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CHE 2120 SOLUTIONS THERMODYNAMICS

Module 2: Solutions Thermodynamics – Theory

FUNDAMENTAL PROPERTY RELATIONS

Homogenous Phases of Constant Composition
Recall the First of Thermodynamics in a closed system with (n) number of moles:

𝑑(𝑛𝑈) = 𝑑𝑄𝑟𝑒𝑣 + 𝑑𝑊𝑟𝑒𝑣

Recall the Second Law of Thermodynamics:
𝑑𝑄𝑟𝑒𝑣 = 𝑇𝑑(𝑛𝑆)
Recall the PV-Work Equation:
𝑑𝑊𝑟𝑒𝑣 = −𝑃𝑑(𝑛𝑉)
Combining the three equation results to:
𝒅(𝒏𝑼) = 𝑻𝒅(𝒏𝑺) − 𝑷𝒅(𝒏𝑽)

Additional Thermodynamic Properties by Definition:

1. Enthalpy 𝐻 ≡ 𝑈 + 𝑃𝑉 𝑑 (𝑛𝐻) = 𝑑(𝑛𝑈) + [𝑃 𝑑 (𝑛𝑉 ) + (𝑛𝑉 ) 𝑑𝑃]
2. Helmholtz Energy 𝐺 ≡ 𝐻 − 𝑇𝑆 𝑑 (𝑛𝐺) = 𝑑(𝑛𝐻) − [𝑇 𝑑 (𝑛𝑆) + (𝑛𝑆) 𝑑𝑇]
3. Gibbs Energy 𝐴 ≡ 𝑈 − 𝑇𝑆 𝑑 (𝑛𝐴) = 𝑑 (𝑛𝑈) − [𝑇 𝑑 (𝑛𝑆) + (𝑛𝑆) 𝑑𝑇]

Helmholtz Energy (A) - Energy available to do non-PV work in a thermodynamic closed system at constant
volume and temperature.
Gibbs Energy (G) - the energy available to do non-PV work in a thermodynamic closed system at constant
pressure and temperature. Gibbs energy relates the tendency of a physical or chemical system to simultaneously
lower its energy H and increase its disorder S in a spontaneous natural process.
Replacing the 𝑑(𝑛𝑈) in the differential form of Helmholtz energy with 𝑑(𝑛𝑈) = 𝑇𝑑(𝑛𝑆) − 𝑃𝑑(𝑛𝑉)
𝑑(𝑛𝐴) = 𝑇𝑑(𝑛𝑆) − 𝑃𝑑(𝑛𝑉) − [𝑇 𝑑(𝑛𝑆) + (𝑛𝑆) 𝑑𝑇]

𝑑(𝑛𝐴) = 𝑇𝑑(𝑛𝑆) − 𝑃𝑑(𝑛𝑉) − [𝑇 𝑑(𝑛𝑆) + (𝑛𝑆) 𝑑𝑇]

𝒅(𝒏𝑨) = −𝑷𝒅(𝒏𝑽) − (𝒏𝑺)(𝒅 𝑻)

Replacing the 𝑑(𝑛𝑈) in the differential form of enthalpy with 𝑑(𝑛𝑈) = 𝑇𝑑(𝑛𝑆) − 𝑃𝑑(𝑛𝑉)
𝑑 (𝑛𝐻) = 𝑇𝑑(𝑛𝑆) − 𝑃𝑑(𝑛𝑉 ) + [𝑃 𝑑(𝑛𝑉 ) + (𝑛𝑉 ) 𝑑𝑃]
𝑑 (𝑛𝐻) = 𝑇𝑑(𝑛𝑆) − 𝑃𝑑(𝑛𝑉 ) + [𝑃 𝑑(𝑛𝑉 ) + (𝑛𝑉 ) 𝑑𝑃]

𝒅(𝒏𝑯) = 𝑻𝒅(𝒏𝑺) + (𝒏𝑽) 𝒅𝑷

Using this derived equation substitute in the derivative form of Gibb’s free energy

𝑑 (𝑛𝐺) = 𝑇𝑑(𝑛𝑆) + (𝑛𝑉 ) 𝑑𝑃 − [𝑇 𝑑 (𝑛𝑆) + (𝑛𝑆) 𝑑𝑇]

𝑑 (𝑛𝐺) = 𝑇𝑑(𝑛𝑆) + (𝑛𝑉 ) 𝑑𝑃 − [𝑇 𝑑 (𝑛𝑆) + (𝑛𝑆) 𝑑𝑇]

𝒅(𝒏𝑮) = (𝒏𝑽) 𝒅𝑷 − (𝒏𝑺)(𝒅 𝑻)

Fundamental Property Relations

𝒅(𝒏𝑼) = 𝑻𝒅(𝒏𝑺) − 𝑷𝒅(𝒏𝑽) 𝒅(𝒏𝑯) = 𝑻𝒅(𝒏𝑺) + (𝒏𝑽) 𝒅𝑷
𝒅(𝒏𝑮) = (𝒏𝑽) 𝒅𝑷 − (𝒏𝑺)(𝒅 𝑻) 𝒅(𝒏𝑨) = −𝑷𝒅(𝒏𝑽) − (𝒏𝑺)(𝒅 𝑻)
*Single-phase fluid in a closed system with constant composition

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
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Consider the functional relation for Gibb’s Energy: 𝑛𝐺 = 𝐺(𝑃, 𝑇, 𝑛)

Getting the differentiating the equation, partial derivatives are present:

𝝏(𝒏𝑮) 𝝏(𝒏𝑮)
𝑑 (𝑛𝐺 ) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇
𝝏𝑷 𝑻,𝒏 𝝏𝑻 𝑷,𝒏

these terms in the equation have physical significant meanings which are

𝝏(𝒏𝑮) 𝝏(𝒏𝑮)
[ ] = 𝒏𝑽 [ ] = −𝒏𝑺
𝝏𝑷 𝑻,𝒏 𝝏𝑻 𝑷,𝒏

That is why the fundamental property relation for Gibbs Energy is 𝒅(𝒏𝑮) = (𝒏𝑽) 𝒅𝑷 − (𝒏𝑺)(𝒅 𝑻)

