THERMODYNAMICS 2

Prepared by Gulyaz Najafova

 Chapter 4. Gas mixtures
• Mass and mole fraction
• P-V-T behavior of gas mixtures: Ideal and Real gases

Reference: "Thermodynamics, an engineering approach" Eighth edition. Yunus A. Cengel, Michael A. Boles. Chapter 13
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis

𝑘 𝑘
𝑚𝑚 =∑ 𝑚𝑖 𝑛𝑚 =∑ 𝑛𝑖 is the mass of the mixture
𝑖=1 𝑖=1 is the mole number of the mixture

The number of moles of a nonreacting

mixture is equal to the sum of the
number of moles of its components.
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis

𝑘 𝑘
𝑚𝑚 =∑ 𝑚𝑖 𝑛𝑚 =∑ 𝑛𝑖 is the mass of the mixture
𝑖=1 𝑖=1 is the mole number of the mixture

𝑚𝑖 𝑛𝑖 is the mass fraction

𝑚𝑓 𝑖 = 𝑦 𝑖=
𝑚𝑚 𝑛𝑚 is the mole fraction

The number of moles of a nonreacting

mixture is equal to the sum of the
number of moles of its components.
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis

𝑘 𝑘
𝑚𝑚 =∑ 𝑚𝑖 𝑛𝑚 =∑ 𝑛𝑖 is the mass of the mixture
𝑖=1 𝑖=1 is the mole number of the mixture
𝑘 𝑘
𝑚𝑓 𝑖 =
𝑚𝑖
𝑚𝑚
𝑦 𝑖=
𝑛𝑖
𝑛𝑚
is the mass fraction
is the mole fraction ∑ 𝑚 𝑓 𝑖 =1 ∑ 𝑦 𝑖 =1
𝑖=1 𝑖 =1

The sum of the mole fractions of a

mixture is equal to 1.

The number of moles of a nonreacting

mixture is equal to the sum of the
number of moles of its components.
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis

𝑘 𝑘
𝑚𝑚 =∑ 𝑚𝑖 𝑛𝑚 =∑ 𝑛𝑖 is the mass of the mixture
𝑖=1 𝑖=1 is the mole number of the mixture
𝑘 𝑘
𝑚𝑓 𝑖 =
𝑚𝑖
𝑚𝑚
𝑦 𝑖=
𝑛𝑖
𝑛𝑚
is the mass fraction
is the mole fraction ∑ 𝑚 𝑓 𝑖 =1 ∑ 𝑦 𝑖 =1
𝑖=1 𝑖 =1

The sum of the mole fractions of a

𝑘 𝑘
mixture is equal to 1.
∑ 𝑚𝑖 ∑ 𝑛𝑖 𝑀 𝑖 𝑘
𝑚𝑚 𝑖=1 is the apparent (or average) molar mass of a mixture
𝑀 𝑚= = = 𝑖 =1 =∑ 𝑦 𝑖 𝑀 𝑖
𝑛𝑚 𝑛𝑚 𝑛𝑚 𝑖=1

The number of moles of a nonreacting

mixture is equal to the sum of the
number of moles of its components.
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis

𝑘 𝑘
𝑚𝑚 =∑ 𝑚𝑖 𝑛𝑚 =∑ 𝑛𝑖 is the mass of the mixture
𝑖=1 𝑖=1 is the mole number of the mixture
𝑘 𝑘
𝑚𝑓 𝑖 =
𝑚𝑖
𝑚𝑚
𝑦 𝑖=
𝑛𝑖
𝑛𝑚
is the mass fraction
is the mole fraction ∑ 𝑚 𝑓 𝑖 =1 ∑ 𝑦 𝑖 =1
𝑖=1 𝑖 =1

The sum of the mole fractions of a

𝑘 𝑘
mixture is equal to 1.
∑ 𝑚𝑖 ∑ 𝑛𝑖 𝑀 𝑖 𝑘
𝑚𝑚 𝑖=1 is the apparent (or average) molar mass of a mixture
𝑀 𝑚= = = 𝑖 =1 =∑ 𝑦 𝑖 𝑀 𝑖
𝑛𝑚 𝑛𝑚 𝑛𝑚 𝑖=1

