Outline

• Definition of fugacity and fugacity coefficient

• Fugacity in the gas phase
CHE 507 Solution Thermodynamics & • Fugacity and fugacity coefficient of pure gases
• Fugacity and fugacity coefficient of species i in a gas mixture
Phase Equilibria • Fugacity in the liquid phase
• Fugacity and fugacity coefficient of pure liquids
• Fugacities in a liquid mixture using EOS
• Application of fugacity in vapor-liquid equilibria
Lecture 4. Phase Equilibria: Fugacity Concept • Fugacity in the solid phase

References: Tosun Chp 5,7; Koretsky Chp 7

1 2

Definition of Fugacity and Fugacity Definition of Fugacity and Fugacity

Coefficient Coefficient
• The expression for the differential change of Gibbs energy in a mixture:

• Since energies never have absolute values, we need a reference state for the partial
• Using the Maxwell relations: molar Gibbs energy. The reference state is indicated by a superscript “o”. The reference
chemical potential, µio, is the chemical potential at the reference pressure, Po, and at the
same temperature as the chemical potential of interest, T.
𝜕 𝐺 𝜕 𝜕𝐺 𝜕 𝜕𝐺 𝜕𝑆
= = =− → or
𝜕𝑇𝜕𝑛 𝜕𝑇 𝜕𝑛 𝜕𝑛 𝜕𝑇 𝜕𝑛 • Integrating between a reference state and the state of the system, we get:
,
𝑅𝑇
𝑑𝜇 = 𝑑𝑃 →
• Thus, 𝑃
• Starting from the ideal gas, and applying the definition of partial volume for ideal gases • The chemical potential describes the contribution of species i to the Gibbs energy of the
mixture; thus, it is convenient to multiply the top and bottom in the log term by the mole
fraction of species i, yi:

3 4
 Definition of Fugacity and Fugacity Definition of Fugacity and Fugacity
Coefficient Coefficient
𝑅𝑇
𝑑𝜇 = 𝑑𝑃 →
𝑃
• where pi = P.yi is the partial pressure of the gas. The use of partial pressure is valid since
we are considering ideal gases. • Accordingly, fugacity has units of pressure. Comparison of the equations
• The equation above exposes the mathematical problems associated with the chemical above shows that fugacity plays the same role in real gases that partial
potential in two very important limits: (1) as the mole fraction of species i goes to zero, pressure plays in ideal gases. In this sense fugacity can be thought of as a
that is, infinite dilution, and (2) as the pressure goes to zero, that is, the ideal gas limit. In “corrected pressure/corrected partial pressure.”
both these cases, the value of µi goes to negative infinity.
• G. N. Lewis had tremendous insight and inductively defined a new thermodynamic • Fugacity can roughly be translated from Latin as “the tendency to escape.”
property, the fugacity, 𝑓 , in analogy to the above Equation. Fugacity is defined as: • This defining equation is valid for an isothermal change from the reference
state chemical potential to that of the system for all real species. Lewis did
𝑅𝑇 not restrict the fugacity to the gas phase! It applies to liquid or solids as
𝑑𝜇 = 𝑑𝑃 →
𝑃 well.
5 6

Definition of Fugacity and Fugacity Definition of Fugacity and Fugacity

Coefficient
• The definition above is not complete. The reference state is arbitrary; we are free to
choose the most convenient reference state imaginable. As the pressure goes to zero, all
gases behave ideally; consequently, we define:
• The group, , 𝑓 /𝑝 , often shows up in our encounters with fugacity; we call it the fugacity
coefficient, , 𝜙 :
• The fugacity coefficient represents a dimensionless quantity that compares the fugacity
of species i to the partial pressure species i would have in the system as an ideal gas.
Coefficient
• A fugacity coefficient of one represents the case where attractive and repulsive forces
balance and is usually indicative of an ideal gas. If 𝜙 1 the corrected pressure, or
“tendency to escape,” is less than that for an ideal gas. In this case, attractive forces
dominate the system behavior. Conversely, when 𝜙 1 repulsive forces are stronger.
• Warning: We define the fugacity coefficient relative to the system partial pressure, not
the partial pressure of the reference state. A common mistake is to use the wrong
pressure here.
• The fugacity and fugacity coefficient are given a hat instead of a bar to remind us that
while they represent the contribution of species i in solution, they do not represent the
mathematical definition of a partial molar property, that is,