Open Systems with Variable Amounts and Composition

For an open system, it can comprise of more than one composition, thus the equation 𝑛𝐺 = 𝐺(𝑃, 𝑇, 𝑛) also
becomes a function of the number of moles of the chemical species present in the mixture

𝒏𝑮 = 𝑮(𝑷, 𝑻, 𝒏𝟏 , 𝒏𝟐 , 𝒏𝟑 , … , 𝒏𝒊 )
Differentiating the equation results to:
𝜕(𝑛𝐺 ) 𝜕(𝑛𝐺 ) 𝝏(𝒏𝑮) 𝝏(𝒏𝑮) 𝝏(𝒏𝑮)
𝑑(𝑛𝐺) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇 + [ ] 𝒅𝒏 + [ ] 𝒅𝒏 + ⋯ + [ ] 𝒅𝒏
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝝏𝒏𝟏 𝑷,𝑻,𝒏≠𝟏 𝟏 𝝏𝒏𝟐 𝑷,𝑻,𝒏≠𝟐 𝟐 𝝏𝒏𝒊 𝑷,𝑻,𝒏≠𝒊 𝒊

Simplifying the term in blue we get a summation

𝜕(𝑛𝐺) 𝜕(𝑛𝐺) 𝜕(𝑛𝐺) 𝜕(𝑛𝐺)
[ ] 𝑑𝑛1 + [ ] 𝑑𝑛2 + ⋯ + [ ] 𝑑𝑛𝑖 = ∑ [ ] 𝑑𝑛𝑖
𝜕𝑛1 𝑃,𝑇,𝑛≠1 𝜕𝑛2 𝑃,𝑇,𝑛≠2 𝜕𝑛𝑖 𝑃,𝑇,𝑛≠𝑖 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑖 𝑗

Where nj refers to all number of moles except for ni.

The total differential is now:

𝜕(𝑛𝐺 ) 𝜕(𝑛𝐺 ) 𝜕 (𝑛𝐺 )

𝑑 (𝑛𝐺 ) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇 + ∑ [ ] 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑖 𝑗

𝒏𝑽 −𝒏𝑺 𝝁𝒊
By definition, chemical potential is expressed as:
𝜕(𝑛𝐺 )
𝜇𝑖 ≡ [ ] = 𝐺̅𝑖
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗

The differential now becomes:

𝒅(𝒏𝑮) = (𝒏𝑽) 𝒅𝑷 − (𝒏𝑺)(𝒅 𝑻) + ∑ 𝝁𝒊 𝒅𝒏𝒊

𝒊

If the total number of moles in the system is 1mol (n = 1), n i = xi

𝒅𝑮 = 𝑽 𝒅𝑷 − 𝑺 𝒅𝑻 + ∑ 𝝁𝒊 𝒅𝒙𝒊
𝒊

THE CHEMICAL POTENTIAL AND PHASE EQUILIBRIA

Chemical potential - It is the tendency of a substance to react or the tendency of a substance to change its
chemical composition. It is also the tendency of a substance to change its phase.

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
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Let us consider a closed system consisting of two phases in equilibrium, each phase is open to the other, and
mass transfer between phases may occur. The implication of equilibrium is that the temperature T and pressure
P are uniform throughout the closed system.

For the vapor () phase:

𝑑(𝑛𝐺)𝛼 = (𝑛𝑉)𝛼 𝑑𝑃 − (𝑛𝑆)𝛼 𝑑𝑇 + ∑ 𝜇𝑖𝛼 𝑑𝑛𝑖𝛼

𝑖

For the liquid () phase:

𝛽 𝛽
𝑑(𝑛𝐺)𝛽 = (𝑛𝑉)𝛽 𝑑𝑃 − (𝑛𝑆)𝛽 𝑑𝑇 + ∑ 𝜇𝑖 𝑑𝑛𝑖
𝑖

For the whole two-phase system, considered to be a closed system recall that:
𝑑(𝑛𝐺) = (𝑛𝑉) 𝑑𝑃 − (𝑛𝑆)(𝑑 𝑇)
Total-System Property:

(𝑛𝐺) = (𝑛𝐺)𝛼 + (𝑛𝐺)𝛽

Change in Total-System Property = Sum of Changes in Phase Properties

𝑑(𝑛𝐺) = 𝑑(𝑛𝐺)𝛼 + 𝑑(𝑛𝐺)𝛽

𝛽 𝛽
𝑑(𝑛𝐺) = (𝑛𝑉) 𝑑𝑃 − (𝑛𝑆)(𝑑 𝑇) + ∑𝑖 𝜇𝑖𝛼 𝑑𝑛𝑖𝛼 + ∑𝑖 𝜇𝑖 𝑑𝑛𝑖

At equilibrium, the equation becomes

∑𝑖 𝜇𝑖𝛼 𝑑𝑛𝑖𝛼 + ∑𝑖 𝜇𝑖𝛽 𝑑𝑛𝑖𝛽 = 0

Note that the number of moles in the liquid phase and in the vapor phase
are a result of mass transfer between the two phases. Since it is a closed
system in equilibrium, no new moles are added and law of mass
conservation applies. Therefore any addition of moles in the vapor phase
has an equivalent decrease in the liquid phase. Mathematically:
𝛽
𝑑𝑛𝑖𝛼 = −𝑑𝑛𝑖

Substituting the value in the previous equation

∑𝑖 𝜇𝑖𝛼 𝑑𝑛𝑖𝛼 + ∑𝑖 𝜇𝑖𝛽 (−𝑑𝑛𝛼𝑖 ) = 0

Rearranging we get the term
𝛽
∑(𝜇𝑖𝛼 − 𝜇𝑖 )𝑑𝑛𝑖𝛼 = 0
𝑖

For the statement to hold true then

𝛽
𝜇𝑖𝛼 = 𝜇𝑖
PARTIAL PROPERTIES
The chemical potential of a pure component is an intensive property