𝑅𝑢 is the gas constant of a mixture

𝑅𝑚 =
𝑀𝑚

The number of moles of a nonreacting

mixture is equal to the sum of the
number of moles of its components.
 COMPOSITION OF A GAS MIXTURE: MASS AND MOLE FRACTIONS
There are two ways to describe the composition of a mixture: either by specifying the number of moles of each component,
called molar analysis, or by specifying the mass of each component, called gravimetric analysis

𝑘 𝑘
𝑚𝑚 =∑ 𝑚𝑖 𝑛𝑚 =∑ 𝑛𝑖 is the mass of the mixture
𝑖=1 𝑖=1 is the mole number of the mixture
𝑘 𝑘
𝑚𝑓 𝑖 =
𝑚𝑖
𝑚𝑚
𝑦 𝑖=
𝑛𝑖
𝑛𝑚
is the mass fraction
is the mole fraction ∑ 𝑚 𝑓 𝑖 =1 ∑ 𝑦 𝑖 =1
𝑖=1 𝑖 =1

The sum of the mole fractions of a

𝑘 𝑘
mixture is equal to 1.
∑ 𝑚𝑖 ∑ 𝑛𝑖 𝑀 𝑖 𝑘
𝑚𝑚 𝑖=1 is the apparent (or average) molar mass of a mixture
𝑀 𝑚= = = 𝑖 =1 =∑ 𝑦 𝑖 𝑀 𝑖
𝑛𝑚 𝑛𝑚 𝑛𝑚 𝑖=1

𝑅𝑢 is the gas constant of a mixture

𝑅𝑚 =
𝑀𝑚
𝑚𝑖 𝑛𝑖 𝑀𝑖 𝑀𝑖 The number of moles of a nonreacting
𝑚𝑓 𝑖 = = = 𝑦𝑖 mixture is equal to the sum of the
𝑚 𝑚 𝑛𝑚 𝑀 𝑚 𝑀𝑚 number of moles of its components.
Mass and mole fractions of a mixture
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES

The prediction of the P-v-T behavior of gas mixtures is usually based on two models:
Dalton’s law of additive pressures and Amagat’s law of additive volumes
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES
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

Dalton’s law of additive pressures for a

mixture of two ideal gases.

John Dalton
1766 – 1844
English chemist, physicist,
and meteorologist
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES
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
Dalton’s law of additive pressures for a
mixture of two ideal gases.

Amagat’s law of additive volumes for

a mixture of two ideal gases.
John Dalton Émile Hilaire Amagat
1766 – 1844
1841-1915
English chemist, physicist,
and meteorologist French physicist
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES

𝑘
Dalton’s law: 𝑃 𝑚=∑ 𝑃 𝑖 (𝑇 𝑚 ,𝑉 𝑚 )
𝑖=1 Exact for ideal gases,
approximate
𝑘 for real gases
Amagata’s law: 𝑉 𝑚=∑ 𝑉 𝑖 (𝑇 𝑚 , 𝑃 𝑚 )
𝑖=1
P-v-T BEHAVIOR OF GAS MIXTURES: IDEAL AND REAL GASES

𝑘
Dalton’s law: 𝑃 𝑚=∑ 𝑃 𝑖 (𝑇 𝑚 ,𝑉 𝑚 )
𝑖=1 Exact for ideal gases,
approximate
𝑘 for real gases
Amagata’s law: 𝑉 𝑚=∑ 𝑉 𝑖 (𝑇 𝑚 , 𝑃 𝑚 )
𝑖=1

is called the component pressure is called the component volume . Note that is the volume a component would occupy if it
existed alone at , not the actual volume occupied by the component in the mixture.

Also, the ratio is called the pressure fraction and the ratio is called the volume fraction of component i.

The volume a component would

occupy if it existed alone at the
mixture T and P is called the
component volume (for ideal gases, it
is equal to the partial volume yiVm).
Ideal-Gas Mixtures

𝑃 𝑖 (𝑇 𝑚 , 𝑉 𝑚) 𝑛𝑖 𝑅𝑢 𝑇 𝑚 /𝑉 𝑚 𝑛 𝑖
= = =𝑦 𝑖
𝑃𝑚 𝑛𝑚 𝑅𝑢 𝑇 𝑚 /𝑉 𝑚 𝑛𝑚
𝑃 𝑖 𝑉 𝑖 𝑛𝑖
So, = = = 𝑦𝑖
𝑃 𝑚 𝑉 𝑚 𝑛𝑚
𝑉 𝑖 (𝑇 𝑚 , 𝑃 𝑚) 𝑛𝑖 𝑅𝑢 𝑇 𝑚 / 𝑃 𝑚 𝑛𝑖
= = = 𝑦𝑖
𝑉𝑚 𝑛𝑚 𝑅𝑢 𝑇 𝑚 / 𝑃 𝑚 𝑛𝑚

