Lecture Three : Fugacity

 What is the fugacity ?

 Technical aspect.
 Fugacity and chemical potential.
 Additional methods for calculating fugacity.
 Fugacity coefficient.
 Fugacity (f) of Pure Real Gas, Fugacity (f):
 measure the pressure for real gases.
 Pure Real Gas System:
 General equation for Real Pure gases:
 How is calculate the fugacity ?
 The Fugacity of van der Waals.
 Fugacity calculate from law of corresponding state.

)CH 631( ‫الديناميكا الحراراية لإلنظمة غير المثالية‬

‫عبدالحكيم علي جنقر‬/ ‫د‬
‫ قسم الكيمياء – كلية العلوم – جامعة طرابلس‬:‫أستاد مشارك في الكيمياء الفيزيائية‬
 Technical aspect of Fugacity
 Fugacity is a state function of matter at fixed temperature.
 It only becomes useful when dealing with substances other than an ideal gas.
 For an ideal gas, fugacity is equal to pressure.
 In the real world, though under low pressures and high temperatures some substances approach ideal behavior,
no substance is truly ideal, so we use fugacity not only to describe non-ideal gases, but liquids and solids as
well.
 The fugacity coefficient is defined as the ratio fugacity/pressure.
 For gases at low pressures (where the ideal gas law is a good approximation), fugacity is roughly equal to
pressure.
 Thus, for an ideal gas, the ratio φ = f/P between fugacity f and pressure P (the fugacity coefficient) is equal to
1.
 This ratio can be thought of as 'how closely the substance behaves like an ideal gas,' based on how far it is from
1.
dG 𝑽ഥdP
 For a given temperature T, the fugacity f satisfies the following differential relation: d ln f = =
RT RT
fo
 Where; G is the Gibbs free energy, R is the gas constant, V is the fluid's molar volume, and fo 1 bar.
 For is a reference fugacity which is generally taken as that of an ideal gas at an ideal gas, when f = P, this
equation reduces to the ideal gas law.
 Thus, for any two mutually-isothermal physical states, represented by subscripts 1 and 2, the ratio of the two
fugacities is as follows: f2 1 𝑮 1 𝑷 ഥ
= exp ( ‫ = )𝑮𝒅 𝟐 𝑮׬‬exp ( ‫𝑽 𝟐 𝑷׬‬dP)
f 1 RT 𝟏 RT 𝟏
 Fugacity and chemical potential
 For every pure substance, we have the relation dG = –SdT + VdP for Gibbs free energy and we can integrate this expression
remembering the chemical potential is a function of T and P. We must also set a reference state. In this case, for an ideal gas
μ 𝑷
ഥ dP
the only reference state will be the pressure, and we set P = 1 bar: ‫ 𝒐 ׬‬dμ = ‫𝑽 𝒐 ׬‬
μ 𝑷

 Now, for the ideal gas: ഥ = 𝑹𝑻

𝑽 𝑷
𝐏 𝐑𝐓 𝐏
μ – μo = ‫𝐨𝐩׬‬ dP = RT ln 𝐏𝐨
𝐏
𝐏
 Reordering, we get: μ = μo + RT ln 𝐏𝐨

 Which gives the chemical potential for an ideal gas in an isothermal process, where the reference state is P =1 bar.
𝑷
ഥ dP ; because we do not have a simple expression for a real gas’ molar volume.
 For a real gas, we cannot calculate ‫𝑽 𝒐𝑷׬‬
 On the other hand, even if we did have one expression for it (we could use the Van der Waals equation or any other
equation of state), it would depend on the substance being studied and would be therefore of a very limited usability.
 We would like the expression for a real gas’ chemical potential to be similar to the one for an ideal gas.
𝒇
 We can define a magnitude, called fugacity, so that the chemical potential for a real gas becomes: μ = μo + RT ln 𝒇𝒐

 with a given reference state (discussed later).We can see that for an ideal gas, it must be f = P. But for P → 0, every gas is an
ideal gas.
 Therefore, fugacity must obey the limit equation: 𝐥𝐢𝐦 𝑷𝒇 = 𝟏
𝑷→ 𝟎

𝑷𝑽 −𝑹𝑻
 We determine f by defining a function: Φ =
𝑷
 We can obtain values for Φ experimentally easily by measuring V, T and P. (note that for an ideal gas, Φ = 1).
 From the expression above we have : 𝑽 ഥ = 𝑹𝑻 + Φ
𝑷