𝜇𝑖,𝑝𝑢𝑟𝑒 = 𝐺𝑖 𝑖𝑛 𝐽/𝑚𝑜𝑙

The chemical potential of a species in a mixture is a partial molar Gibbs energy

𝜕(𝑛𝐺)
𝜇𝑖 = 𝐺̅𝑖 = [ ] 𝑖𝑛 𝐽/𝑚𝑜𝑙
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
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For any generic property of the solution we denote it as 𝑀 𝑎𝑛𝑑 𝑀 ̅𝑖 which can be unit-mass or unit-mole based.
̅𝑖 refers to any partial molar property of species i which is defined as
𝑀

̅𝑖 ≡ [𝜕(𝑛𝑀)]
𝑀 ̅𝑖 = 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑀 𝑜𝑓 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑀
𝜕𝑛 𝑖 𝑃,𝑇,𝑛𝑗 𝑐ℎ𝑎𝑛𝑔𝑒 𝑖𝑛 𝑚𝑜𝑙𝑒𝑠 𝑜𝑓 𝑐𝑜𝑚𝑝 𝑖

Solution properties 𝑀, 𝑉, 𝑈, 𝐻, 𝑆, 𝐺
Partial properties ̅𝑖
𝑀 𝑉̅𝑖 , 𝑈
̅𝑖 , 𝐻
̅𝑖 , 𝑆𝑖̅ , 𝐺̅𝑖

Pure-species properties 𝑀𝑖 , 𝑉𝑖 , 𝑈𝑖 , 𝐻𝑖 , 𝑆𝑖 , 𝐺𝑖

Equations Relating Molar and Partial Molar Properties

Similarly to how 𝒏𝑮 = 𝑮(𝑷, 𝑻, 𝒏𝟏 , 𝒏𝟐 , 𝒏𝟑 , … , 𝒏𝒊 ) can be differentiated, we can do the same for any property M.

Eqn (1): 𝒏𝑴 = 𝒇(𝑷, 𝑻, 𝒏𝟏 , 𝒏𝟐 , … , 𝒏𝒊 )

𝜕(𝑛𝑀) 𝜕(𝑛𝑀) 𝜕(𝑛𝑀)
Eqn (2): 𝑑(𝑛𝑀) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇 + ∑𝑖 [ ] 𝑑𝑛𝑖
𝜕𝑃 𝑇,𝑛 𝜕𝑇 𝑃,𝑛 𝜕𝑛𝑖 𝑃,𝑇,𝑛
𝑗

̅𝑖 , we can replace it in the equation:

By definition of 𝑀
𝜕(𝑀) 𝜕(𝑀)
Eqn (3): 𝑑(𝑛𝑀) = 𝑛 [ ] 𝑑𝑃 + 𝑛 [ ] ̅𝑖 𝑑𝑛𝑖
𝑑𝑇 + ∑𝑖 𝑀
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥

The equation is in simpler form, where subscript x denotes differentiation at constant composition. Because mole
fraction xi is ni/n, the equation becomes:
𝜕𝑀 𝜕𝑀
Eqn (4a): 𝑑𝑀 = [ ] 𝑑𝑃 + [ ] ̅𝑖 𝑑𝑥𝑖
𝑑𝑇 + ∑𝑖 𝑀
𝜕𝑃 𝑇,𝑥 𝜕𝑇 𝑃,𝑥

Eqn (4b): ̅𝑖
𝑀 = ∑𝑖 𝑥𝑖 𝑀 (defines the summability)

Eqn (5): ̅𝑖 (alternative expression)

𝑛𝑀 = ∑𝑖 𝑛𝑖 𝑀

̅𝑖 . Therefore if we look
For Example we use to property of Volume so we write 𝑉 instead of 𝑀 and 𝑉𝑖 instead of 𝑀
at the partial molar volume in terms of the summability:

̅ 𝟏 + 𝒙𝟐 𝑽
𝑽 = 𝒙𝟏𝑽 ̅ 𝟐 + … + 𝒙𝒊 𝑽
̅ 𝒊 + … + 𝒙𝑵 𝑽
̅𝑵
Volume of Partial Molar Partial Molar Partial Molar Partial Molar
Mixture Volume of Volume of Volume of Volume of
per mole Component 1 Component 2 Component i Component n

Example 11.3 (page 388, 7th Edition Smith & Van Ness):

The need arises in a laboratory for 2000 cm 3 of an antifreeze solution consisting of 30 mole % methanol in water. What
volumes of pure methanol and of pure water at 25℃ (298.15 K) must be mixed to form the 2000 cm 3 of antifreeze, also at
25℃ (298.15 K)? Partial molar volumes for methanol and water in a 30 mole % methanol solution and their pure-species
molar volumes, both at 25℃ (298.15 K), are:

Methanol (1): 𝑉̅1 = 38.632 𝑐𝑚3 𝑚𝑜𝑙 −1 𝑉1 = 40.727 𝑐𝑚3 𝑚𝑜𝑙 −1

Water (2) 𝑉̅2 = 17.765 𝑐𝑚3 𝑚𝑜𝑙 −1 𝑉2 = 18.068 𝑐𝑚3 𝑚𝑜𝑙 −1

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
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Active Learning Opportunity 3.3:

Partial Molar Property M

Eqn (1) ̅𝑖 ≡ [𝜕(𝑛𝑀)]

𝑀 𝜕𝑛 𝑖 𝑃,𝑇,𝑛𝑗≠𝑖

̅𝑖
Eqn (2) 𝑀 = ∑𝑖 𝑥𝑖 𝑀

Write the equivalent expressions of Eqns (1) and (2) for the following thermodynamic properties:

(a) Internal Energy, U

̅𝑖 ≡ [𝜕(𝑛𝑈)]
𝑈 𝑈 = ∑𝑖 𝑥𝑖 𝑈𝑖
𝜕𝑛 𝑖 𝑃,𝑇,𝑛𝑗≠𝑖

̅ 𝟏 + 𝒙𝟐 𝑼
𝑼 = 𝒙𝟏 𝑼 ̅ 𝟐 + … + 𝒙𝒊 𝑼
̅ 𝒊 + … + 𝒙𝑵 𝑼
̅𝑵

(b) Enthalpy, H

̅𝑖 ≡ [𝜕(𝑛𝐻)]
𝐻 𝑈 = ∑𝑖 𝑥𝑖 𝐻𝑖
𝜕𝑛 𝑖 𝑃,𝑇,𝑛𝑗≠𝑖

̅ 𝟏 + 𝒙𝟐 𝑯
𝑯 = 𝒙𝟏 𝑯 ̅ 𝟐 + … + 𝒙𝒊 𝑯
̅ 𝒊 + … + 𝒙𝑵 𝑯
̅𝑵

(c) Entropy, S
𝜕 (𝑛𝑆)
𝑆𝑖̅ ≡ [ ] 𝑆 = ∑𝑖 𝑥𝑖 𝑆𝑖
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗≠𝑖

𝑺 = 𝒙𝟏 𝑺𝟏 + 𝒙𝟐 ̅
𝑺𝟐 + … + 𝒙𝒊 ̅
𝑺𝒊 + … + 𝒙𝑵 ̅
𝑺𝑵
(d) Helmholtz Energy, A
𝜕(𝑛𝐴)
𝐴̅𝑖 ≡ [ ] 𝐴 = ∑𝑖 𝑥𝑖 𝐴𝑖
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗≠𝑖

̅ 𝟏 + 𝒙𝟐 𝑨
𝑨 = 𝒙𝟏 𝑨 ̅ 𝟐 + … + 𝒙𝒊 𝑨𝒊 + … + 𝒙𝑵𝑨
̅𝑵

Gibbs/Duhem Equation
𝝏𝑴 𝝏𝑴
[ ] 𝒅𝑷 + [ ̅𝒊 = 𝟎
] 𝒅𝑻 − ∑ 𝒙𝒊 𝒅𝑴
𝝏𝑷 𝑻,𝒙 𝝏𝑻 𝑷,𝒙
𝒊

at constant temperature and pressure, Gibbs/Duhem Eqn is reduced to:

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
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̅𝒊 = 𝟎
∑ 𝒙𝒊 𝒅𝑴
𝒊

Partial Properties of Binary Solutions

For any binary solution we have components with mole fractions 𝒙𝟏 and 𝒙𝟐 , where 𝒙𝟐 can also be expressed as
(𝟏 − 𝒙𝟏 )
̅𝑖 , Partial Properties for binary solutions are written as
From the summability equation 𝑀 = ∑𝑖 𝑥𝑖 𝑀
̅ 𝟏 + 𝒙𝟐 𝑴
𝑴 = 𝒙𝟏 𝑴 ̅𝟐 (A)
Differentiating the equation (using product rule)
̅𝟏 + 𝑴
𝒅𝑴 = 𝒙𝟏 𝒅𝑴 ̅ 𝟏 𝒅𝒙𝟏 + 𝒙𝟐 𝒅𝑴
̅𝟐 + 𝑴
̅ 𝟐 𝒅𝒙𝟐 (B)
At constant temperature and pressure, the Gibbs/Duhem Equation becomes:
̅ 𝟏 + 𝒙𝟐 𝒅𝑴
𝒙𝟏 𝒅𝑴 ̅𝟐 = 𝟎 (C)

Since 𝑥1 + 𝑥2 = 1 it follows that 𝑑𝑥1 = −𝑑𝑥2 . Eliminating 𝑑𝑥2 in equation (B) and combining the result with
equation (C) give:
𝒅𝑴 𝒅𝑴
̅𝟏 − 𝑴
=𝑴 ̅𝟐 or ̅𝟐 − 𝑴
=𝑴 ̅𝟏 (D)
𝒅𝒙𝟏 𝒅𝒙𝟐

Eliminating 𝒙𝟏 or 𝒙𝟐 in equation A:
̅1 − 𝑥2 (𝑀
𝑀 =𝑀 ̅1 − 𝑀
̅2 ) or ̅1 − 𝑀
𝑀 = 𝑥1 (𝑀 ̅2 ) + 𝑀
̅2

and combining with equation (D) result to:

̅ 𝟏 = 𝑴 + 𝒙𝟐 𝒅𝑴
𝑴 (E1) or ̅ 𝟐 = 𝑴 − 𝒙𝟏 𝒅𝑴
𝑴 (E2)
𝒅𝒙𝟏 𝒅𝒙𝟏

Gibbs/Duhem equation (C) may be written in derivatives form:

At constant T and P:
̅𝟏
𝒅𝑴 ̅𝟐
𝒅𝑴 ̅𝟏
𝒅𝑴 ̅𝟐
𝒙𝟐 𝒅𝑴
𝒙𝟏 + 𝒙𝟐 =𝟎 or =− (F)
𝒅𝒙𝟏 𝑑𝑥1 𝒅𝒙𝟏 𝒙𝟏 𝑑𝑥1

̅𝟏
𝒅𝑴 ̅𝟐
𝒅𝑴
lim =0 (Provided lim is finite) (G)
𝑥1→1 𝒅𝒙𝟏 𝑥1→1 𝒅𝒙𝟏

̅𝟐
𝒅𝑴 ̅𝟏
𝒅𝑴
or: lim =0 (Provided lim is finite)
𝑥2→1 𝒅𝒙𝟏 𝑥2→1 𝒅𝒙𝟏

Example 11.4 (page 389, 7th Edition Smith & Van Ness):

The enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented by the equation:
𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 )
̅1 and 𝐻
where H is in J/mol. Determine expressions for 𝐻 ̅2 as functions of 𝑥1 , numerical values for the pure-species
̅1∞ and 𝐻
enthalpies 𝐻1 and 𝐻2 , and numerical values for the partial enthalpies at infinite dilution 𝐻 ̅2∞ .