𝑦 𝑖 𝑃 𝑚is called the partial pressure (identical to the component pressure for ideal gases)
𝑦 𝑖 𝑉 𝑚 is called the partial volume (identical to the component volume for ideal gases)
 Real Gas Mixtures
First method

In the van der Waals equation, for example, the two constants for the mixture
are determined from
 Real Gas Mixtures
First method

In the van der Waals equation, for example, the two constants for the mixture
are determined from

Second method: Z- compressibility factor

for an ideal gas

PROPERTIES OF GAS MIXTURES: IDEAL AND REAL GASES

Do you remember extensive properties?

PROPERTIES OF GAS MIXTURES: IDEAL AND REAL GASES

Do you remember extensive properties? The extensive properties of a mixture are

determined by simply adding the
properties of the components
 PROPERTIES OF GAS MIXTURES: IDEAL AND REAL GASES

Do you remember extensive properties? The extensive properties of a mixture

are determined by simply adding the
properties of the components

The total internal energy, enthalpy, and entropy of a gas mixture can be expressed, respectively, as
𝑘 𝑘 𝑘
𝑈 𝑚=∑ 𝑈 𝑖=∑ 𝑚𝑖 𝑢𝑖 =∑ 𝑛𝑖 𝑢𝑖 (𝑘𝐽 )
𝑖=1 𝑖=1 𝑖=1
𝑘 𝑘 𝑘
𝐻 𝑚 =∑ 𝐻 𝑖 =∑ 𝑚𝑖 h𝑖=∑ 𝑛𝑖 h𝑖 (𝑘𝐽 )
𝑖=1 𝑖=1 𝑖=1
𝑘 𝑘 𝑘
𝑆𝑚 =∑ 𝑆𝑖 =∑ 𝑚𝑖 𝑠𝑖 =∑ 𝑛𝑖 𝑠 𝑖 (𝑘𝐽 )
𝑖=1 𝑖=1 𝑖=1
By following a similar logic, the changes in internal energy, enthalpy, and entropy of a gas mixture during a process can
be expressed, respectively, as

𝑘 𝑘 𝑘
∆ 𝑈 𝑚 =∑ ∆𝑈 𝑖 =∑ 𝑚 𝑖 ∆ 𝑢𝑖 =∑ 𝑛𝑖 ∆ 𝑢𝑖 (𝑘𝐽 )
𝑖=1 𝑖=1 𝑖=1
𝑘 𝑘 𝑘
∆ 𝐻 𝑚 =∑ ∆ 𝐻 𝑖 =∑ 𝑚𝑖 ∆ h𝑖=∑ 𝑛𝑖 ∆ h𝑖 (𝑘𝐽 )
𝑖=1 𝑖=1 𝑖=1
𝑘 𝑘 𝑘
∆ 𝑆𝑚=∑ ∆ 𝑆𝑖 =∑ 𝑚𝑖 ∆ 𝑠 𝑖=∑ 𝑛𝑖 ∆ 𝑠𝑖 (𝑘𝐽 )
𝑖=1 𝑖=1 𝑖=1
Do you remember intensive properties?
 Do you remember intensive properties?

The intensive properties of a mixture

are determined by weighted averaging.

The internal energy, enthalpy, and entropy of a mixture per unit mass or per unit mole
of the mixture can be determined by dividing the equations above by the mass or the
mole number of the mixture

𝑘 𝑘
𝑢𝑚 =∑ 𝑚 𝑓 𝑖 𝑢𝑖 ( 𝑘𝐽 /𝑘𝑔 ) 𝑢𝑚 =∑ 𝑦 𝑖 𝑢 𝑖 ( 𝑘𝐽 /𝑘𝑚𝑜𝑙 )
𝑖=1 𝑖=1
𝑘 𝑘
h𝑚 =∑ 𝑚 𝑓 𝑖 h𝑖 ( 𝑘𝐽 /𝑘𝑔 ) h𝑚 =∑ 𝑦 𝑖 h𝑖 ( 𝑘𝐽 / 𝑘𝑚𝑜𝑙 )
𝑖=1 𝑖=1
𝑘 𝑘
𝑠 𝑚=∑ 𝑚 𝑓 𝑖 𝑠 𝑖 ( 𝑘𝐽 /𝑘𝑔 ) 𝑠 𝑚 =∑ 𝑦 𝑖 𝑠 𝑖 ( 𝑘𝐽 /𝑘𝑚𝑜𝑙 )
𝑖=1 𝑖=1
 Similarly, the specific heats of a gas mixture can be expressed as

