ENCH-633: Chemical

Thermodynamics

Sathish Ponnurangam
Fall 2018

Week - 5: Fugacities in gas mixture

(Reading: Chap-5 Molecular Thermodynamics Of Fluid-Phase Equilibria by Prausnitz et. al.,
Additional reading: Chap-6,7 Engineering and Chemical thermodynamics by Koretsky)
Virial EoS
Γ 𝑟
∞ − 𝑘𝑇
•𝐵= 2𝜋𝑁𝐴 0 1−𝑒 𝑟 2 𝑑𝑟
2
8𝜋2 𝑁𝐴 ∞ ∞ 𝑟12 +𝑟13
•𝐶= − 0 0 𝑟12 −𝑟13
𝑓12 𝑓13 𝑓23 𝑟12 𝑟13 𝑟23 𝑑𝑟12 𝑑𝑟13 𝑑𝑟23
3
Γ𝑖𝑗
• 𝑓𝑖𝑗 ≡ exp − −1
𝑘𝑇
• Assumption pairwise additive: Γ𝑖𝑗𝑘 = Γ𝑖𝑗 + Γ𝑗𝑘 + Γ𝑖𝑘

• For mixtures,
Γij 𝑟
∞ −
• 𝐵𝑖𝑗 = 2𝜋𝑁𝐴 0 1−𝑒 𝑘𝑇 𝑟 2 𝑑𝑟
• 𝐵𝑚𝑖𝑥 = 𝑦𝑖2 𝐵𝑖𝑖 + 𝑦𝑖 𝑦𝑗 𝐵𝑖𝑗 +𝑦𝑗2 𝐵𝑗𝑗

2
8𝜋2 𝑁𝐴 ∞ ∞ 𝑟𝑖𝑗 +𝑟𝑖𝑘
• 𝐶𝑖𝑗𝑘 = − 0 0 𝑟𝑖𝑗 −𝑟𝑖𝑘
𝑓12 𝑓13 𝑓23 𝑟12 𝑟13 𝑟23 𝑑𝑟12 𝑑𝑟13 𝑑𝑟23
3
Γ𝑖𝑗
• 𝑓𝑖𝑗 ≡ exp − −1
𝑘𝑇
Show the following
𝑃𝑣 𝐵𝑚𝑖𝑥𝑡 𝐶𝑚𝑖𝑥𝑡
• Given, 𝑧𝑚𝑖𝑥𝑡 = =1+ +
𝑅𝑇 𝑣 𝑣2
• Show the following
𝟐 𝒎 𝟑 𝒎 𝒎
• 𝐥𝐧 𝝋𝒊 = 𝚺𝒋=𝟏 𝒚𝒋 𝑩𝒊𝒋 + 𝟐 𝜮 𝒋=𝟏 𝜮 𝒌=𝟏 𝒚𝒋 𝒚𝒌 𝑪𝒊𝒋𝒌 − 𝒍𝒏𝒛𝒎𝒊𝒙𝒕
𝒗 𝟐𝒗
• Ignoring 3-body interactions
𝟐 𝒎
• 𝐥𝐧 𝝋𝒊 = 𝚺𝒋=𝟏 𝒚𝒋 𝑩𝒊𝒋 − 𝒍𝒏𝒛𝒎𝒊𝒙𝒕
𝒗
Virial coefficients from potential functions
𝚪 𝒓

• 𝐼𝑓 Γ = 0 at all r?
∞ −
𝑩= 𝟐𝝅𝑵𝑨 𝟎 𝟏−𝒆 𝒌𝑻 𝒓𝟐 𝒅𝒓
𝑩=𝟎
• Ideal-gas potential

• 𝐼𝑓 Γ = 0 for r > 𝜎
𝚪 𝒓
∞ −
𝑩= 𝟐𝝅𝑵𝑨 𝟎 𝟏 − 𝒆 𝒌𝑻 𝒓𝟐 𝒅𝒓
𝚪 𝒓 𝝈
𝝈 − 𝒌𝑻 𝒓𝟑
= ∞ for r ≤ 𝜎 𝑩= 𝟐𝝅𝑵𝑨 𝟎 𝟏 − 𝒆 𝒓𝟐 𝒅𝒓 = 𝟐𝝅𝑵𝑨 𝟑
𝟎
𝝈𝒊 +𝝈𝒋 𝟑
• Hard-sphere potential 𝑩=
𝟐𝝅𝑵𝑨 𝝈𝟑
; for mixtures, 𝑩 =
𝟐𝝅𝑵𝑨 𝟐
𝟑 𝟑