Solution:
̅1 and 𝐻
Expressions for 𝐻 ̅2 as functions of 𝑥1

̅ 𝟏 = 𝑴 + 𝒙𝟐 𝒅𝑴
using equation (E1): 𝑴
𝒅𝒙𝟏

𝑑𝐻 𝑑𝐻
̅1 = 𝐻 + 𝑥2
𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 ) + 𝑥2
𝑑𝑥1 𝑑𝑥1

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 Page |7

𝐻 = 400𝑥1 + 600(1 − 𝑥1 ) + 𝑥1 (1 − 𝑥1 )[40𝑥1 + 20(1 − 𝑥1 )]

𝐻 = 600 − 180𝑥1 − 20𝑥1 3

𝑑𝐻
differentiating the equation: = −180 − 60𝑥1 2
𝑑𝑥1

𝑑𝐻
̅1 = 𝐻 + 𝑥2
𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 ) + 𝑥2 (−180 − 60𝑥1 2 )
𝑑𝑥1

̅ 𝟏 = 600 − 180𝑥1 − 20𝑥1 3 + (1 − 𝑥1 )( − 180 − 60𝑥1 2 )

𝑯
simplifying the above equation:
̅1 = 420 − 60𝑥1 2 + 40𝑥1 3
𝐻 (Ans)

̅2 = 𝑀 − 𝑥1 𝑑𝑀
using equation (E2): 𝑀
𝑑𝑥1

̅2 = 600 − 180𝑥1 − 20𝑥1 3 − 𝑥1 (−180 − 60𝑥1 2 )

𝐻
simplifying the above equation:
̅2 = 600 + 40𝑥1 3
𝐻 (Ans)

𝐻 = 600 − 180𝑥1 − 20𝑥1 3

𝑱
𝑯𝟏 = 𝟔𝟎𝟎 − 𝟏𝟖𝟎(𝟏) − 𝟐𝟎(𝟏𝟑 ) = 𝟒𝟎𝟎 (Ans)
𝒎𝒐𝒍

𝐻 = 400 + 240𝑥2 − 60𝑥2 2 + 20𝑥2 3

𝑱
𝑯𝟐 = 𝟒𝟎𝟎 + 𝟐𝟒𝟎(𝟏) − 𝟔𝟎(𝟏)𝟐 + 𝟐𝟎(𝟏)𝟑 = 𝟔𝟎𝟎 (Ans)
𝒎𝒐𝒍

̅1∞ and 𝐻
Numerical values for the the partial enthalpies at infinite dilution 𝐻 ̅2∞
𝑱
when 𝑥1 = 0; ̅1 = 𝐻
𝐻 ̅1∞ ̅ 𝟏 = 𝟒𝟐𝟎 − 𝟔𝟎𝒙𝟏 𝟐 + 𝟒𝟎𝒙𝟏 𝟑 𝑯
𝑯 ̅∞
𝟏 = 𝟒𝟐𝟎 (Ans)
𝒎𝒐𝒍

𝑱
when 𝑥1 = 1; ̅2 = 𝐻
𝐻 ̅2∞ ̅ 𝟐 = 𝟔𝟎𝟎 + 𝟒𝟎𝒙𝟏 𝟑
𝑯 ̅∞
𝑯 𝟑
𝟐 = 𝟔𝟎𝟎 + 𝟒𝟎(𝟏) = 𝟔𝟒𝟎 (Ans)
𝒎𝒐𝒍

Active Learning Opportunity 3.4:

The enthalpy of a binary solution changes with composition in the manner described by :
𝐻 = 12𝑥1 𝑥2
Given the expression shown for the enthalpy of a binary solution as a function of mole fractions x 1 and x2,
1. What would be the expression for the partial molar property of species 1?
2. What would be the expression for the partial molar property of species 2?
Solution:
𝐻 = 12𝑥1 (1 − 𝑥1 )

𝐻 = 12𝑥1 − 12𝑥12
𝑑𝐻
= 12 − 24𝑥1
𝑑𝑥1

𝒅𝑴
̅ 𝟏 = 𝑴 + 𝒙𝟐
𝑴
𝒅𝒙𝟏
̅1 = 12𝑥1 (1 − 𝑥1) + (1 − 𝑥1)(12 − 24𝑥1 )
𝐻
̅1 = 12𝑥12 − 24𝑥1 + 12
𝐻
𝒅𝑴
̅ 𝟐 = 𝑴 − 𝒙𝟏
𝑴
𝒅𝒙𝟏
̅2 = 12𝑥1 (1 − 𝑥1 ) − 𝑥1(12 − 24𝑥1)
𝐻
̅2 = 12𝑥12
𝐻

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 Page |8

Problem 11.13 (7th Edition Smith & Van Ness):

The molar volume (cm3 mol-1) of a binary liquid mixture at T and P is given by:
𝑉 = 120𝑥1 + 70𝑥2 + (15𝑥1 + 8𝑥2 )𝑥1 𝑥2
Find expression for the partial molar volumes of species 1 and 2 at T and P.
̅𝑖 , the
(a) Show that when these expressions are combined in accord with summability equation, 𝑀 = ∑𝑖 𝑥𝑖 𝑀
given equation for V is recovered.
̅ 𝒊 = 𝟎, the Gibbs/Duhem equation.
(c) Show that these expressions satisfy ∑𝒊 𝒙𝒊 𝒅𝑴

(d) Show that (𝑑 𝑉̅1⁄𝑑𝑥1 )𝑥1=1 = (𝑑 𝑉̅2 ⁄𝑑𝑥1 )𝑥1=0 = 0

(e) Plot values of 𝑉, 𝑉̅1 , 𝑎𝑛𝑑 𝑉̅2 calculated by the given equation for V and by the equations developed in (a)
vs x1. Label points 𝑉1 , 𝑉2 , 𝑉̅1∞ , 𝑎𝑛𝑑 𝑉̅2∞ , show their values

Solution (Part a):

𝑉 = 120𝑥1 + 70𝑥2 + (15𝑥1 + 8𝑥2 )𝑥1 𝑥2
𝑉 = 120𝑥1 + 70(1 − 𝑥1 ) + (15𝑥1 + 8(1 − 𝑥1 ))𝑥1 (1 − 𝑥1 )

