CE2106 Week 4

PVT Properties of Real Fluids

Content
 Chemical potential
 Fugacity and fugacity coefficient

Learning outcomes
 Understand the definition and use of Chemical potential,
fugacity and fugacity coefficient
 Able to find fugacity and fugacity coefficient of gaseous
species i as a pure species
 Identify the appropriate reference state
The chemical potential and the fugacity
Chemical potential (µ ) is a form of potential energy that can be
absorbed or released during a chemical reaction and/or a phase
transition.
Chemical potential of component i is its partial molar Gibbs free energy
when pressure, temperature and others in the system are constant.
𝜕𝜕𝐺𝐺
𝜇𝜇𝑖𝑖 ≡ 𝐺𝐺�𝑖𝑖 =
𝜕𝜕𝑛𝑛𝑖𝑖 𝑃𝑃, T, nj

Particles tend to move from higher chemical potential to lower 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.

For an one component system For a multiple component system

𝜇𝜇𝑖𝑖=0 ∑𝑖𝑖 𝜇𝜇𝑖𝑖=0

Like Gibbs free energy, chemical potential is a state function.

The chemical potential and the fugacity
We know that: dG= −SdT +VdP

If we assume constant temperature, and deal with 1 mole of the

substance of interest (called i) then we know that dT=0 and V= ʋm
~
dµI = dGi = ʋmdP
If substance i is an ideal gas, then ʋm=RT/P,

RT
dµi = dP = RTd lnP
P
Integrating this equation from pressure P*= 1 atm to any P value gives:
P
µi (T, P) = µ i (T, P *) + RT ln
P*
P
µi = µ 0 + RT ln
P0
i
The chemical potential and the fugacity
Fugacity (f) of a real gas is an effective pressure which replaces
the true mechanical pressure in accurate chemical equilibrium
calculations.

Fugacity (f) equals to the pressure of an ideal gas which has the
same chemical potential as the real gas.

For example, nitrogen gas (N2) at 0°C and a pressure of P=100 atm
has a fugacity of f = 97.03 atm.

This means that the chemical potential of real nitrogen at a pressure

of 100 atm is less than that if nitrogen were an ideal gas; the value of
the chemical potential is that which nitrogen as an ideal gas would
have at a pressure of 97.03 atm.
The chemical potential and the fugacity
P
µi = µ 0 + RT ln
P0
i

For real gases, deviations to the equation are observed.

Ideal gas
Chemical Potential µ

µ 0 Repulsions dominant ( f > p )

Attractions dominant ( f < p )

O
P0
Pressure P
The chemical potential and the fugacity
To be able to keep equations having a similar form, the fugacity f
is introduced in place of the pressure P. P and f are related by

f= φP
where φ is the fugacity coefficient, a correction factor
accounting for the non-perfection.

μi (T,P) = μ i(T,P*) + RT ln(

f
) = μ (T,P*) + RT ln(
φP)
P* i
P*

P/bar φN2 at 273K

As all gases become perfect as P close to 0, 1 0.99955
10 0.9956
100 0.9703
and φ = 1 and f = P 200 0.9721
400 1.062
1000 1.839
Estimating the fugacity of a pure compound
If we assume constant temperature, and deal with 1 mole of the substance
of interest (called i) then we know that for a real gas:

dμ = RTdlnP = RTdln( φ P )
i i

~
Since : dμi = d Gi = ʋm dP

We have: dμi = RTdln( φi P)= ʋm dP

RT
Rearrange: RTdlnφi + dP = ʋm dP
P
Estimating the fugacity of a pure compound

RT ʋm = Z i RT
RTdln φi + dP = ʋm dP but also
P P

replacing ʋm in the first equation we get :

1
dlnφi = (Z i - 1)dP
P

Integrate the equation between P=0 and P=P, we get φi .

Estimating the fugacity of a pure compound
P=P P 1 P dP
∫P=0
dlnφi = ∫
0 P
(Z i -1)dP = ∫0
(Z i -1)
P

P dP
lnφi P=P − lnφi P=0 = ∫ (Z i -1)
0 P

But this can be simplified since we know that at P = 0,φi = 1

Therefore lnφi P=0 =0

P dP
Finally lnφi = ∫ (Z i -1)
0 P
The chemical potential and the fugacity
Fugacity ( 𝑓𝑓 ) of a real gas is an effective pressure which
replaces the true mechanical pressure in accurate chemical
equilibrium calculations.

It is equal to the pressure of an ideal gas which has the same

chemical potential as the real gas.

For example, nitrogen gas at 0°C and a pressure of P=100 atm

has a fugacity of 𝑓𝑓 = 97.03 atm.

The fugacity coefficient Φ is used as a correction factor to account

for the non-perfection from ideal gas: 𝑓𝑓 = Φ P

P dP
lnφ i = ∫
0
(Z i -1)
P
Estimating the fugacity of a pure compound

We now have an expression that gives us φi, but it is a

function of Zi, which varies with the pressure.