 We can then write : ‫׬‬μμ𝒐 dμ = ‫𝑽 𝒐𝑷𝑷׬‬

ഥ dP = ‫ 𝑻𝑹 𝒐𝑷׬‬dP + ‫ 𝒐𝑷׬‬Φ dP
𝒑 𝑷 𝒑

𝑷 𝑷
 Where; μ = μo + RT ln 𝑷𝒐 + ‫ 𝒐𝒑׬‬Φ dP
𝒇
 Since the expression for an ideal gas was chosen to be , we must have μ = μo + RT ln 𝒇𝒐
𝒇 𝑷 𝑷 𝒐

μo + RT ln
𝒇
= μo + RT ln
𝑷
+
𝑷
‫ 𝒐𝒑׬‬Φ dP → RT ln 𝒇𝒐 - RT ln 𝑷𝒐 = ‫ 𝒐𝒑׬‬Φ dP → RT ln 𝒇𝑷𝒐 = ‫ 𝒐𝑷׬‬Φ dP
𝒇𝒐 𝑷𝒐 𝑷𝒇 𝒑
𝒇 𝑷
 Suppose we choose P → 0. Since , we obtain: 𝐥𝐢𝐦 𝒇=𝑷 = 𝟏 ∶ RT ln 𝑷 = ‫ 𝟎׬‬Φ dP
𝑷→ 𝟎
𝒇 𝟏 𝑷
 The fugacity coefficient will then verify: ln𝑷 = 𝑹𝑻 ‫ 𝟎׬‬Φ dP

 The integral can be evaluated via graphical integration if we measure experimentally values for φ while varying P. We
can then find the fugacity coefficient of a gas at a given pressure P and calculate: f = φ
 The reference state for the expression of a real gas’ chemical potential is taken to be “ideal gas, at P = 1 bar and work T”.
 Since in the reference state the gas is considered to be ideal (it is an theoretical reference state), we can write that
𝒇
for the real gas: μ = μo + RT ln
𝑷𝒐
 Additional methods for calculating fugacity
ƒ Φ𝑷
 If we suppose that Φ is constant between 0 and P (assuming it is possible to do this approximation), we have: = 𝑒 𝑹𝑻
𝑷

ƒ Φ𝑷 𝟏
ഥ ഥ /RT -1 = P𝑽
ഥ )/RT
 Expanding in Taylor series about 0, ≈1+ =1+ (P𝑽 − 𝑹T /P ) P = 1 + P𝑽
𝑷 𝑹𝑻 𝑹𝑻

𝑷𝟐𝑽
 Finally, we get: ƒ≈
𝑹𝑻

 This formula allows us to calculate quickly the fugacity of a real gas at P, T, given a value for V (which could
be determined using any equation of state), if we suppose is constant between 0 and P.
 We can also use generalized charts for gases in order to find the fugacity coefficient for a given reduced
temperature.
 Fugacity could be considered a “corrected pressure” for the real gas, but should never be used to replace
pressure in equations of state (or any other equations for that matter). That is, it is untrue to write expressions
such as f V = nRT.
 Fugacity is strictly a tool, conveniently defined so that the chemical potential equation for a real gas turns out to
be similar to the equation for an ideal gas.
 Fugacity
 It is simply a measure of molar Gibbs energy of a real gas.
 Modifying the simple equation for chemical potential of an ideal gas by introducing the concept of a fugacity (f).
 The fugacity is an “effective pressure” which forces the equation below to be true for real gases:
f
µ)P,T) = µ)T) + RT ln ( 𝜽) (1) ;Where; Pθ = 1.0 atm
𝑷
 A plot of the chemical potential for an ideal and real gas is shown as a function of the pressure at constant
temperature.
 The fugacity has the units of pressure. As the pressure approaches zero, the real gas approach the ideal gas
behavior and f approaches the pressure.

 If fugacity is an “effective pressure” i.e., the pressure that gives the right value for the chemical potential of a
real gas.
 So, the only way we can get a value for it and hence for µ is from the gas pressure.
 Thus we must find the relation between the effective pressure f and the measured pressure P in equation below :
 Let us: f=φP (2)

 Where; φ is defined as the fugacity coefficient; φ is the “fudge factor” that modifies the actual measured
pressure to give the true chemical potential of the real gas.
 By introducing φ we have just put off finding f directly.
 Thus, now we have to find φ.
 Substituting for φ in the above equation (2) gives:
P
µ(P,T) =µ𝛉(T) + RT ln ( 𝛉) + RT ln φ = µ(ideal gas) + RT ln φ (3)
𝐏
µ)P,T( - µ(ideal gas) + RT ln φ (4)
 Equation (4) shows that the difference in chemical potential between the real and ideal gas lies in the term
RT ln φ.
 This is the term due to molecular interaction effects.
 The equation relating f or φ to the measured pressure P.
 Note that as P → 0, the real gas → ideal gas, so that f → P and φ → 1.
 The fugacity coefficient (φ( = f /p is given by:

 Thus the fugacity of a gas is readily calculated at same pressure P if Z is known as a function of
pressure up to that particular pressure.