𝑉 = 120𝑥1 + (70 − 70𝑥1) + (15𝑥1 + 8 − 8𝑥1)(𝑥1 − 𝑥21 )

𝑉 = 120𝑥1 + (70 − 70𝑥1 ) + (7𝑥1 + 8)(𝑥1 − 𝑥12 )

𝑉 = 120𝑥1 + (70 − 70𝑥1 ) + (8𝑥1 − 7𝑥13 − 𝑥12 )

𝑉 = 70 + 58𝑥1 − 𝑥12 − 7𝑥13

𝑑𝑉
= 58 − 2𝑥1 − 21𝑥12
𝑑𝑥1

𝑉̅1 = 70 + 58𝑥1 − 𝑥12 − 7𝑥13 + (1 − 𝑥1 )(58 − 2𝑥1 − 21𝑥12 )

̅𝑽̅̅𝟏̅ = 𝟏𝟐𝟖 − 𝟐𝒙𝟏 − 𝟐𝟎𝒙𝟐𝟏 + 𝟏𝟒𝒙𝟑𝟏

𝑉̅2 = 70 + 58𝑥1 − 𝑥12 − 7𝑥13 − 𝑥1 (58 − 2𝑥1 − 21𝑥12 )

̅𝑽̅̅𝟐̅ = 𝟕𝟎 + 𝒙𝟐𝟏 + 𝟏𝟒𝒙𝟑𝟏

Solution (Part b):

̅𝑖
𝑀 = ∑ 𝑥𝑖 𝑀
𝑖

𝑉 = ∑ 𝑥𝑖 𝑉̅𝑖 = 𝑥1 𝑉̅1 + 𝑥2 𝑉̅2

𝑖

𝑉 = ∑ 𝑥𝑖 𝑉̅𝑖 = 𝑥1 (128 − 2𝑥1 − 20𝑥12 + 14𝑥13 ) + (1 − 𝑥1 )(70 + 𝑥12 + 14𝑥13 )

𝑖

𝑉 = (128𝑥1 − 2𝑥1 2 − 20𝑥13 + 14𝑥14 ) + [(70 + 𝑥12 + 14𝑥13 ) + (−70𝑥1 − 𝑥13 − 14𝑥14 )]

𝑉 = 70 + 128𝑥1 − 70𝑥1 − 2𝑥1 2 + 𝑥12 − 20𝑥13 + 14𝑥13 − 𝑥13 + 14𝑥14 − 14𝑥14

𝑽 = 𝟕𝟎 + 𝟓𝟖𝒙𝟏 − 𝒙𝟏 𝟐 − 𝟕𝒙𝟑𝟏

Solution (Part c):

̅𝑖 = 0
∑ 𝑥𝑖 𝑑𝑀
𝑖

∑ 𝑥𝑖 𝑑𝑉̅𝑖 = 𝑥1 𝑑𝑉̅1 + 𝑥2 𝑑𝑉̅2 = 𝑥1 𝑑𝑉̅1 + (1 − 𝑥1 )𝑑𝑉̅2 = 0

𝑖

𝑉̅1 = 128 − 2 − 20𝑥12 + 14𝑥13

𝑑𝑉̅1 = −2 − 40𝑥1 + 42𝑥12

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 Page |9

𝑉̅2 = 70 + 𝑥12 + 14𝑥13

𝑑𝑉̅2 = 2𝑥1 + 42𝑥12

𝑥1 𝑑𝑉̅1 + (1 − 𝑥1 )𝑑𝑉̅2 = 𝑥1 (−2 − 40𝑥1 + 42𝑥12 ) + (1 − 𝑥1 )(2𝑥1 + 42𝑥12 ) = 0

−2𝑥1 − 40𝑥12 + 42𝑥13 + 2𝑥1 + 42𝑥12 − 2𝑥12 − 42𝑥13 = 0

0=0

Solution (Part d):

(𝑑 𝑉̅1 ⁄𝑑𝑥1 )𝑥1=1 = (𝑑 𝑉̅2 ⁄𝑑𝑥1 )𝑥1=0 = 0

(𝑑 𝑉̅1 ⁄𝑑𝑥1 )𝑥1=1 = −2 − 40(1) + 42(1)2 = −42 + 42 = 0

(𝑑 𝑉̅2 ⁄𝑑𝑥1 )𝑥1=0 = 2(0) + 42(0)2 = 0

Solution (Part e):

x1 V 𝑉̅ 1 𝑉̅ 2
0 70 128 70
0.1 75.783 127.614 70.024
0.2 81.504 126.912 70.152
0.3 87.121 125.978 70.468
0.4 92.592 124.896 71.056
0.5 97.875 123.75 72
0.6 102.928 122.624 73.384
0.7 107.709 121.602 75.292
0.8 112.176 120.768 77.808
0.9 116.287 120.206 81.016
1 120 120 85

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 10

Graphical Representation of Equations of Partial Molar Properties

Relation of Partial Properties

Let us show now how partial properties, (𝑒. 𝑔. , 𝑉̅𝑖 , 𝑈
̅𝑖 , 𝐻
̅𝑖 , 𝑆𝑖̅ , 𝐺̅𝑖 ) are related to one another.