Therefore we need to evaluate Zi first. This can be done using

either analytical equations or the generalized method (graphic
method).
Estimating the fugacity of a pure compound
Estimation by Redlich-Kwong equation:
RT a
R-K equation: P= − 1/2
Vm − b T Vm (Vm + b)

P dP
When combined with lnφi = ∫ (Z i -1)
0 P

It can be demonstrated that:

𝑏𝑏𝑏𝑏 𝑎𝑎 𝑏𝑏
𝑙𝑙𝑙𝑙∅ = 𝑍𝑍𝑝𝑝=𝑝𝑝 − 1 − ln 𝑍𝑍𝑝𝑝=𝑝𝑝 − − / ln(1 + )
𝑅𝑅𝑅𝑅 𝑏𝑏𝑏𝑏𝑏𝑏3 2 𝑉𝑉𝑚𝑚 𝑎𝑎𝑎𝑎𝑎𝑎=𝑃𝑃

Where a and b are coefficients (see estimation of Z)

Estimating the fugacity of a pure compound
Using the generalized method (graphic method)
P dP
lnφi = ∫ (Z i -1)
0 P
Estimating the fugacity of a pure compound
Generalised fugacity charts
Estimating the fugacity of a pure compound
Generalised fugacity charts
Example 1
Calculate the fugacity of isobutane at 154.5 0C and 8620 kPa by
generalised graphical method. The molar volume of isobutane under
such condition is 0.154 m3/kmol.
(For isobutane: Tc=135 0C, Pc=3648 kPa and ω=0.1756)
Example 1
Calculate the fugacity of isobutane at 154.5 0C and 8620 kPa by
generalised graphical method. The molar volume of isobutane under
such condition is 0.154 m3/kmol.
(For isobutane: Tc=135 0C, Pc=3648 kPa and ω=0.1756)

Solution:

Tr=1.05, Pr=2.36

From the generalised fugacity coefficient chart, ф=0.43

F=ф P=0.43x8620=3707kPa
Estimating the fugacity of a pure compound
Generalised fugacity charts
Example 1 Alternative Solution

P dP
lnφi = ∫ (Z i -1)
0 P
Example 2
Using thermodynamic properties from steam table,
determine the fugacity and fugacity coefficient for saturated
steam at 1 atm.
Example 2 Solution
P
For ideal gas we have µi = µ 0 + RT ln
P0
i

f
For real gas we have µi = µ 0 + RT ln 0
P
i

𝑓𝑓
Rearrange 𝜇𝜇𝑖𝑖 − 𝜇𝜇𝑖𝑖𝑜𝑜 = ∆𝜇𝜇𝑖𝑖 ≡ ∆𝑔𝑔𝑖𝑖 = 𝑅𝑅𝑅𝑅𝑅𝑅𝑅𝑅 𝑜𝑜
𝑃𝑃
∆𝑔𝑔 = ∆ℎ − 𝑇𝑇∆𝑠𝑠
From superheated steam table
T, K P, bar h, kJ/kg s, kJ/kg
373 0.1 2687.5 8.4489
373 1.014 2675.6 7.3545
∆h/∆s -11.9 -1.094

∆𝑔𝑔 = −11.9 − 373 × −1.094 =396.31 kJ/kg=7133.60kJ/kmol

𝑓𝑓 ∆𝑔𝑔𝑖𝑖 7133.60 𝑓𝑓
𝑙𝑙𝑙𝑙 = = =2.300 =exp(2.300)=9.98
𝑃𝑃𝑜𝑜 𝑅𝑅𝑅𝑅 8.314×373.15 𝑃𝑃𝑜𝑜

𝑓𝑓 0.998
𝑓𝑓=9.98𝑃𝑃𝑜𝑜 = 9.98 × 0.1𝑏𝑏𝑏𝑏𝑏𝑏 = 0.998 𝑏𝑏𝑏𝑏𝑏𝑏 ∅= = =0.985
𝑃𝑃 1.01325
Example 3

Isobutane is considered as ideal gas at T=154.5 0C and

P=8.0 kPa. Calculate its fugacity under this condition.
(For isobutane: Tc=135 0C, Pc=3648 kPa, ω=0.1756,
Da=0.35, Db=0.56)

Solution:
The T>Tc, and P<<Pc. We can assume the isobutane is very
close to ideal gas.

If the Isobutane is considered as an ideal gas then f = P

Example 4
Calculate the fugacity of isobutane at 154.5 0C and 8620 kPa by using
the Redlich-Kwong-Soave equation. The molar volume of isobutane
under such condition is 0.154 m3/kmol.
(For isobutane: Tc=135 0C, Pc=3648 kPa and ω=0.1756)

𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑏𝑏𝑏𝑏

𝑙𝑙𝑙𝑙∅ = 𝑍𝑍𝑝𝑝=𝑝𝑝 − 1 − ln 𝑍𝑍𝑝𝑝=𝑝𝑝 − − ln(1 + )
𝑅𝑅𝑅𝑅 𝑏𝑏𝑏𝑏𝑏𝑏 𝑅𝑅𝑅𝑅𝑅𝑅𝑃𝑃=𝑃𝑃

𝑅𝑅2 𝑇𝑇𝑐𝑐2
𝑎𝑎 = 0.42747
𝑃𝑃𝑐𝑐

We need to calculate a, b, α and Zp=p first.

Example 1 Solution by an analytical method

𝑅𝑅2 𝑇𝑇𝑐𝑐2
𝑎𝑎 = 0.42747 = 1.35
𝑃𝑃𝑐𝑐

0.0867RTc
b= = 8.065 x10-5
Pc

= 0.965

Zp=p= PVm/(RT)= 0.3733

𝑏𝑏𝑏𝑏 𝑎𝑎𝑎𝑎 𝑏𝑏𝑏𝑏

𝑙𝑙𝑙𝑙∅ = 𝑍𝑍𝑝𝑝=𝑝𝑝 − 1 − ln 𝑍𝑍𝑝𝑝=𝑝𝑝 − − ln(1 + )
𝑅𝑅𝑅𝑅 𝑏𝑏𝑏𝑏𝑏𝑏 𝑅𝑅𝑅𝑅𝑅𝑅𝑃𝑃=𝑃𝑃

lnφ= -0.8127 and φ=0.4436

f= φP=3824 kPa