 At low to intermediate pressures Z<1, attraction dominates and the area under the curve of the RHS plot,

is Negative.  Thus f = p exp (negative power). and f < p, f < 1.

 At high pressures Z > 1, repulsion dominates and > 0 and f > p, f > 1.
 The Fugacity of van der Waals

 From the compressibility factor Z of a Van der Waals:

 From the fugacity equation:

Example: Given that the van der Walla's constants of nitrogen are: a = 1.408 L2 atm mol-2 and b =
0.03913 L mol-1. Calculate the fugacity of nitrogen gas at 50bar and 298K.

Fugacity (f ) = 48.2 bar

 Fugacity ( f ): measure the pressure for real gases.
It a measure like quantity used measure the pressure of real gas measured by atmosphere unit. It is used to
measure the Gibbs free energy change of real gas.

Variable : (substance in state) A ↔ (substance in state) B

Pressure : PA PB
Gibbs free energy: GA GB

Case 1: by applied for ideal gas:

(∂G/∂P)T = V ; for ideal gas : ∂G = (RT/ P) ∂P and (n =1)
𝐆𝐁 𝐏𝐁 𝐑𝐓
‫𝐏𝐝 𝐏 𝐀𝐏׬ = 𝐆𝐝 𝐀𝐆׬‬ (1)
GB - GB = RT ln PB / PA or GB - GB = RT ln PB - RT ln PA
RT ln PB = GB + RT ln PA - GA
ln PB = GB / RT + ( ln PA – GA / RT) (2)

For Real gas: ( P → f ) :

ln fB = GB / RT + ( ln fA – GA / RT) (3)
at PA → 0 ; then : ∴ fA = PA , pressure produced from Escaping.
ln fB = GB / RT + 𝐥𝐢𝐦 ( 𝐥𝐧 𝐟𝐀 – 𝐆𝐀/𝐑𝐓) (4)
𝐏→𝟎
right side constant at given T
Therefore; ln fB = GB / RT (5)
By equation (5) becomes measure G by f :
 In General case: ∂GB = RT ∂ ln fB (6)
 Effect of Pressure on Fugacity:
(∂G/∂P)T = V , (RT∂ ln f /∂P)T = V
∴ (∂ lnf /∂P)T = V/RT (7)
 we used equation (7) for real gas also solid and liquid.
𝒇𝟐 𝑷𝟐 𝑽
‫𝟏𝒇׬‬ 𝒅𝒍𝒏𝒇 = ‫𝑷𝒅 𝑻𝑹 𝟏𝑷׬‬ (8)
𝑽
ln ( f2 / f1) = (P2 – P1) (9)
𝑹𝑻
 From equation (9) the fugacity don’t measure but calculated from pressure, but have to know P2 and
P1.

 Effect of Temperature on Fugacity:

∂G = RT ln f
Substance ↔ Vapor
G G*
f f*
𝑮∗ 𝒇∗
‫𝒇 𝒏𝒍𝒅𝑻𝑹 𝒇׬ = 𝑮𝒅 𝑮׬‬
G* - G = RT ln∗ f*/ f (10)
𝝏𝑮 𝝏𝑮 𝝏𝒍𝒏 𝒇∗/𝒇
- = RT
∗ 𝝏𝑻 𝝏𝑻 𝝏𝑻
𝑮 −𝑮 𝑹𝑻 𝝏𝒍𝒏𝒇∗ 𝑹𝑻𝝏𝒍𝒏𝒇
𝑻
=
𝝏𝑻
- 𝝏𝑻
 𝛛𝐆 𝐆 −𝐇 𝐆−𝐇
(∂G/∂T)P = - s ; G = H – Ts → ( )= or - s =
∗ ∗ 𝛛𝐓
∗ 𝐓 𝐓
𝐆 −𝐇 𝐆−𝐇 𝐆 −𝐆 𝑹𝑻𝝏𝒍𝒏𝒇∗ 𝑹𝑻𝝏𝒍𝒏𝒇
∴ =( )= + - 𝝏𝑻
𝐓 𝐓 𝐓 𝝏𝑻
 (H*- H)= ∆Hvap → heat of Vaporization:
𝑯∗ 𝑯
 If f * is very small (f * = P) → - + = independent of T at constant P.
𝑻 𝑻
 At low f and P = constant , f * independent on T.
𝑯∗ 𝑯 𝑹𝑻𝝏𝒍𝒏𝒇
 Multiply equation (11) on (-1) , then; ( - )= (11)
𝑻 𝑻 𝝏𝑻