Start with: 𝒅(𝒏𝑮) = (𝒏𝑽) 𝒅𝑷 − (𝒏𝑺)(𝒅 𝑻) + ∑𝒊 𝝁𝒊 𝒅𝒏𝒊

𝝏(𝒏𝑮) 𝝏(𝒏𝑮) 𝜕(𝑛𝐺)
𝐺 = 𝐺(𝑃, 𝑇, 𝑛) 𝑑(𝑛𝐺) = [ ] 𝑑𝑃 + [ ] 𝑑𝑇 +[ ] 𝑑𝑛𝑖 𝜇𝑖 = 𝐺̅𝑖
𝝏𝑷 𝑻,𝒏 𝝏𝑻 𝑷,𝒏 𝜕𝑛𝑖 𝑃,𝑇,𝑛
≠𝑖

𝝏(𝒏𝑮) 𝝏(𝒏𝑮)
[ ] = 𝒏𝑽 [ ] = −𝒏𝑺
𝝏𝑷 𝑻,𝒏 𝝏𝑻 𝑷,𝒏

𝝏𝟐 (𝒏𝑮) 𝝏(𝒏𝑽) 𝝏𝟐 (𝒏𝑮) 𝝏(𝒏𝑺)

Condition for exactness: [ ] =[ ] [ ] = −[ ]
𝝏𝑷𝝏𝑻 𝒏 𝝏𝑻 𝑷,𝒏 𝝏𝑻𝝏𝑷 𝒏 𝝏𝑷 𝑻,𝒏

𝝏𝑽 𝝏𝑺
[ ]𝑷,𝒏 = −[ ]𝑻,𝒏 (one of the Maxwell Relations-Ch 6)
𝝏𝑻 𝝏𝑷

The process of deriving the above equation can be applied to the fundamental property relations for A, H, and
U.

𝝏𝑽 𝝏𝑺
𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇 [ ]𝑷 = −[ ]𝑻
𝝏𝑻 𝝏𝑷

𝝏𝑷 𝝏𝑺
𝑑𝐴 = −𝑃𝑑𝑉 − 𝑆𝑑𝑇 [ ]𝑽 = [ ]𝑻 Chapter 6
𝝏𝑻 𝝏𝑽
𝝏𝑻 𝝏𝑷
𝑑𝑈 = 𝑇𝑑𝑆 − 𝑃𝑑𝑉 [ ]𝑺 = −[ ]𝑽
𝝏𝑽 𝝏𝑺
Maxwell’s Equations
𝝏𝑻 𝝏𝑽
𝑑𝐻 = 𝑇𝑑𝑆 + 𝑉𝑑𝑃 [ ]𝑺 = −[ ]𝑷
𝝏𝑷 𝝏𝑺

Equations that relate partial properties by analogy:

(1) Partial molar property is a partial derivative of the solution property with respect to changes in the number of
moles of that component, keeping the temperature, pressure, and molar amounts of the rest of the components
constant. We define the partial molar property of component i (𝑀 ̅𝑖 ) as:

̅𝑖 = [𝜕(𝑛𝑀)] 𝑇,𝑃,𝑛
𝑀 (By definition)
𝜕𝑛𝑖 𝑗

As an example: 𝐻 = 𝑈 + 𝑃𝑉

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 11

𝜕(𝑛𝐻) 𝜕(𝑛𝑈) 𝜕(𝑛𝑉)

[ ] 𝑇,𝑃,𝑛𝑗 = [ ] 𝑇,𝑃,𝑛𝑗 + 𝑃[ ] 𝑇,𝑃,𝑛𝑗
𝜕𝑛𝑖 𝜕𝑛𝑖 𝜕𝑛𝑖

̅𝒊 = 𝑼
𝑯 ̅ 𝒊 + 𝑷𝑽
̅𝒊 this equation is said to be the partial-property analogy of 𝑯 = 𝑼 + 𝑷𝑽
(2) Consider a constant-composition solution:
𝝏(𝒏𝑮) ̅ 𝒊)
𝝏(𝑮 𝜕(𝑛𝑉)
[ ] = 𝒏𝑽 [ ] =[ ] = 𝑉̅𝑖
𝝏𝑷 𝑻,𝒏 𝝏𝑷 𝑻,𝒏 𝜕𝑛𝑖 𝑇,𝑃,𝑛𝑗

𝝏𝑮 ̅ 𝒊)
𝝏(𝑮
for n = 1: [ ]𝑻,𝒙 = 𝑽 [ ] ̅𝒊
=𝑽 these equations are analogous
𝝏𝑷 𝝏𝑷 𝑻,𝒙

𝝏(𝒏𝑮) ̅ 𝒊)
𝝏(𝑮 𝝏(𝒏𝑺)
same with: [ ] = −𝒏𝑺 [ ] = −[ ] = −𝑆𝑖̅
𝝏𝑻 𝑷,𝒏 𝝏𝑻 𝑷,𝒏 𝝏𝒏𝒊 𝑻,𝑷,𝒏𝒋

𝝏𝑮 ̅ 𝒊)
𝝏(𝑮
for n = 1: [ ]𝑷,𝒙 = −𝑺 [ ] = −𝑆𝑖̅
𝝏𝑻 𝝏𝑻 𝑷,𝒙

(3) 𝑑𝐺̅𝑖 = 𝑽
̅ 𝒊 𝑑𝑃 − 𝑆𝑖̅ 𝑑𝑇 this equation may be compared with 𝑑𝐺 = 𝑉𝑑𝑃 − 𝑆𝑑𝑇

THE IDEAL-GAS MIXTURE MODEL

General Partial Property Equation

̅ 𝒊𝒈 (𝑻, 𝑷) = 𝑴𝒊𝒈 (𝑻, 𝒑𝒊 )

𝑴 𝒊 𝒊
Partial Molar Volume:
All ideal gases, whether pure or mixed, have the same molar volume at the same T and P.
𝑖𝑔 𝜕(𝑛𝑉) 𝜕(𝑛𝑅𝑇/𝑃) 𝑅𝑇 𝜕𝑛 𝑅𝑇
𝑉̅𝑖 = [ ] =[ ] = ( ) =
𝜕𝑛𝑖 𝑃,𝑇,𝑛𝑗 𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝑃 𝜕𝑛𝑖 𝑛 𝑃
𝑗 𝑗

̅ 𝒊𝒈 = 𝑽𝒊𝒈 = 𝑽𝒊𝒈 partial molar volume, pure-species molar volume, and mixture molar volume are identical at
𝑽 𝒊 𝒊
given T and P.

