLE: Nitrogen gas (N2) at 0C and a
pressure of P=100 atm has a fugacity of f =
97.03 atm.[1]
This means that the chemical potential of
real nitrogen at a pressure of 100 atm is
less than if nitrogen were an ideal gas;
76
the value of the chemical potential
is

Definition of Chemical

Potential

In chemical thermodynamics, the chemical


potential, (also known as partial molar
free energy) is a form of potential energy
that can be absorbed or released during a
chemical reaction.
The chemical potential of a species in the
mixture can be defined as the derivative of
the free energy of the system with respect
to a change in the number of moles of just
that species.
Thus, it is the partial derivative of the free
energy with respect to the amount of the
species, all other species' concentrations in
77
the mixture remaining constant, and
at

Definition of Chemical
Potential

At chemical equilibrium (or in phase


equilibrium) the total sum of chemical
potentials is zero, as the free energy is at
a minimum.

The fundamental equation of chemical


thermodynamics for a system containing n
constituent species, with the I - th species
having Ni particles is, in terms of Gibbs energy:

At constant temperature and pressure we


get:

78

The chemical potential is therefore

Definition of Fugacity

From this definition it is clear that the


fugacity has
units of pressure, and that
f P, when P 0; that is, the fugacity
becomes equal to the pressure at pressures
low enough that the fluid approaches the
ideal gas state.

The fugacity function has been


introduced because its relation to the
Gibbs energy makes it useful for phase
I
G
=
equilibrium calculations
G"

The present criterion


for equilibrium
between two
phases was:

with the restriction that: temperature


and
79

Definition of Fugacity of a Pure


Component

Equation

becomes by substitution

and with

equation above becomes:

80

Equilibrium Criterion with


Fugacity
of aofPure
Component
Or in terms
the fugacity:
Equilibrium
Condition

and using the fugacity coefficients:


These equations follow directly from the
equality of the molar Gibbs Free Energy
in each of the two phases:
important forms of the equilibrium
81
criteria ;

Equilibrium Criterion with


Fugacity
of a
Pure
Important
forms
of Component
the equilibrium
criteria ;
follow directly from the equality of the
molar Gibbs energy in each phase at
phase equilibrium
In all equations of state pressure is an
explicit function of volume and
temperature.
Therefore, it is useful to have an
equation relating the fugacity to an
integral over volume (not pressure).
From equation
82

Equilibrium Criterion with


Fugacity
of a Pure Component
From equation

and

we obtain by changing the variable of


integration:

with Z = P V / R T , the compressibility


83
factor

Equilibrium Criterion with


Fugacity
of a Pure Component

In addition we know
and for the temperature dependence of
the fugacity given as the temperature
dependence of the logarithm of the
fugacity coefficient (f/P)
we get

84

Equilibrium Criterion with


Fugacity
of afunction
Pure Component
The fugacity
is of central
importance in phase equilibrium calculations,
therefore we consider here the computation
of the fugacity for pure gases, liquids, and
solids
Fugacity of a Pure Gaseous Species

Using the above EOS, where the superscript


V is used to designate the fugacity and Z
the compressibility of the vapor phase
85

Fugacity Pure Gaseous Species

If we accept that EOS is applicable up to


the pressure of interest, the fugacity of
a pure gas can be computed by integration
of this equation:

At very low pressures, where a gas can be


described by the ideal gas equation of
state
the following equations are valid, i.e.
86
fugacity is equal to total pressure

Fugacity of a Pure Gas


EXAMPLE
Fugacity Calculation
Calculate the fugacity of steam at 300 oC and
8 MPa using the data given at the steam
tables (superheated steam)
SOLUTION

We use following equation:

From the superheated vapour steam Tables


at 300C, we have at different pressures:
87

Superheated Vapor Steam Tables at


300C

88

Fugacity of a Pure Gas


EXAMPLE
We carry out numerical integration of the
equation using the data above and we find :

and finally we find the fugacity f:

Also, the fugacity coefficient, , in this


case is
89

Example: Calculation of
Fugacity
EXAMPLE 2 of a Pure Component
Fugacity Calculation
Calculate the fugacity of steam at 300 oC and
8 MPa using the data given at the steam
tables (superheated steam)

At 300 oC and 0.01 MPa we have from the


steam tables:
= 3076.5 kJ/kg and = 9.28 13 kJ/(kg K).