K
• 𝐼𝑓 Γ =− 6 for r > 𝜎
r
= ∞ for r ≤ 𝜎
• Sutherland potential
L-J potential
• 2-parameter potential
• Small non-polar molecules
• Repulsive part is not vertical but has a finite slope
𝚪 𝒓
∞ −
• 𝑫𝒊𝒇𝒇𝒊𝒄𝒖𝒍𝒕 𝒕𝒐 𝒊𝒏𝒕𝒆𝒈𝒓𝒂𝒕𝒆, 𝑩 = 𝟐𝝅𝑵𝑨 𝟎 𝟏−𝒆 𝒌𝑻 𝒓𝟐 𝒅𝒓
• Numerical integration
• In many cases, two parameters obtained from fitting B
are not same as obtained using other methods
(viscosity)
• L-J potential is the reality even for simple fluids such as argon
Square-well potential
• Easy to integrate B
𝚪 𝒓
∞ − 𝐑𝟑 −𝟏 𝝐
•𝑩= 𝟐𝝅𝑵𝑨 𝟎 𝟏−𝒆 𝒌𝑻 𝒓𝟐 𝒅𝒓 = 𝐛𝟎 𝐑𝟑 𝟏 − 𝟑 𝐞𝐱𝐩
𝐑 𝑹𝑻

• Three adjustable parameters, good fit to

experimental data
Kihara Potential
• LJ – soft-sphere potential: molecules can
completely go through each other, as long as
sufficient KE is available
• Kihara: hard core (2a) and soft shell
• Intermolecular distance: distance between edges of core
than atom centers
• Core can be spherical, rod, tetrahedra, triangles, prisms etc..,
• Kihara potential: The parameters from fitting
data is more consistent than L-J method
• 3 parameters: hence better than L-J to model a large
number of non-polar
• Core diameter is also consistent with value
obtained by other methods
LJ vs. Kihara
Stockmayer potential
• What about Keesom and Debye interactions?
• Debye can already be considered as a part of 2-
or 3- parameter r6 potentials
• Keesom is temperature-dependent (orientation)
• Stockmayer = LJ+Keesom
• Two parameter equation
• Dipole moment is a fixed value and angle depend on T
• : is still defined where vdW attr=repulsive (excluding
Keesom)
Stockmayer potential

L-J
Third virial coefficient
• Fitting B data using Kihara potential and
assuming pairwise additivity:
Non-additive corrections
• Non-additive corrections were made for small
non-polar molecules using quantum mechanical
calculations
• Kihara + non-additive corrections = best fit for C
Virial Coefficients from Molecular
Corresponding States Correlations
• B can be related to (𝜀, 𝜎) through any two parameter potential function
model:
Γ 𝑟
• 𝜀
=𝐹 𝜎
𝚪 𝒓
∞ −
• 𝑩= 𝟐𝝅𝑵𝑨 𝟎 𝟏−𝒆 𝒌𝑻 𝒓𝟐 𝒅𝒓
𝚪 𝒓 𝒓
𝜺 𝜺 𝜺𝑭
𝑩 ∞ − 𝒓 𝟐 𝒓 ∞ − 𝝈 𝒓 𝟐 𝒓
• = 𝟏−𝒆 𝒌𝑻 𝒅 𝟏−𝒆 𝒌𝑻 𝒅
𝟐𝝅𝑵𝑨 𝝈𝟑 𝟎 𝝈 𝝈 𝟎 𝝈 𝝈

• If we connect these constants (𝜀, 𝜎) to critical constants (𝑣𝑐 , 𝑇𝑐 )