7 8
 Definition of Fugacity and Fugacity
Derivation of the Fugacity for the Pure State
Coefficient
• We can also define the pure species fugacity, fi, 𝑑𝐺 = 𝑉 𝑑𝑃 − 𝑆 𝑑𝑇 → 𝑑𝐺 = 𝑉 𝑑𝑃 =
𝑅𝑇
𝑑𝑃 (constant T, ideal gas)
𝑃

Pure State Mixture 𝑅𝑇 𝑓

𝑑𝐺 = 𝑑𝑃 → 𝐺 − 𝐺 = 𝑅𝑇 ln (𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 𝑇)
𝑃 𝑓
𝑓 𝑓
𝐺 − 𝐺 = 𝑅𝑇𝑙𝑛 𝜇 − 𝜇 = 𝐺̅ − 𝐺̅ = 𝑅𝑇𝑙𝑛
𝑓 𝑓 Set reference state as ideal gas at T, P:
𝑓 𝑓 𝑅𝑇 𝑓
lim =1 lim =1 𝑑𝐺 = 𝑑𝑃 → 𝐺 − 𝐺 = 𝑅𝑇 ln
→ 𝑃 → 𝑃𝑦 𝑃 𝑃
𝑓 𝑓 𝑓
𝜙 = 𝜙 = = 𝑓 (𝑇, 𝑃) 𝐺 −𝐺 ,
𝐻 −𝐻 ,
𝑆 −𝑆 ,
𝑃 𝑃𝑦 𝑝 ln = = −
𝑃 𝑅𝑇 𝑅𝑇 𝑅
fi = fugacity of component i in the pure state 𝒇𝒊 = fugacity of component i in a mixture
𝐺 − 𝐺 = Gibbs energy departure function
φi = fugacity coefficient of component i in the pure state 𝝓𝐢 = fugacity coefficient of component i in a mixture
𝐻 − 𝐻 = Enthalpy departure function
9
𝑆 − 𝑆 = Entropy departure function 10

Criteria for Chemical Equilibria in Terms of

Derivation of the Fugacity for the Pure State
Fugacity
• The concept of fugacity works so well because the criterion for chemical equilibria is just
Alternatively, set reference state as ideal gas at T and standard pressure, Po:
as simple as that using chemical potential. Equating chemical potentials for α and β
( , )
𝑅𝑇 𝑓 phases:
𝑑𝐺 = 𝑑𝑃 → 𝐺 (𝑇, 𝑃) − 𝐺 (𝑇, 𝑃 ) = 𝑅𝑇 ln
( , ) 𝑃 𝑃

• Apply a mathematical relationship to the quotient in the logarithms and rearrange:

Constant

Equation above forms the criterion for

chemical equilibrium in terms of fugacity.
11 12
 Criteria for Chemical Equilibria in Terms of Summary of Fugacity and Fugacity
Fugacity Coefficient Facts
• Thus equilibrium criteria become: • Fugacity is nothing but a thermodynamic function, which
• gives a measure of non-ideality
• can be treated as corrected pressure or corrected partial pressure
for mixtures • identifies whether attractive or repulsive forces are dominant
• can be applied to gas, liquid, or solid phases as well as phase
• It is just as simple as that for chemical potential. Fugacity is also mathematically much
better behaved. For example, for vapor–liquid equilibria, we have:
equilibria
• is the driving force for mass transfer i.e. mass is transferred from
higher fugacity to lower fugacity
• Once we have examined how to calculate fugacities for the vapor and liquid phases
• is the criteria for the chemical equilibrium i.e can be used to
separately, we can merely equate the two expressions and then calculate the calculate equilibrium conditions and compositions.
composition of species i in each phase.
Note: 𝑓 ∝ = 𝑓 applies to pure states as the criterion of chemical equilibria
13 14