Therefore, for the Gibbs free energy:

90

Calculation of Fugacity
of a Pure Component
EXAMPLE
Fugacity Calculation
By multiplying with the mole number
(water: 18 g/mol) we get the molar Gibbs
Free Energy:

We have assumed a very low pressure P


= 0.01MPa; steam behaves like an ideal
gas:

91

Calculation of Fugacity
of a Pure Component
Fugacity Calculation
Then we obtain G IG [300 oC, 8 MPa] by
substitution:

92

Calculation of Fugacity
of a Pure Component

Fugacity Calculation
For real steam at 300C and 8 MPa, we
have, from the steam tables:
= 2785.0 kJkg and = 5.7906 kJ/(kg K),
so that
from: = - T

REAL [300 C, 8 MPa] = 2785.0 kJkg 573K x


5.7906 kJ/kg K
= - 533.88 KJ/Kg
o

And for the molar Gibbs free energy:


G

REAL

= - 533.88 KJ/Kg x 18 g/mol


93
= -9 617 J/mol

[300 oC, 8 MPa]

Calculation of Fugacity
of a Pure Component
Fugacity Calculation
Finally to calculate fugacity we use the
equation below:

And obtain:

Therefore fugacity, f
MPa

[300 oC , 8 Mpa]
94

= 6.402

Calculation Of Fugacity
Coefficient

Fugacity Coefficient
Finally we can calculate the fugacity
coefficient:

And = = 0.8003
These values are in excellent agreement
with the results obtained in the previous
Example

95

Calculation of Fugacity of
Saturated Steam
EXAMPLE 3
Compute the fugacity of saturated
steam at 300 oC
First find the saturation pressure of steam
(from the steam tables) at 300C: PSAT =
8.581 MPa
Following the previous illustration, we
have

REAL

96
[300 oC, 8.581 MPa] = -520.15
kJ/kg;

Calculation of Fugacity of
Saturated Steam
EXAMPLE
Compute the fugacity of saturated
steam at 300 oC

Then we obtain for the fugacity:

Thus the fugacity of the vapour is:


f V = 6.7337 MPa ; At equilibrium
f L = 6.7337 MPa ; therefore f V = f
97

Calculation of Fugacity using


the virial equation of state

At low to moderate pressures, the virial


equation of state shortened after the
second virial coefficient
if data for B(T) are available

Then we obtain for the fugacity:

with Z
98

Calculation of Fugacity using


the virial equation of state
EXAMPLE
Compute the fugacities of pure ethane and
pure butane at 373.15 K and 1, 10, and 15
bar, assuming the virial equation of state
can describe these eases at these
conditions
Given:

SOLUTION
We use the equations:

99

Calculation of Fugacity using


the virial equation of state
Then we obtain for the fugacities:

Since the pressures are not very high, these


results are reasonably accurate
However, the virial equation with only the
second virial coefficient will be less accurate
as the pressure increases.
In fact, at slightly above 15 bar and 373 K, nbutane condenses to form a liquid!
In this case the virial equation description is
100
inappropriate

Calculation of Fugacity of a
Gas
at Higher aPressures
At higher pressures,
more complicated

equation of state (or higher terms in the virial


- expansion) must be used
By using the van der Waals equation, (not
very accurate! ) we obtain:

This equation is sometimes applicable but:


101

Calculation of Fugacity of a
Gas
using
the PengaRobinson
EOS
At higher
pressures,
more complicated

equation of state (or higher terms in the virial


- expansion) must be used
For hydrocarbons and simple gases, the
Peng-Robinson equation provides a more
accurate description

102

Calculation of Fugacity of a
Gas
using
the Peng
Robinson
Fugacities
calculation
with the
PengRobinson equationEOS

with A = P/(RT)2 and B = Pb/RT

Obviously, the mathematical calculations


increase significantly, but there is software
available that significantly facilitates matters
103

Procedure for Calculation of


Fugacity of a Gas Higher Order
EOS
To use either the virial,
the van der Waals,
Peng-Robinson, or other equation of state
to calculate the fugacity of a gaseous
species, the following procedure is used:
1. For a given value of T and P, use the
chosen equation of state to calculate the
molar volume V or, equivalently, the
compressibility factor Z
2. When using cubic or other compIicated
equations of state , the low-density (large V
or Z) solution is used.
3. This value of V( or Z) is then used in the
appropriate Fugacity equations to calculate
104 f/P, and
the species fugacity coefficient,

