Real Gases: Fugacity !

To introduce fugacity (f), a thermodynamic property of non-ideal gas, and to show how to calculate it! Highlights! Denition of fugacity and fugacity coefcient! Relation between fugacity and compressibility factor! Calculating fugacity of pure non-ideal gases!

Fugacity!
Idea: Keep the basic form of the equations that were derived! for ideal gases, but use an effective pressure (fugacity). !
Fugacity f = f(P) would deviate from the real pressure P at high pressures. At low pressures it approaches the real pressure:!

The denition of fugacity !

The chemical potential of a perfect gas:!

" p% = + RT ln $ ! ' #p &

!

For a real gas, replace the true pressure, p, by an effective! pressure, f, then the fugacity of a real gas is dened as:!

" f % = + RT ln $ ! ' #p &

!

The name 'fugacity' comes from the Latin for 'eetness' in the sense of 'escaping tendency'. Fugacity has the same dimension as pressure.!

The denition of fugacity !

The " of a real gas!

Standard states of real gases!

A perfect gas is in its standard state when its pressure is (po,1 bar): the pressure arises solely from the kinetic energy of the molecules and there are no intermolecular forces to take into account!

The standard state of a real gas is a hypothetical state in which the gas is at a pressure po and behaving perfectly.!

$ # ' d = ! SdT + Vdp " & ) = Vm % #p(T $ f ' = + RT ln & * ) %p (

*

The relation between fugacity and pressure!

The fugacity coefcient, !, is dened as:!

f != p

f =!p

The fugacity coefcient, ! :! 1). Dimensionless;! 2). depends on the identity of the gas, the pressure, and the temperature!

" f % = + RT ln $ ! ' #p &

! !

"( p% = + RT ln $ ! ' # p &

The relation between fugacity and pressure!

In terms of fugacity coefcient:!

#" p& # p& ! = + RT ln % ! ( = + RT ln % ! ( + RT ln " $ p ' $p '

!

The same as ideal gas

The entire effect of all intermolecular forces

For all gases, !

p ! 0, f = p

f lim = 1 p!0 p

For a prefect gas: f = p and ! =1; for a real gas: f # p and ! # 1. ! is a measure of a real gas derived from the perfect gas.!

The relation between fugacity and pressure!

d = Vm dp

is true for all gases under constant temperature.

Let f denotes the fugacity when the pressure is p and f' the fugacity when the pressure is p', from the denition of fugacity we have!

# f & = " Vm dp = + RT ln % ! ( $p ' p!

f

# f '& ' = " Vm dp = + RT ln % ! ( $p ' p!

f'

The relation between fugacity and pressure!

" f% Vm dp = ! ' = RT ln $ ' ( # f '& p'

p

For ideal gas !

" p% Videal ,m dp = ideal ! ideal ' = RT ln $ ' ( # p'& p'

p

The difference of the two equations is:!

( " f% " p %+ ! ln $ ' , (Vm ! Videal ,m ) dp = RT )ln $ ' . # p'& * # f '& p'
p

The relation between fugacity and pressure!

" f p'% 1 ln $ ! ' = # p f ' & RT

) (V
p'

( Videal ,m ) dp

p ' ! 0 , the gas behaves perfectly, and f=p, thus p/f=1!

If we take this limit, this equation becomes:!

! f$ 1 ln # & = " p % RT
With !!

( (V
0

' Videal ,m ) dp

= f /p

The relation between fugacity and pressure!

! f$ 1 ln # & = " p % RT

( (V
0

' Videal ,m ) dp

Substituting Vm = ZRT/P and Videal,m = RT/P, we arrive at:!

( Z ! 1) ln( f / p ) = " dP P 0
P

where Z is the compression factor of the gas. This equation is an explicit expression for the fugacity coefcient at any pressure p. The fugacity of the gas at that pressure can be obtained by!

f =!p

Calculating the Fugacity of a Pure Gas!

( Z " 1) ln ! = # dP P 0
P

at a given temperature !

To calculate the fugacity of a pure, non-ideal gas, all we need is information on the relationship of Z as a function of P at T. ! ! Experimental data! ! Equations of State ! ! Correlations!

Real gases: the fugacity!

( Z " 1) ln ! = # dP P 0
P

#" p& # p& ! = + RT ln % ! ( = + RT ln % ! ( + RT ln " $ p ' $p '

!

Z < 1,ln ! < 0,! < 1 " f < p

The molecules tend to stick together and the chemical potential of the gas is less than that of a perfect gas;!

Real gases: the fugacity!

( Z " 1) ln ! = # dP P 0
P

#" p& # p& ! = + RT ln % ! ( = + RT ln % ! ( + RT ln " $ p ' $p '

!

Z > 1,ln ! > 0,! > 1 " f > p

The repulsive interactions are dominant and tend to drive the particles apart, and the chemical potential of the gas is greater than that of a perfect gas!

Real gases: the fugacity!

!The expression for chemical potential!

d = dGm = Vm dp
!The chemical potential of a perfect gas :!

" p% = + RT ln $ ! ' #p &

!

!The chemical potential of a real gas and the fugacity, f:!

!The fugacity coefcient, ! (f,p) ! (Z,p):!

" f % "( p% ! = + RT ln $ ! ' = + RT ln $ ! ' #p & # p &

!

( Z " 1) ln ! = # dP P 0
P

Calculating a fugacity!
Suppose that the attractive interactions between gas particles can be neglected, and nd an expression for the fugacity of a van der Waals gas in terms of the pressure.! Estimate its value for ammonia at 10.00 atm and 298.15 K.! Method: The starting point for the calculation is equation!

( Z " 1) ln ! = # dP P 0
P

Calculating a fugacity!
The fugacity coefcient of a certain gas at 290 K and 2.1MPa is 0.68. Calculate the difference of its chemical potential from that of a perfect gas in the same state.!

Method!

ideal

" p% = + RT ln $ ! ' #p &

!

" f % "( p% ! = + RT ln $ ! ' = + RT ln $ ! ' #p & # p &

!

! ideal = RT ln "

ideal

" p% = + RT ln $ ! ' #p &

!

" f % "( p% ! = + RT ln $ ! ' = + RT ln $ ! ' #p & # p &

!

! ideal = RT ln "