𝑯∗ 𝑯 𝑹𝑻𝝏𝒍𝒏𝒇
 Therefore; - + =- (12)
𝑻 𝑻 𝝏𝑻
∗
𝝏𝒍𝒏𝒇 (𝐇 −𝐇)
= (13)
𝝏𝑻 𝐑𝐓𝟐
where; (H* - H) is the ideal heat of vaporization.
𝒇𝟐 𝑻𝟐 𝐇∗ −𝐇
 Integration the equation (13) : ‫𝒇 𝒏𝒍𝝏 𝟏𝒇׬‬ = ‫𝑻𝝏 𝟐𝐓𝐑 𝟏𝑻׬‬
𝒇𝟐 𝐇∗ −𝐇 𝟏 𝟏 ∆𝑯𝒗𝒂𝒑 𝟏 𝟏
ln ( 𝒇𝟏) = ( ) [ - ] or ln ( 𝒇𝟐 )=( )[ - ] (14)
𝐑 𝐓𝟐 𝐓𝟏 𝒇𝟏 𝑹 𝑻𝟐 𝑻𝟏
 Equation (14) is valid for real gas, solid and liquid materials.
 Pure Real Gas System
 For ideal gas → PV = nRT
 For real gas:(Vander wall’s equation)→ (P +a /V2)(V – b) = nRT , n= 1.
 Virial equations: PV = A + B/V + C/V2 + D/V3 + …………
where; A = first Viral coefficient & B = second Viral coefficient and
C = Third Viral coefficient.
Pressure : PV = A + BP + CP2 + DP3 + …………
How is useful from this equation to calculate fugacity ?
(∂G/∂P)T = V & (RT∂ ln f /∂P)T = V
𝝏𝒍𝒏𝒇 𝑽 𝝏𝒍𝒏𝑷
= subtract on (15)
𝝏𝑷 𝑹𝑻 𝝏𝑷
𝛛𝐥𝐧𝒇 𝛛𝐥𝐧𝑷 𝐕 𝛛𝐥𝐧𝑷 𝛛𝑷
− = − , where; ln P =
𝛛𝐏 𝛛𝐏 𝐑𝐓 𝛛𝐏 𝐏
𝛛𝐥𝐧𝒇/𝑷 𝐕 𝛛𝑷 𝐕 𝟏
= - =( - ) , by integration this equation:
𝛛𝐏 𝐑𝐓 𝐏𝛛𝐏 𝐑𝐓 𝐏
𝒇/𝑷 𝛛𝐥𝐧 𝒇/𝑷 𝑷 𝐕 𝟏
‫𝟎׬‬ 𝛛𝐏
= ‫ 𝐓𝐑( 𝟎׬‬− 𝐏 )𝝏𝑷
 Produced the general equation for Real Pure gases:
𝑷 𝑽 𝟏
ln ( 𝒇𝑷 ) = ‫ ( 𝟎׬‬− )𝒅𝑷 (16)
𝑹𝑻 𝑷

Case 1: for ideal gas : when (n=1): PV= RT → V = RT/P.

𝑷 𝐕 𝟏
ln ( 𝒇𝑷 ) = ‫ ( 𝟎׬‬− )𝒅𝑷 , if ln ( 𝒇𝑷 ) = 0 → ( 𝒇𝑷 ) = 1 ; then : f = P .
𝐑𝐓 𝐏
Case 2: by applied for gas slightly imperfect:
𝑹𝑻
PV = A + BP = RT + BP ∴ V = + B , Therefore;
𝑷
𝑷 𝐕 𝟏 𝑷 𝐑𝐓 𝑩 𝟏
ln ( 𝒇𝑷 ) = ‫( 𝟎׬‬ − )𝒅𝑷 = ‫( 𝟎׬‬ + − )𝒅𝑷
𝐑𝐓 𝐏 𝐑𝐓𝐏 𝐑𝐓 𝐏
𝑩𝑷
∴ ln ( 𝒇𝑷 ) = or ( 𝒇𝑷 ) = 𝒆𝑩𝑷/𝑹𝑻 ( 17 )
𝐑𝐓
where; B = second Viral coefficient
when we know B can evaluated the change between ( 𝒇𝑷) or calculate f by pressure and by using B.
Note:
𝒙𝟐 𝒙𝟑
𝒆𝒙 = 1 + x + + , but 2i and 3i are very small, then; 𝒆𝒙 = 1 + x.
𝟐𝒊 𝟑𝒊