Procedure for Hand Calculation


of Fugacity of a Gas
For hand calculations it is simpler, but
less accurate, to compute the fugacity
of a species using a specially prepared
corresponding-states fugacity chart.
To do this, we note that since, for simple
gases and hydrocarbons, the
compressibility factor Z obeys a
corresponding-states relation (see Sec.
6.6), the fugacity coefficient f/P given by
Eq. 7.4-6 can aIso be written in
corresponding-states form as follows:

105

Procedure for Hand Calculation


of Fugacity of a Gas
This can be simplified to:

the fugacity coefficient can be tabulated in


the corresponding-states manner.
The corresponding-states correlation for
the fugacity coefficient of nonpolar
gases and liquids given in following Fig. 7.41 was obtained using Eq. above and the
compressibility correlation
106

107

Equilibrium State Of A System


Of Several Phases - Gibbs
Phase Rule

GIBBS phase rule for a onecomponent System

We know that to completely fix the


equilibrium thermodynamic state of a onecomponent, single-phase system, we must
specify the values of two state variables
EXAMPLE
to fix the equilibrium thermodynamic state in either the
vapour, liquid, or solid region
both the temperature and
pressure are needed
108

Equilibrium State - System Of


Several Phases - Gibbs Phase
Rule

Thus, we say that a one-component,


single-phase system has two degrees of
freedom.
Further, to fix the total size or extent of the
system we must also specify its mass or one
of its extensive properties, such as total
volume or total energy, from which the mass
can be calculated!

equilibrium, single-component, multiphase


system.
QUESTIONS

How many state variables must be


specified to completely fix the
109
thermodynamic state of each phase when

Equilibrium State Of A System


Of Several Phases - Gibbs
Phase Rule
QUESTIONS

How many additional variables need be


specified, (of what type?), to fix the
distribution of mass (or number of moles)
between the phases, therefore fixing the
overall molar properties of the composite,
multiphase system? Finally,

what additional information is needed to


fix the total size of the multiphase system?

It might appear that if P phases are


present, the system would have 2P degrees
of freedom.;
However, actual number of degrees of
freedom is fewer, since the requirement
110

Equilibrium State Of A System


Of Several Phases - Gibbs
Phase Rule
QUESTIONS

It might appear that if P phases are


present, the system would have 2P degrees
of freedom.;
Equilibrium constraint: TI = TII
P- 1 relations to be satisfied
Similarly: at equilibrium the pressure in
each phase must be the same:
PI = PII
so that there are an additional P- 1
restrictions
Finally, at equilibrium, the molar Gibbs
energies must be the same in each phase:
111
GI (T, P) = GII (T, P)

Equilibrium State Of A System


Of Several Phases - Gibbs
Rule on the 2P
A total of 3(P- Phase
1) restrictions
state variables needed to fix the
thermodynamic state of each of the P
phases, the number of degrees of
freedom for the single-component,
multiphase system is:

112

Gibbs Phase Rule - Discussion

We have already indicated that a singlephase (P = 1) system has two degrees of


freedom;
Gibbs Phase Rule; F = 3 P = 2
To specify the thermodynamic state of each
phase in a two-phase system (i.e., vaporliquid, vapor-solid, or solid-liquid coexistence
regions), it is clear from Fig.
that we need specify only the
temperature or the pressure of
the system; the value of the other
variable can then be obtained
from the appropriate coexistence
Curve!
113

Gibbs Phase Rule - Discussion

Setting P = 2 confirms that a two-phase


system has only a single degree of
freedom.
Finally, since the solid, liquid, and vapor
phases coexist at only a single point, the
triple point, a single-component, threephase system has no degrees of freedom :
Phases Number: P = 3
F=3-P=33=0
Hence, to fix the thermodynamic state of each of the P
phases in equilibrium, we must
specify 3 - properties of the
individual phases.
114

Gibbs Phase Rule - Discussion

If there are P phases, there are P values of


i the mass fraction in phase i, which
must be determined.
Sum of mass fractions must be unity

Then we need P - 1 additional equations of


the form:

115

Gibbs Phase Rule - Discussion

For example, if we know that steam and


water are in equilibrium at some
temperature T (which fixes the singledegree freedom of this two-phase system:
F= 3 P = 3 2 = 1) ),
the equation of state or the steam tables
can be used to obtain the equilibrium
pressure, specific enthalpy, entropy, and
volume of each of the phases,
but not the mass distribution between the
phases.
However, if the volume [or enthalpy or
entropy, etc.) per unit mass of the twophase mixture were known, this
116 would be