Expression of Fugacity Coefficient of a

Fugacity of a Pure Gas
Pure Gas Using Tables:
• Starting from: and • Tables of thermodynamic properties typically have 𝐻, 𝑆, T, and P. From the first three
properties, 𝐺 can be calculated.
• Subtraction of the term ‘RT d[ln P]’ from both sides of the Eqn above and integration • Example 5.2 (Tosun): Calculate the fugacity of steam at 873 K and 50 bar using the
from an ideal gas state to any state lead to: following data:

which is applicable to gases, liquids, and solids.

• In order to obtain the fugacity of a real gas, we must have appropriate thermodynamic
property data available. We will explore three possible sources of data for pure gases:
1) Tables • Please also see Example 7.1 in Koretsky’s book (page 397).
2) Equation of states
3) Generalized correlations/Principle of corresponding states
15 16
Example 5.2 (Tosun): Calculate the fugacity of Expression for the Fugacity Coefficient of a
Pure Gas Using Equations of State
steam at 873 K and 50 bar using the following data:

• Starting from the general expression:

• At low pressures gas behave ideally with ZiV = 1, Then:

• İf EOS is volume explicit i.e. 𝑉 = 𝑉 𝑇, 𝑃 , the above equations can be applied easily as in
the following example:

18

Fugacity Coefficient from the Virial Equation

of State
• Starting from the general expressions:

• At low to moderate pressures, it is possible to truncate the virial equation of state after
the second term:

• Plug this EOS into the general expression:

20
 Fugacity from Cubic Equations of State Fugacity from Cubic Equations of State
• The cubic equations of state are pressure-explicit, i.e. P = P(𝑉 , T), and the use of:

is not practical for this case. Therefore, it is useful to have an equation relating fugacity to • Substitution of the cubic equation of state into Eqn above and integration lead to
an integral over volume rather than pressure. Starting from EOS of real gases: the following general expression for calculating fugacity coefficients in the vapor
phase:
• Differentiation at constant T yields:

• where the term ΘiV is given in Table 5.1 depending on the equation of state.
• Substitute last two equations in the first equation gives:

21 22

• Look up Tc, Pc, and ω

• Calculate Tr, Pr
• Calculate Ai, Bi, p, q, r from Table 3.2
• Solve:
𝑍 𝑝𝑍 𝑞𝑍 𝑟 = 0
• Get the highest root for 𝑍
• Use the following equation to get 𝜑
𝐴
ln 𝜑 = 𝑍 − 1 − ln 𝑍 − 𝐵 −
𝑍

Note: Get the highest root for 𝑍

Fugacity from Generalized Correlations/Principle
of Corresponding States
• Using principle of corresponding states:
in which the enthalpy and entropy departure functions are calculated from Eqns
(3.6-24) and (3.6-25) in Tosun’s book respectively.
25
Fugacity from Generalized Correlations/Principle
of Corresponding States
• Using Lee Kesler charts:
• Once we have determined the reduced temperature and pressure for a given system, we
can then use the form:
• These same data are reported in tabular form in Appendix C (Tables C.7 and C.8) and
Figure 7.1 and Figure 7.2 for φ(0) and φ(1) respectively. The expression that was used to
generate these values is described in Appendix E. (Koretsky)
• These data are reported as a base-10 logarithm (log) as opposed to the natural logarithm
(ln), which is base-e. So be careful.
• See Example 7.3. in Koretsky’s textbook (page 402).
26
 Property Changes of Mixing for Ideal Gas Property Changes of Mixing for Ideal Gas
• Partial Molar Gibbs Free energy of an ideal mixture: • Any total property in an ideal gas mixture is the sum of individual species making up the
• Ideal mixture: Low density mixture so that no appreciable interactions between the mixture, each evaluated at the mixture temperature and its own partial pressure.
molecules. The EOS for an ideal gas mixture can be written as:

in which the superscript “IGM” stands for “ideal gas mixture.” In an ideal gas mixture, the
partial pressure of species i, pi, is expressed as:

• We derived entropy as:

• At constant T,
29 30

Property Changes of Mixing for Ideal Gas Property Changes of Mixing for Ideal Gas

• Integration at constant temperature from P to pi yields:

• The partial molar Gibbs energy of species i in an ideal gas mixture can be calculated as:

∆𝐺 =𝐺 − 𝑦𝐺 = 𝑦 𝐺̅ −𝐺 = 𝑦 𝜇 −𝐺
• However, there will be a positive entropy change of mixing, since the ideal gas mixture
has more possible configurations (i.e., is more random) than the separated pure
species.The Gibbs energy of an ideal gas mixture is: ∆𝐺 = 𝑅𝑇 𝑦 ln 𝑦

31 32
 Fugacity and Fugacity Coefficient of Species i
Property Changes of Mixing for Ideal Gas
in a Gas Mixture
• We now extend our discussion of fugacity in the gas phase to
include mixtures.
• In addition to temperature and pressure, the fugacity of
species i depends on what other species are present in the
mixture.
∆𝐺 = 𝑅𝑇 𝑦 ln 𝑦 0 𝑦 1 → ln 𝑦 0 → ∆𝐺 0 → mixing is spontaneous • In a mixture, the chemical nature of the interactions
• Figure 7.4 shows the Gibbs energy of ideal gas species a and b. Curve 1 plots the value of 𝐺 for a between species i and all the other species in the mixture
given mixture composition when the two gases exist separately, as pure species, while curve 2
plots the value of 𝐺 in the mixture. The lowering of 𝐺 when a and b mix is due to the Gibbs must be taken into account.
energy of mixing, ∆𝐺 .
• In other words, the fugacity and fugacity coefficient in the
• Note that the Gibbs energy of the mixture is always lower than the weighted average of the pure
species. Thus, two ideal gases can lower their Gibbs energy if they are allowed to mix; this mixture are functions of the composition of the mixture.
indicates that the mixing process occurs spontaneously.
33 34

Fugacity and Fugacity Coefficient of Species i Fugacity and Fugacity Coefficient of Species i
in a Gas Mixture in a Gas Mixture
• These figures shows the impact of the interactions • To calculate the fugacity coefficient of a component in a mixture we need to choose a
between the different species in a mixture in our reference state, which is ideal gas mixture:
calculations. We compare binary mixtures of (i) ̅ ( , , )
𝑅𝑇 𝑃𝑥 𝑝 𝐺̅ 𝑇, 𝑃, 𝑥 − 𝐺 (𝑇, 𝑃)
methane–ethane and (ii) methane–n-pentane. 𝑑𝐺̅ = 𝑑𝑃 → ln = ln =
( , ) 𝑃 𝑃 𝑃 𝑅𝑇
• At the same T, P, and methane mole fraction, the
deviation from ideality of the methane in n- • Lewis proposed that the fugacity of a component i in a mixture, 𝑓 , is expressed in the
pentane is generally greater than when methane form by taking ideal gas mixture as a reference state:
is mixed with ethane.
̅ ( , , )
• Moreover, the differences between the two binary 𝑅𝑇 𝑓 𝐺̅ (𝑇, 𝑃, 𝑥 ) − 𝐺̅ (𝑇, 𝑃, 𝑥 )
𝑑𝐺̅ = 𝑑𝑃 → ln =
systems become more pronounced at lower ̅ ( , , ) 𝒑𝒊 𝑃 𝑃𝑥 𝑅𝑇
methane mole fraction, where a methane
molecule is more likely to interact with the other 𝜙 =
𝑓
= fugacity coefficient of a component i in a mixture
component in the mixture. Indeed, the chemical 𝑃𝑥
composition of the mixture is a major factor in
determining the fugacity coefficient of species i.
35 36
Fugacity and Fugacity Coefficient of Species i Fugacity and Fugacity Coefficient of Species i
in a Gas Mixture in a Gas Mixture
• Alternative expression: • At constant T:
̅ ( , , )
𝑅𝑇 𝑓 𝐺̅ (𝑇, 𝑃, 𝑥 ) − 𝐺 (𝑇, 𝑃 ) • Subtraction of the term RT d[ln(xiP)] from both sides of the equation above and
𝑑𝐺̅ = 𝑑𝑃 → ln = integration result in:
( , ) 𝑃 𝑃 𝑅𝑇

