P-V-T behaviour of gas

mixtures
Introduction
• So far we have focused on the properties of pure compounds
• Many important thermodynamic applications, however, involve
mixtures of several pure substances
• It is possible to prepare tables of properties and charts for mixtures
e.g. air
• However it is not practical since a limitless number of mixtures can be
prepared
• Hence there must be rules to compute the properties of the mixtures
• These rules may differ for ideal and real gases
Revision on concentration
• If 𝑦𝑖 is mole fraction of a component i in the mixture
• 𝑤𝑖 is the mass fraction of component i in the mixture
• 𝑛𝑖 is number of moles of component i in the mixture
• 𝑛ሶ 𝑖 is the molar flowrate of component i in the mixture
• 𝑚𝑖 is mass of component i in the mixture
𝑛𝑖 𝑛ሶ 𝑖
• 𝑦𝑖 = =
σ𝑘
𝑖=1 𝑛𝑖 σ𝑘
𝑖=1 𝑛ሶ 𝑖
𝑚𝑖 𝑚ሶ 𝑖
• 𝑤𝑖 = =
σ𝑘
𝑖=1 𝑚𝑖 σ𝑘
𝑖=1 𝑚ሶ 𝑖
More on the basic definitions
1
• 𝑀𝑤𝑚 = σ𝑖=𝐼 𝑦
𝑖=1 𝑖 𝑀𝑤𝑖 = σ𝑖=𝐼
𝑖=1 (𝑤𝑖 /𝑀𝑤𝑖 )
Where 𝑀𝑤𝑚 is the molecular weight of the mixture
𝑀𝑤𝑖 is the molecular weight of component I
𝑅𝑢
• 𝑅𝑚 =
𝑀𝑤𝑚
• 𝑅𝑚 is the gas constant for the mixture
Additive law
• The prediction of the P-v-T behaviour of gas mixtures is
usually based on two models
• Dalton’s law of additive pressures: The pressure of a gas
mixture is equal to the sum of the pressures each gas would
exert if it existed alone at the mixture temperature and
volume

• Amagat’s law of additive volumes: The volume of a gas

mixture is equal to the sum of the volumes each gas would
occupy if it existed alone at the mixture temperature and
pressure
More on additive law
• Dalton’s and Amagat’s laws hold exactly for ideal-gas mixtures, but
only approximately for real-gas mixtures
• For ideal gases, these two laws are identical and give identical results

• Dalton’s law of additive pressures and Amagat’s law of additive

volumes can also be used for real gases, often with reasonable
accuracy
• They are usually used together with the compressibility factor
More on additive law
• 𝑃𝑚 𝑉𝑚 = 𝑁𝑍𝑚 𝑅𝑢 𝑇𝑚
• 𝑍𝑚 = σ𝑘𝑖=1 𝑦𝑖 𝑍𝑖
• 𝑍𝑖 is determined from either 𝑇𝑚 and 𝑉𝑚 (Dalton’s law) and 𝑇𝑚 and 𝑃𝑚
(Amagat’s law)
Pseudo-pure substance approach
• Another approach for predicting the P-v-T behaviour of a gas mixture
is to treat the gas mixture as a pseudo-pure substance
• One of such techniques is the Kay’s rule
′
• The technique uses use of a pseudocritical pressure 𝑃𝐶,𝑚 and
′
pseudocritical temperature 𝑇𝐶,𝑚 for the mixture
′
• Where 𝑃𝐶,𝑚 = σ𝑘𝑖=1 𝑦𝑖 𝑃𝐶,𝑖 and 𝑇𝐶,𝑚
′
= σ𝑘𝑖=1 𝑦𝑖 𝑇𝐶,𝑖
• The compressibility factor of the mixture, 𝑍𝑚 can be determine using
′ ′
𝑃𝐶,𝑚 and 𝑇𝐶,𝑚
More on Pseudo-pure substance approach
• Another approach is to apply a real gas equation such as Van der
Waal’s equation, Peng-Robinson etc.

