TDA 301T - 2015-10 - Thermodynamic Properties Real Substances

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

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

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?

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

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

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

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

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

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

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

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

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

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

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

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
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
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
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

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

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
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
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
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
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
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
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.

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

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:.

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

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

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

EOS
where V and L are fractions of vapour
and liquid, on a molar basis and
=1
And
53
Maxwell or Lever Rule

=1
And
54
Maxwell or Lever Rule

=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

Two-Phase Mixture
SOLUTION
We obtain by substitution into :
Using corresponding equation we get

the enthalpy as well :
57

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

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:

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 ;

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

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

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

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
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
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
of a Pure Component
Then we obtain G IG [300 oC, 8 MPa] by
substitution:
92
of a Pure Component
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]
of a Pure Component
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

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

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
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
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

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

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)

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
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
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
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

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

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

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
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
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.
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
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

Vapor
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

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
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
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

TDA 301T - 2015-10 - Thermodynamic Properties Real Substances

Загружено:

Сведения о документе

Оригинальное название

Авторское право

Доступные форматы

Поделиться этим документом

Поделиться или встроить документ

Параметры публикации

Этот документ был вам полезен?

Это неприемлемый материал?

Авторское право:

Доступные форматы

TDA 301T - 2015-10 - Thermodynamic Properties Real Substances

Загружено:

Авторское право:

Доступные форматы

APPLIED THERMODYNAMICS

Prof Alex Sofianos

Assessment TDA 301T

Criteria for Equilibrium

Criteria for Equilibrium

Thermodynamics we remember that for

the system was chosen in such a way that

Criteria for Equilibrium

is fixed in a closed, one-component

entropy function can only increase in value

Criteria for Equilibrium

Equilibrium criterion for a closed, isolated

This equilibrium criterion can be used for

Example for Equilibrium Criterion

Example for Equilibrium Criterion

Example for Equilibrium Criterion

change in the entropy of system 1 due to

Example for Equilibrium Criterion

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

Total number of moles, total volume and

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

Example for Equilibrium Criterion

for all system variations at constant N, U,

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

Example for Equilibrium Criterion

In other words, the equilibrium condition

Example for Equilibrium Criterion

Example for Equilibrium Criterion

Example for Equilibrium Criterion

equations, and using the fact that: T dS =

This last part stems from the fact that T =

Example for Equilibrium Criterion

Example for Equilibrium Criterion

constant and positive: T and gen

This is the most important of the

Example for Equilibrium Criterion

Choose the two metal blocks as the system

or by introducing of heat capacity:

The equilibrium equation can be satisfied

Proving the Equality of Gibbs Energies

Proving the Equality of Gibbs Energies

Proving the Equality of Gibbs Energies

at this vapor-liquid phase equilibrium state

Suppose that a small fluctuation in a

Problem of the intrinsic stability of the

Using the subdivision of the system into

for all system variations consistent with the

Now we write an expression for the

It now remains to evaluate the various

Starting with equation below:

Which for an open system becomes:

Thermal Stability Criterion

Similarly we can derive

And with quite a lot of Algebra we obtain:

Which can be reduced to

Mechanical Stability Criterion

Mechanical Stability Criterion

Mechanical Stability Criterion

> 0 or Cv < 0 has yet been

Determination of requirements for the

An example of this is a vapor and a liquid

For this system we have:

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