(Eqn I)

where λi(T) is the molar Gibbs energy of pure component i at unit fugacity, • Using

(Eqn II)
• Differentiate with respect to P
• The fugacity of a pure component can be calculated as follows:

(Eqn III)

37 38

Fugacity and Fugacity Coefficient of Species i

Lewis Fugacity Rule
in a Gas Mixture
• Subtraction of the Eqn III from Eqn I gives: • As we have seen, the fugacity coefficient (or fugacity) depends not only on T and
P but also on the composition (chemical nature) of all the other species in the
(Eqn IV) mixture.
• Eqns I, II, and IV can be used to calculate the fugacity of component i in a mixture, and all
• However, we can sometimes approximate the fugacity coefficient of species i in a
equations are valid for gases, liquids, and solids. mixture by its pure species fugacity coefficient:
• Note that the evaluation of integrals in these equations requires either the equation of
state or the volumetric data in tabular form to be known.
• This approximation is known as the Lewis fugacity rule. It approximates all
(Eqn I) interactions in the mixture as being identical to the i-i interaction and simplifies
calculations significantly because the pure species fugacity coefficient does not
depend on the other species in the mixture but rather depends only on T and P.
(Eqn II)

39 40
 Lewis Fugacity Rule
Therefore, to calculate the fugacity coefficient of a mixture, we may choose from three
levels of rigor:
1) Solve the full problem with compositional-dependent fugacity coefficients. It requires
mixing rules for the EOS parameters to account for the i-j interactions of a mixture:
2) Assumption: Lewis fugacity rule. This approach treats all the interactions as the same
(i-i interactions). The advantage of this approach is that mixing rules are not needed,
and it is mathematically much easier (the use of Lewis fugacity coefficient):
3) Assumption: Ideal gas behavior, in which case there are no intermolecular interactions
present, and the fugacity of species i is simply equal to its partial pressure:
41
Expression of the Fugacity Coefficient of a
Gas Mixture Using EOS
• Fugacity from the Virial Equation of State:
• At moderate pressures, the truncated form of virial EOS:
• For binary mixtures
• See example 7.3. in Tosun’s book.
43
Lewis Fugacity Rule
• When is the Lewis fugacity rule a good approximation?
• Fugacity derived from van der Waals EOS for binary mixtures can give insights:
• Lewis fugacity rule is a good approximation when the term in the exponential is
small. This condition is valid when the following are true:
1. The pressure is low or the temperature is high. This condition corresponds to an ideal
gas.
2. Component a is present in large excess (yb is small).
3. The chemical nature of species a is similar to that of all the other components aa ≈ ab.
42
Expression of the Fugacity Coefficient of a
Gas Mixture Using EOS
• Fugacity from the Cubic Equation of State:
• Since the cubic equations of state are pressure-explicit, i.e.
• Then, it is useful to have an equation relating the fugacity of component i in a mixture to
an integral over volume rather than pressure. By skipping the intermediate steps, the
final form of fugacity coefficient relation becomes:
44
 Expression of the Fugacity Coefficient of a Expression of the Fugacity Coefficient of a
Gas Mixture Using EOS Gas Mixture Using EOS
• van der Waals equation of state: • Soave-Redlich-Kwong equation of state:

• Redlich-Kwong equation of state:

• Peng-Robinson equation of state:
Note: Take the highest root for 𝑍
See Example 7.6 in Tosun’s book