• The two constants of the mixture can be calculated by

𝑘 0.5 2
• 𝑎𝑚 = σ𝑖=1 𝑦𝑖 𝑎𝑖 , 𝑏𝑚 = σ𝑘𝑖=1 𝑦𝑖 𝑏𝑖
Example
A rigid tank contains 2 kmol of N2 and 6 kmol of CO2 gases at 300 K and
15 MPa. Estimate the volume of the tank on the basis of
• the ideal-gas equation of state,
• Kay’s rule,
• compressibility factors and Amagat’s law
• compressibility factors and Dalton’s law.
Solution
𝑁 𝑇 𝑅𝑈 𝑇
• 𝑉𝑖𝑑𝑒𝑎𝑙 =
𝑃
• 𝑁𝑇 = 2 + 6 = 8𝑘𝑚𝑜𝑙
8×8.314×300
• 𝑉𝑖𝑑𝑒𝑎𝑙 = = 1.3𝑚3
15000
• For the real gas, 𝑉𝑅𝑒𝑎𝑙 = 𝑍𝑉𝑖𝑑𝑒𝑎𝑙 ,
𝑇𝑐𝑁2 = 126.2𝐾, 𝑃𝑐𝑁2 = 3.39𝑀𝑃𝑎, 𝑇𝑐𝐶𝑂2 = 304.2𝐾, 𝑃𝑐𝐶𝑂2 = 7.39𝑀𝑃𝑎
• For Kay’s rule
𝑇𝐶 = 𝑦𝑁2 𝑇𝑐𝑁2 + 𝑦𝐶𝑂2 𝑇𝑐𝐶𝑂2 = 0.25 × 126.2 + 0.75 × 304.2 = 259.7𝐾
𝑃𝐶 = 𝑦𝑁2 𝑃𝑐𝑁2 + 𝑦𝐶𝑂2 𝑃𝑐𝐶𝑂2 = 0.25 × 3.39 + 0.75 × 7.39 = 6.39MPa
 𝑃 15 𝑇 300
• 𝑃𝑟 = = = 2.3, 𝑇𝑟 = = = 1.2
𝑃𝑐 6.39 𝑇𝑐 259.7
• 𝑍 = 0.49,𝑉𝑅𝑒𝑎𝑙 = 0.49 × 1.33 = 0.65𝑚3
For Amagat Law
• 𝑍𝑚 = 𝑦𝑁2 𝑍𝑁2 + 𝑦𝐶𝑂2 𝑍𝐶𝑂2
𝑃 15 𝑇 300
• For N2 𝑃𝑟 = = = 4.4, 𝑇𝑟 = = = 2.4, 𝑍𝑁2 = 1.02
𝑃𝑐 3.39 𝑇𝑐 126.2
𝑃 15 𝑇 300
• For CO2 𝑃𝑟 = = = 2, 𝑇𝑟 = = = 0.99, 𝑍𝐶𝑂2 = 0.3
𝑃𝑐 7.39 𝑇𝑐 304.2
• 𝑍𝑚 = 0.25 × 1.02 + 0.75 × 0.3 = 0.48
• 𝑉𝑅𝑒𝑎𝑙 = 0.48 × 1.33 = 0.64𝑚3
• For Dalton’s law
• 𝑍𝑚 = 𝑦𝑁2 𝑍𝑁2 + 𝑦𝐶𝑂2 𝑍𝐶𝑂2
𝑉 1.33 𝑇 300
• For N2 𝑉𝑟 = 𝑁𝑇 𝑅 𝑈 𝑇𝐶 = 2×8.314×126.2 = 2.14, 𝑇𝑟 = = = 2.4, 𝑍𝑁2 = 0.99
𝑇𝑐 126.2
𝑃𝐶 3390
𝑉 1.33 𝑇 300
• For CO2 V𝑟 = 𝑁𝑇 𝑅𝑈 𝑇𝐶 = 6×8.314×304.2 = 0.64, 𝑇𝑟 = = = 0.99, 𝑍𝐶𝑂2 = 0.56
𝑇𝑐 304.2
𝑃𝐶 7390

• 𝑍𝑚 = 0.25 × 0.99 + 0.75 × 0.56 = 0.67

• 𝑉𝑅𝑒𝑎𝑙 = 0.67 × 1.33 = 0.89𝑚3 , this V is now used again
• For N2 𝑉𝑟 = 1.44. For CO2 V𝑟 = 0.43
 Vr (N2) Vr (CO2) Z(N2) Z(CO2) Zm V

1 2.1 0.64 0.99 0.56 0.67 0.89

2 1.44 0.4 0.97 0.42 0.56 0.74
3 1.2 0.36 1 0.37 0.52 0.7
Estimation of other properties for mixtures
• ℎ𝑚 = σ𝑘𝑖=1 𝑤𝑖 ℎ𝑖 , ℎത 𝑚 = σ𝑘𝑖=1 𝑦𝑖 ℎത 𝑖
• 𝑢𝑚 = σ𝑘𝑖=1 𝑤𝑖 𝑢𝑖 ,ത
𝑢𝑚 = σ𝑘𝑖=1 𝑦𝑖 𝑢ത 𝑖
• 𝑐𝑣,𝑚 = σ𝑘𝑖=1 𝑤𝑖 𝑐𝑣,𝑖 , 𝑐𝑣,𝑚
ҧ = σ𝑘𝑖=1 𝑦𝑖 𝑐𝑣,𝑖
ҧ
• 𝑐𝑃,𝑚 = σ𝑘𝑖=1 𝑤𝑖 𝑐𝑃,𝑖 , 𝑐𝑣,𝑚
ҧ = σ𝑘𝑖=1 𝑦𝑖 𝑐𝑃,𝑖
ҧ
Example
Air is a mixture of N2, O2, and small amounts of other gases, and it can
be approximated as 79 percent N2 and 21 percent O2 on mole basis.
During a steady-flow process, air is cooled from 220 to 160 K at a
constant pressure of 10 MPa . Determine the heat transfer during this
process per kmol of air, using
• the ideal-gas approximation,
• Kay’s rule
• Amagat’s law