𝜀
• Set 𝑣𝑐 = 𝜎 𝑎𝑛𝑑 ∝ 𝑇𝑐
𝑘
𝐵 𝑇
• Then, = 𝐹𝐵
𝑣𝑐 𝑇𝑐
• For e.g., from experimental B values for pure species of simple fluids, following equation
can be fitted
−1 −2
𝐵 𝑇 𝑇
• = 0.43 − 0.886 − 0.694 (small non polar molecules)
𝑣𝑐 𝑇𝑐 𝑇𝑐
−1 −2 −4.5
𝐵 𝑇 𝑇 𝑇
• = 0.43 − 0.886 − 0.694 − 0.0375(𝑛 − 1) (large non polar molecules)
𝑣𝑐 𝑇𝑐 𝑇𝑐 𝑇𝑐
For mixtures

• To find cross-coefficient Bij,

𝐵𝑖𝑗 𝑇 −1 𝑇 −2
• = 0.43 − 0.886 − 0.694
𝑣𝑐𝑖𝑗 𝑇𝑐𝑖𝑗 𝑇𝑐𝑖𝑗

• Given,

• Then, Volume averaging

Geometric mean – upper limit and not good for asymmetric molecules

Simplified expression for asymmetric molecules

3 parameter equation (𝒗𝒄 , 𝑻𝒄 , 𝒏)
−1 −2 −2
𝐵 𝑇 𝑇 𝑇
• = 0.43 − 0.886 − 0.694 − 0.0375(𝑛 − 1) (large non polar molecules)
𝑣𝑐 𝑇𝑐 𝑇𝑐 𝑇𝑐

• n is the number of carbon atom • 𝐹𝑜𝑟 𝑚𝑖𝑥𝑡𝑢𝑟𝑒𝑠,

Instead of n, can  be used?
• Pitzer-Tsonopoulos correlation:
• Tsonopoulos correlation
Tsonopoulos correlation good for normal fluids For polar & H-bonding fluids
(moderate size, non-polar or slightly polar, no
association (H-bonds))

When T is small,
effective of  is high
Deviations due to chemical interactions

• Equilibrium constant for dimerization and B can established

• Both are two body interactions
• Trimerization constant and C
• Association leads to z<1
• Dissociation: z>1
Strong Dimerization

• Assuming 1 mole of acetic acid

initially and ideal gas behavior

• With PVT data and , • Let  be the fraction molecules that

dimerized
• K can be found for pure
species association
Cross-association

• A & B are similar hence

above method works
Weak dimerizations
• Consider pure polar gas, A
• Intermolecular interaction = non-polar (dispersion)+association forces
• 𝑃𝑉 = 𝑛 𝑇 (𝑅𝑇 + 𝐵𝑃)
• 𝐵 = 𝐵𝑛𝑜𝑛𝑝𝑜𝑙𝑎𝑟 + 𝐵𝑝𝑜𝑙𝑎𝑟
• Bpolar and dimerization constant can be related as follows
𝑅𝑇𝐾
• 𝐵𝑝𝑜𝑙𝑎𝑟 = − 0
𝑃
• 𝐵𝑛𝑜𝑛𝑝𝑜𝑙𝑎𝑟 is negative and typically small compared to 𝐵𝑝𝑜𝑙𝑎𝑟
• Hence most correlations for 𝐵𝑛𝑜𝑛𝑝𝑜𝑙𝑎𝑟 is sufficient (Pitzer’s)
• However, 𝐵𝑛𝑜𝑛𝑝𝑜𝑙𝑎𝑟 can be positive at high Tr for stable gases (no
dissociation)
• Use, excluded volume (inaccessible volume of the molecules) to account for the positive
Fugacities at high densities
• Virial EoS with only B is not good for high
densities, typically
• If C,D.., are neglected, not applicable for densities >
1.5c
• If D, .., are neglected, not applicable for densities >
1.75c
• Calculation of gas phase fugacities at high
densities – semi-empirical methods (empirically
derived EoS)
Solubilities of Solids and Liquids in
Compressed gases
•  for low P gases ~ 1
•  for high P ǂ 1
• Liquids or solids solubility in high P gases need  to
be evaluated
• Consider solid-gas equilibrium
• Consider that gas (1) dissolution in solid (2) is negligible
(typically true)
• Hence solid phase is pure (ideal)
• Gas phase non-ideal