𝑘 𝑘
𝑐 𝑉 ,𝑚 =∑ 𝑚 𝑓 𝑖 𝑐 𝑉 , 𝑖 ( 𝑘𝐽 /𝑘𝑔 ∗ 𝐾 ) 𝑐 𝑉 ,𝑚 =∑ 𝑦 𝑖 𝑐𝑉 ,𝑖 ( 𝑘𝐽 /𝑘𝑚𝑜𝑙 ∗ 𝐾 )
𝑖=1 𝑖=1

𝑘 𝑘
𝑐 𝑃 , 𝑚=∑ 𝑚 𝑓 𝑖 𝑐 𝑃 , 𝑖 ( 𝑘𝐽 /𝑘𝑔 ∗ 𝐾 ) 𝑐 𝑃 , 𝑚=∑ 𝑦 𝑖 𝑐 𝑃 ,𝑖 ( 𝑘𝐽 /𝑘𝑚𝑜𝑙 ∗ 𝐾 )
𝑖=1 𝑖=1

Notice that properties per unit mass involve mass fractions and properties per unit mole involve mole fractions ().
 Ideal-Gas Mixtures
Gibbs–Dalton law
Under the ideal-gas approximation, the properties of a gas are not influenced by the presence of other gases, and each gas
component in the mixture behaves as if it exists alone at the mixture temperature Tm and mixture
volume Vm.

The partial pressure of a component in an ideal-gas mixture is simply , where is the mixture pressure

The entropy change of individual gases in an ideal-gas mixture during a process can be
determined from:

∘ ∘ 𝑃 𝑖 ,2 𝑇 𝑖, 2 𝑃 𝑖, 2
∆ 𝑠𝑖 =𝑠𝑖 ,2 − 𝑠 𝑖 , 1 − 𝑅 𝑖 ln ≅ 𝑐 𝑃 , 𝑖 ln − 𝑅𝑖 ln
𝑃𝑖 ,1 𝑇 𝑖, 1 𝑃 𝑖, 1 is the molar entropy
𝑃𝑖 ,2 𝑇 𝑃 is the average entropy
∆ 𝑠𝑖 =𝑠∘𝑖 ,2 − 𝑠∘𝑖 , 1 − 𝑅 𝑖 ln ≅ 𝑐 𝑃 , 𝑖 ln 𝑖 , 2 − 𝑅 𝑖 ln 𝑖 , 2
𝑃𝑖 ,1 𝑇 𝑖, 1 𝑃 𝑖 ,1

𝑃 𝑖, 2=𝑦 𝑖,2 𝑃 𝑚,2 𝑃 𝑖,1 =𝑦 𝑖 ,1 𝑃𝑚 ,1

Notice that the partial pressure of each component is used in the Partial pressures (not the mixture
evaluation of the entropy change, not the pressure) are used in the evaluation of
mixture pressure entropy changes of ideal-gas mixtures
Real-Gas Mixtures

Consider the following relation for a gas mixture:

𝑑h 𝑚=𝑇 𝑚 𝑑𝑠𝑚 +𝑉 𝑚 𝑑𝑃 𝑚
It can also be expressed as

𝑑 (∑ 𝑚 𝑓 𝑖 h𝑖)=𝑇 𝑚 𝑑 (∑ 𝑚 𝑓 𝑖 𝑠𝑖)+(∑ 𝑚 𝑓 𝑖 𝑉 𝑖) 𝑑𝑃 𝑚
or

∑ 𝑚 𝑓 𝑖 ( 𝑑h𝑖 −𝑇𝑚 𝑑𝑠𝑖 −𝑉 𝑖 𝑑 𝑃𝑚)=0 It is difficult to predict the behavior of

nonideal-gas mixtures because of the
influence of dissimilar molecules on
each other.
which yields

𝑑 h𝑖 =𝑇 𝑚 𝑑 𝑠𝑖 +𝑉 𝑖 𝑑 𝑃 𝑚