Gibbs Phase Rule - Use


EXAMPLE
Use of the Gibbs Phase Rule
a. Show, using the steam tables, that fixing
the equilibrium pressure of a steam-water
mixture at 1.0135 bar is sufficient to
completely fix the thermodynamic states
of each phase
b. Show that additionally fixing the specific
volume of the two-phase system at 1
m3/kg is sufficient to determine the
distribution of mass between the two
phases.
c. What is the total enthalpy of 3.2 m3 of this
steam-water mixture
117

Gibbs Phase Rule - Use


SOLUTION
a. Using the steam tables we show that
fixing the pressure at 1.0135 bar is
sufficient to determine the temperature
and the thermodynamic properties of
each phase:

118

Gibbs Phase Rule - Use


SOLUTION
b. To determine the relative amounts of
each of the phases, we need information
from whichV and L can be determined.
Here the specific volume of the two-phase
mixture is given so we can use Eqs.

to determine the mass distribution


between the two phases:

119

Gibbs Phase Rule - Use


SOLUTION
c. The total mass is given

. From the results in parts (a) and (b) we


can compute the enthalpy per unit mass
of the two-phase mixture:

120

Vapour Pressure of a Fluid

Definition
Vapor pressureorequilibrium vapor
pressureis thepressureexerted by
avaporinthermodynamic equilibrium with
its condensed phases(solid or l iquid) at a
given temperature in a closed system.
The equilibrium vapor pressure is an
indication of a liquid's evaporation rate.
It relates to the tendency of particles to
escape from the liquid (or a solid).
A substance with a high vapor pressure at
normal temperatures is often referred to
asvolatile
121

Vapour Pressure of a Fluid

Vapor pressureof any substance


increases non- linearly with the
temperature according to theClausius
Clapeyron relation.

The atmospheric pressure boiling


pointof a liquid (also known as thenormal
boiling point) is the temperature at which
the vapor pressure
equals the ambient
atmospheric pressure.

With any incremental increase in that


temperature, the vapor pressure becomes
sufficient to overcomeatmospheric
pressureand lift the liquid to form vapor
bubbles inside the bulk of the substance.
122

Vapour Pressure of a Fluid

One phase transition property of high


importance is the slope of the coexistence
curves in the P-T pIane;

the slope of the vapor-liquid equilibrium line


gives the rate of change of the vapor
pressure of the liquid with temperature,

the slope of the vapor-solid coexistence line


is equal
to the change with temperature of
the vapour
pressure of the solid (called the sublimation
pressure), and

the inverse of the slope of the liquidsolid coexistence line gives the change of the
melting temperature of the solid with
123
pressure.

Vapour Pressure of a Fluid

The slope of any of these phase equilibrium


coexistence curves can be found by starting
with Eq .

For a small change we can write:

which the becomes:

Since, at equilibrium, T1 = T2 and P1 = P2

124

Vapour Pressure of a Fluid

Finally we can write:

and

or

which the becomes:


The Clapeyron Equation

the application of Eq. above to the vaporliquid coexistence curve is of great interest,
because this gives the change in vapor
pressure with temperature.
125

Clausius - Clapeyron
Equation

At temperatures for which the vapor


pressure is not very high, it is found that VV
>> VL and
V VV .

If, in addition, the vapor phase is ideal, we


have

And the Clausius Clapeyron Equation:

After integration this becomes:


126

Clausius - Clapeyron
Equation

127

128

Plots of vapour pressure, P vs T are


nonlinear curves (see examples below)

129

However, the Clausius-Clapeyron


equation relates P, T and the enthalpy
of vaporization, Hvap in a straight line
relationship as discussed below:
Plots of vapor pressure, P vs T are
nonlinear curves (see examples below):

With Hvap the enthalpy of


vaporization
130

This form of the equation a linear


equation,
y = mx + b ; where
y = lnP ; x = 1/T,

m = - Hvap / R is the slope, and


b = C (a constant) is the intercept.

