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TDA-301T 2015

Lecture 10a: Equilibrium and

Stability in One-Component

Systems

By

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)

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)

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

equilibrium or for reversible processes:

gen

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,

system,

then: U = constant

= + gen

and equation:

becomes:

gen

during the approach to equilibrium!! Why?

gen 0 !

Answer:

system is:

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:

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

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 :

total internal energy were set to be

constant

Hence under the condition that:

dS =

14

Since

S = maximum or dS = 0

and V we

conclude by comparison of

equations below :

dS =

That:

15

And since T1 = T2

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

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

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 =

- T gen

0

Therefore again:

and as we saw with entropy we get for the

Gibs free energy

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.

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:

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:

if

T1,f = T2,f = Tfinal ;

that is, the final temperature of the two

blocks must be equal:

And

26

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

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

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

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

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

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

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:

constraints led to the requirements that at

equilibrium:

33

Stability of Thermodynamic

Systems

stability requirement d2S < 0 for this

system and obtain:

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

And:

35

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

37

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

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,

stability of

this state.

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

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.

equilibrium (i.e., when dS = O),

TI = TII , P I

42

= P II and G I = G II

Stability Criteria

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!

obtain: (following the same analysis as before:

43

Phases

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.

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

Phases

stability of two interacting subsystems is

that each subsystem be intrinsically stable.

45

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

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

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

EOS

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

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

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

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

and liquid, on a molar basis and

=1

And

54

and liquid, on a molar basis and

=1

And

55

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 :

the enthalpy as well :

57

Two-Phase Mixture

SOLUTION

We obtain by substitution into :

the enthalpy as well :

58

Two-Phase Mixture

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

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

start from:

along an isotherm of the equation of

state,

Then we have:

61

Two-Phase Mixture

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

pressure of the liquid and will be

denoted by Pvap(T).

63

Two-Phase Mixture

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

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

shown in Fig. 7.3-5.

66

Two-Phase Mixture

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

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:

Two-Phase Mixture

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

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

Fugacity of a Pure Component

equation of state to identify the states of

vapor-liquid

equilibrium in a pure fluid.

Gibbs energies in the coexisting phases:

We obtain

and

72

Fugacity of a Pure Component

To compute V as a function of T and P, only

Eq. below will be considered further:

any two

pressures P1 and P2 (at constant

temperature) yields:

ideal gas,

following equation would be

valid:

73

We obtain then by substitution:

Fugacity of a Pure Component

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

Component

function, the fugacity, denoted by the

symbol f .

by division

with the pressure as:

related to the exponential of the

difference

75

Definition of 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

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

equilibrium) the total sum of chemical

potentials is zero, as the free energy is at

a minimum.

thermodynamics for a system containing n

constituent species, with the I - th species

having Ni particles is, in terms of Gibbs energy:

get:

78

Definition of Fugacity

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.

introduced because its relation to the

Gibbs energy makes it useful for phase

I

G

=

equilibrium calculations

G"

for equilibrium

between two

phases was:

and

79

Component

Equation

becomes by substitution

and with

80

Fugacity

of aofPure

Component

Or in terms

the fugacity:

Equilibrium

Condition

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

integration:

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

V is used to designate the fugacity and Z

the compressibility of the vapor phase

85

the pressure of interest, the fugacity of

a pure gas can be computed by integration

of this equation:

described by the ideal gas equation of

state

the following equations are valid, i.e.

86

fugacity is equal to total pressure

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

at 300C, we have at different pressures:

87

300C

88

EXAMPLE

We carry out numerical integration of the

equation using the data above and we find :

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)

steam tables:

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

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:

= 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

5.7906 kJ/kg K

= - 533.88 KJ/Kg

o

G

REAL

93

= -9 617 J/mol

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

f V = 6.7337 MPa ; At equilibrium

f L = 6.7337 MPa ; therefore f V = f

97

the virial equation of state

equation of state shortened after the

second virial coefficient

if data for B(T) are available

with Z

98

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

the virial equation of state

Then we obtain for the fugacities:

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

- expansion) must be used

By using the van der Waals equation, (not

very accurate! ) we obtain:

101

Calculation of Fugacity of a

Gas

using

the PengaRobinson

EOS

At higher

pressures,

more complicated

- 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

increase significantly, but there is software

available that significantly facilitates matters

103

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,

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

of Fugacity of a Gas

This can be simplified to:

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

Of Several Phases - Gibbs

Phase Rule

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

Several Phases - Gibbs Phase

Rule

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!

system.

QUESTIONS

specified to completely fix the

109

thermodynamic state of each phase when

Of Several Phases - Gibbs

Phase Rule

QUESTIONS

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,

fix the total size of the multiphase system?

present, the system would have 2P degrees

of freedom.;

However, actual number of degrees of

freedom is fewer, since the requirement

110

Of Several Phases - Gibbs

Phase Rule

QUESTIONS

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)

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

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

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

i the mass fraction in phase i, which

must be determined.

Sum of mass fractions must be unity

the form:

115

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

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.

between the two phases:

119

SOLUTION

c. The total mass is given

can compute the enthalpy per unit mass

of the two-phase mixture:

120

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

increases non- linearly with the

temperature according to theClausius

Clapeyron relation.

pointof a liquid (also known as thenormal

boiling point) is the temperature at which

the vapor pressure

equals the ambient

atmospheric pressure.

temperature, the vapor pressure becomes

sufficient to overcomeatmospheric

pressureand lift the liquid to form vapor

bubbles inside the bulk of the substance.

122

importance is the slope of the coexistence

curves in the P-T pIane;

gives the rate of change of the vapor

pressure of the liquid with temperature,

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.

coexistence curves can be found by starting

with Eq .

124

and

or

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

pressure is not very high, it is found that VV

>> VL and

V VV .

have

126

Clausius - Clapeyron

Equation

127

128

nonlinear curves (see examples below)

129

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):

vaporization

130

equation,

y = mx + b ; where

y = lnP ; x = 1/T,

b = C (a constant) is the intercept.

determine Hvap for C6F6

(hexafluorobenzene):

131

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

determine Hvap for C6F6

(hexafluorobenzene):

133

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

x103 J/mol

Finally, Hvap = 35.65 kJ/mol

correlation coefficient=0.9999 testifies

both to the

quality of the data and the

134

correctness of the equation.

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

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

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) ]

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

300C and 25 MPa

SOLUTION:

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.

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

previous slide we obtain:

140

Fugacity of Liquids

SOLUTION:

For the fugacity:

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:

solid:

By substitution we obtain:

143

Fugacity of Solids

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:

145

THANK YOU

146

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