𝑩𝑷/𝑹𝑻 𝑩𝑷 𝑹𝑻+𝑩𝑷 𝑷𝑽
𝒆 =1+ = = , where; PV= A + BP = RT + BP
𝑹𝑻 𝑹𝑻 𝑹𝑻

𝑹𝑻 𝑽 𝟏
P+ → =
𝑽 𝑹𝑻 𝑷
𝒇 𝑷
∴= =
𝑷 𝑷𝒊𝒅𝒆𝒂𝒍
Case 3 : For gas Far way in ideal (Real gas):
𝒇 𝑷 𝐕 𝟏
‫ ( 𝟎׬ = ) 𝑷 ( 𝐧𝐥𝝏 ׬‬− )𝝏𝑷
𝐑𝐓 𝐏
(18)
𝑹𝑻
PV = RT + BP+ CP2 ; ∴ V= + B + CP
𝑷
𝑹𝑻+𝑩𝑷+ 𝑪𝑷𝟐 𝑹𝑻 𝑩𝑷 𝑪𝑷𝟐
V = = + +
𝑷𝑹𝑻 𝑷𝑹𝑻 𝑷𝑹𝑻 𝑷𝑹𝑻
𝟏 𝑩 𝐂𝐏
∴V= + + (19)
𝑷 𝑹𝑻 𝑹𝑻
By subtract V value from equation (19) in equation (18) produced:
𝐑𝐓
𝒇 𝑷 𝐏 +𝐁+𝐂𝐏 𝟏
‫𝐓𝐑 ( 𝟎׬= ) 𝑷 ( 𝐧𝐥 𝝏 ׬‬ − )𝝏𝐏
𝐏
𝑷 𝟏 𝑩 𝐂𝐏 𝟏
𝐥𝐧 ( 𝒇𝑷 ) = ‫ ( 𝟎׬‬+ + − )𝝏𝐏
𝑷 𝑹𝑻 𝑹𝑻 𝐏
𝒇 𝑷 𝑩 𝑷 𝐂𝐏
𝐥𝐧 ( 𝑷 ) = ‫𝟎׬‬ 𝝏𝐏 + ‫𝟎׬‬ 𝝏𝐏
𝑹𝑻 𝑹𝑻
𝑩 𝐂𝐏𝟐
∴ 𝐥𝐧( 𝒇𝑷 ) = P + (20)
𝑹𝑻 𝟐𝑹𝑻
How is calculate the fugaciy ?
There are many methods for calculate the fugacity which graphical and mathematical
methods. But we study here the mathematical method.
 Fugacity calculate from law of corresponding state:
 We can calculate the fugacity from this method which related to law of corresponding state:
𝑻 𝑷 𝑽
= TReduced & = PReduced & = VReduced
𝑻𝒄 𝑷𝒄 𝑽𝒄
 The gases which have the same values of TR , VR and PR near from ideality in the same quantity.
𝐏𝐕 𝐏𝐑 .𝐕𝐑
=Z and =Z
𝐑𝐓 𝐑𝐓𝐑
where; Z = compressibility coefficient.
 And also the gases which have the same values of TR , VR and PR must be have the same values of
Z.
𝐏𝐕 𝐙𝐑𝐓
=Z ; PV = ZRT , therefore; V= (21)
𝐑𝐓 𝐏
𝑷 𝐕 𝟏
‫= ) 𝑷𝒇 ( 𝐧𝐥𝝏 ׬‬ ‫𝐓𝐑( 𝟎׬‬
− )𝝏𝑷
𝐏
(22)
 By abstract V value from equation (21) in equation (22) ∶

𝑷 𝐙𝐑𝐓 𝟏 𝑷 𝐙 𝟏
𝐥𝐧 ( 𝒇𝑷 ) = ‫( 𝟎׬‬ − )𝝏𝑷 = ‫ ( 𝟎׬‬− )𝝏𝑷 (23)
𝐏𝐑𝐓 𝐏 𝐏 𝐏

𝒇
∴ 𝐥𝐧 𝑷
= 𝒁 − 𝟏 𝐥𝐧 𝑷 (24)
 Note:
 We need the Z values from the References (Tables) for any gas, will be evaluate the fugacity value
at any pressure by using equation (24).
 Home work
1. The fugacity of liquid water at 25°C is 0.0312 atm . take the heat of vaporization 43.7249 KJ
and calculate the fugacity at 27°C.