Taking the following data , we can


determine Hvap for C6F6
(hexafluorobenzene):
131

Taking the following data , we can


determine Hvap for C6F6
Vapor
(hexafluorobenzene):
Temperature
(K)

Pressure
(torr)

1/T

ln P

280.0

32.42

0.003571

3.478

300.0

92.47

0.003333

4.527

320.0

225.1

0.003125

5.417

330.0

334.4

0.003030

5.812

340.0

482.9

0.002941

6.170

132

Taking the plot of ln P vs 1/T , we can


determine Hvap for C6F6
(hexafluorobenzene):

133

Slope = -4288.1 (K) = -Hvap/R


or Hvap = R x 4288.1 (J/mol-K)x(K)

Hvap = 8.3145 x 4288.1 (J/mol) = 35.65


x103 J/mol
Finally, Hvap = 35.65 kJ/mol

The quality of the "fit" of the line,


correlation coefficient=0.9999 testifies
both to the
quality of the data and the
134
correctness of the equation.

The second form of the ClausiusClapeyron equation


ln(P2 / P1) = Hvap/R(1/T1-1/T2)

is useful to predict the vapour pressure at


one temperature if it is known at
another.
Taking the natural antilog of (or
exponentiating) both sides, we get:

P2/P1 = exp[H/R(1/T1-1/T2) ]

or

P2 = P1exp[H/R(1/T1-1/T2) ]
135
This last expression gives the shape
of

This formula allows us to calculate the


pressure, P2, of a pure gas as a function of
temperature, T, if we know:
P2 = P 1 e

[H/R(1/T1-1/T2) ]

P1 the pressure of the gas at temperature


T1
Hvap the heat of vaporization of the
liquid usually given in kJ/mol
BUT don't forget to CONVERT to J/mol to
be consistent with gas constant value
commonly used
136
R the gas constant in J/mol: R = 8.3145

EXAMPLE
Water, has a heat of vaporisation, Hvap=
44.0 kJ/mol
and its vapour pressure is
1 atm at 100 C.
Find the vapour pressure of water at T 2 =
25 C and at T2 = 125 C?
SOLUTION:
Convert Hvap to J/mol:
Hvap =44.0 kJ/mol x 1000 J/kJ = 44 000
J/mol
Use the gas constant value, R=8.3145 J
mol-1 K-1
Convert temperatures to K:
137
T =373.15 K, T =298.15 K or T = 398.15

Fugacity of Liquids
ILLUSTRATION 7.4-7
Calculation of the Fugacity of Liquid Water
from Density Data

Compute the fugacity of liquid water at


300C and 25 MPa
SOLUTION:

We start from equation above describing


the fugacity of a liquid at a certain
temperature and pressure
138

Fugacity of Liquids
SOLUTION:
The exponential term in this equation,
known as the Poynting pressure
correction, accounts for the increase in
fugacity due to the fact that the system
pressure is higher than the vapour
pressure of the liquid.

We can assume that VL = VL Sat since


water being a liquid, is not compressible
139

Fugacity of Liquids
SOLUTION:
We saw from the previous example that:
f sat (300C) = 6.7337 MPa and from the
steam
tables at 300C :
Pvap = 8.581 MPa and L = 0.001 404
m3/kg,
so that

By substitution into equation of the


previous slide we obtain:
140

Fugacity of Liquids
SOLUTION:
For the fugacity:

Therefore the fugacity of liquid water at


300C and 25 MPa is 7.347 MPa:

141

Fugacity of Solids
ILLUSTRATION 7.4-8
Calculation of the Fugacity of Ice from
Density Data Compute the fugacity of ice at
-5C and pressures of 0.1 MPa, 10 MPa, and
100 MPa . We know that at -5C, the
sublimation pressure of ice is 0.4 kPa and its
specific gravity is 0.915.

SOLUTION
We start from equation below describing
the fugacity of a solid at a certain
temperature and pressure
We assume that ice is incompressible
over the range from 0.4 kPa to 100 MPa,
so that we can calculate its molar volume
142
over this pressure range as:

Fugacity of Solids
SOLUTION
Molar volume of ice over this pressure
range is:

Equation below gives the fugacity of a


solid:

By substitution we obtain:
143

Fugacity of Solids

By substitution we obtain for 0.1 MPa:

We shall see that change in fugacity of a


condensed species (L or S) with small
pressure changes is small.
Here we find that the fugacity of ice
increases by 10 percent for an increase in
pressure from the sublimation pressure
144

Fugacity of Solids
SOLUTION
Similarly we obtain for 10 MPa:

And for 100 MPa

145

THANK YOU

146