45 46

Fugacity of a Pure Liquid Fugacity of a Pure Liquid

• The vapor and liquid phases are in equilibrium with each other at the point of
• We can calculate fiL with a judicious choice of thermodynamic path. intersection of 𝐺 versus P curves in Fig. 5.2, i.e. at 𝑃 . Thus,
• At 𝑃 ,we can determine fiL for the system by equating it to the vapor-phase fugacity
since the vapor and liquid are in equilibrium. • The definition of molar Gibbs free energy of liquid at T, P:
• We then correct for pressure between the saturation pressure and system pressure
utilizing the thermodynamic web.
47 48
 Fugacity of a Pure Liquid Fugacity of a Pure Liquid

• Same but at 𝑃 • At constant temperature, integration 𝐺 from Pivap to P:

• Subtract the last two equations in which the molar volume of liquid is considered constant. Substitution and
rearrangement gives:

• Combine 1st and last equation (replace fiL (T, Pivap) with fiV (T, Pivap):

49 50

Fugacity of a Pure Liquid Fugacity of a Pure Liquid

• The exponential term in above equations is commonly referred to as the Poynting
correction factor (PCF).
• It accounts for the compression of the liquid to a pressure P greater than its vapor
pressure, Pivap. Table 5.2 indicates the variation in PCF as a function of pressure.
• Examination of the values clearly reveals that the PCF is almost unity at low pressures
but may become large at extremely high pressures or low temperatures
• Evaluation of liquid fugacities requires molar volumes of saturated liquids to be known.
Molar volumes of various liquids as a function of temperature are given in Table 5.3.
• If experimental data are unavailable, molar volumes of saturated liquids can be
estimated by the modified Rackett equation:
where ZRA is the Rackett parameter, given by:

• If liquid fugacity is known at (T, P1), the value of the liquid fugacity at (T, P2) can be
calculated from:

51 52
 Fugacity of a Pure Liquid from Cubic
Equations of State
• Since cubic equations of state can describe pure substances in both
the vapor and liquid phases, Eqn (5.3-9) used for vapor phase is
also applicable to liquids, i.e.

• where the term ΘiL is given in Table 5.4 depending on the equation
of state.

54

Fugacities in a Liquid Mixture

Two approaches:
• Use EOS as in gas phase
• Develop an appropriate reference state for the liquid
phase, the ideal solution, and then correct for real
behavior through the activity coefficient, which has
similar meaning of liquid phase fugacity coefficient (will
be covered later)

Note: Get the lowest root for 𝑍

56
 Calculation of Component Fugacities in a Calculation of Component Fugacities in a
Liquid Mixture Using Cubic EOS: Liquid Mixture Using Cubic EOS:
• Cubic equations of state can also describe P-V-T relations of liquid mixtures. By using
van der Waals mixing rules, fugacity coefficients can be calculated as:

57 58

Application of Fugacity Concept into VLE

Problems
 Fugacity of a Pure Solid Fugacity of a Pure Solid

• When the vapor and solid phases are in equilibrium:

• We can calculate fiS with a judicious choice of thermodynamic path, similar to the
calculation of fiL. • Molar Gibbs energy of a pure solid at any temperature and pressure and is expressed as:
• At 𝑃 ,we can determine fiS for the system by equating it to the vapor-phase fugacity
since the vapor and liquid are in equilibrium.
• Molar Gibbs energy of a pure solid at the same temperature and sublimation pressure:
• We then correct for pressure between the sublimation pressure and system pressure
utilizing the thermodynamic web.

61 62

Fugacity of a Pure Solid Fugacity of a Pure Solid

• At constant temperature, integration 𝐺 from Pisub to P

• Subtract:
• in which 𝑉 is considered constant. Substitution and rearrangement gives:

• Combine 1st and last equation (replace fiL (T, Pisub) with fiV (T, Pisub):

63 64
 Fugacity of a Pure Solid

• Sublimation pressure of solids is normally low. Therefore, ideal gas behavior for the gas
phase over the pure solid can be assumed, i.e. φiV (T, Pisub) ≈ 1.

• If solid fugacity is known at (T, P1), the value of the solid fugacity at (T, P2) can be
calculated from:

• Please see Example 5.8 in Tosun’s book.

65