Partial Pressure (𝒑𝒊 ):

The partial pressure of species i in an ideal gas mixture is the pressure that species i would exert if it alone
occupied the molar volume of the mixture.
In a mixture of gases, mole ratio = pressure ratio:
𝑝𝑖 𝑛𝑖 𝑅𝑇
= = 𝑦𝑖 𝑝𝑖 = 𝑦𝑖 𝑃 = 𝑦𝑖 𝑦𝑖 = 𝑚𝑜𝑙𝑒 𝑓𝑟𝑎𝑐𝑡𝑖𝑜𝑛 𝑜𝑓 𝑠𝑝𝑒𝑐𝑖𝑒𝑠 𝑖
𝑃 𝑛 𝑉 𝑖𝑔

Partial Molar Enthalpy: ̅ 𝒊𝒈 (𝑻, 𝑷) = 𝑯𝒊𝒈 (𝑻, 𝒑𝒊 ) = 𝑯𝒊𝒈 (𝑻, 𝑷)

𝑯 𝒊 𝒊 𝒊

Partial Molar Internal energy: ̅ 𝒊𝒈 (𝑻, 𝑷) = 𝑼𝒊𝒈 (𝑻, 𝒑𝒊 ) = 𝑼𝒊𝒈 (𝑻, 𝑷)

𝑼 𝒊 𝒊 𝒊

Partial Molar Enthalpy and Internal Energy are independent in changes in Pressure

Recall that the Change in Entropy for Ideal Gases is:

𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 = 𝐶𝑝 𝑖𝑔 −𝑅
𝑇 𝑃
Integration from 𝑝𝑖 𝑡𝑜 𝑃 and at const T gives:

𝑖𝑔 𝑖𝑔 𝑃 𝑃
𝑆𝑖 (𝑇, 𝑃) − 𝑆𝑖 (𝑇, 𝑝𝑖 ) = −𝑅 𝑙𝑛 = −𝑅 𝑙𝑛 = 𝑅𝑙𝑛𝑦𝑖
𝑝𝑖 𝑦𝑖 𝑃
𝑖𝑔 𝑖𝑔
𝑆𝑖 (𝑇, 𝑝𝑖 ) = 𝑆𝑖 (𝑇, 𝑃) − 𝑅𝑙𝑛𝑦𝑖
𝑖𝑔 𝑖𝑔
𝑆𝑖 (𝑇, 𝑝𝑖 ) = 𝑆𝑖̅ (𝑇, 𝑃)

Partial Molar Entropy:

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
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̅𝒊𝒈 (𝑻, 𝑷) = 𝑺𝒊𝒈 (𝑻, 𝑷) − 𝑹𝒍𝒏𝒚𝒊

𝑺𝒊 𝒊

Partial molar Gibbs Free Energy

For the Gibbs energy of an ideal gas mixture, 𝐺 𝑖𝑔 = 𝐻 𝑖𝑔 − 𝑇𝑆 𝑖𝑔 ; the parallel relation for partial properties is
𝑖𝑔 ̅ 𝑖𝑔 − 𝑇𝑆̅ 𝑖𝑔
𝐺𝑖̅ = 𝐻 𝑖 𝑖
𝑖𝑔 ̅ 𝑖𝑔 − 𝑇𝑆̅ 𝑖𝑔 is combined with molar enthalpy and molar entropy relations:
𝐺𝑖̅ = 𝐻𝑖 𝑖

𝑖𝑔 𝑖𝑔 𝑖𝑔
𝐺𝑖̅ = 𝐻𝑖 − 𝑇(𝑆𝑖 − 𝑅𝑙𝑛𝑦𝑖 )
𝑖𝑔 𝑖𝑔 𝑖𝑔
𝐺̅𝑖 = 𝐻𝑖 − 𝑇𝑆𝑖 + 𝑅𝑇𝑙𝑛𝑦𝑖
𝒊𝒈 𝒊𝒈
̅ = 𝑮𝒊𝒈 + 𝑹𝑻𝒍𝒏𝒚𝒊
𝝁𝒊 ≡ 𝑮 𝒊

The Summability Relation:

̅𝒊
𝑴 = ∑ 𝒙𝒊 𝑴
𝒊
𝒊𝒈
𝑯𝒊𝒈 = ∑𝒊 𝒚𝒊 𝑯𝒊
𝒊𝒈
𝑺𝒊𝒈 = ∑ 𝒚𝒊 𝑺𝒊 − 𝑹 ∑ 𝒚𝒊 𝒍𝒏 𝒚𝒊
𝒊 𝒊

𝑮𝒊𝒈 = ∑𝒊 𝒚𝒊 𝑮𝒊𝒈
𝒊 + 𝑹𝑻 ∑𝒊 𝒚𝒊 𝒍𝒏 𝒚𝒊

Molar Change of Mixing: 𝚫𝑴 = 𝑴 − ∑𝒊 𝑴𝒊

𝚫𝑯𝒊𝒈 = 𝚫𝑼𝒊𝒈 = 𝚫𝑽𝒊𝒈 = 𝟎

𝚫𝑺𝒊𝒈 = −𝑹 ∑𝒊 𝒚𝒊 𝒍𝒏 𝒚𝒊

𝚫𝑮𝒊𝒈 = 𝑹𝑻 ∑𝒊 𝒚𝒊 𝒍𝒏 𝒚𝒊

Problem 11.1 (7th Edition Smith & Van Ness):

What is the change of entropy when 0.7 m3 of CO2 and 0.3 m3 of N2, each at 1 bar and 25 ℃ (298.15 K) blend
to form a gas mixture at the same conditions? Assume ideal gases.

Solution:

∆𝑺𝒊𝒈 = −𝑹 ∑𝒊 𝒚𝒊 𝒍𝒏 𝒚𝒊
for a mixture of gases, mol % = vol %

𝐽 𝐽
∆𝑆 𝑖𝑔 = −8.314 (0.7 × 𝑙𝑛0.7 + 0.3 × 𝑙𝑛0.3) = 5.0787
𝑚𝑜𝑙−𝐾 𝑚𝑜𝑙−𝐾

Active Learning Opportunity 3.5:

What is the entropy change when you mix one mole of butane gas with one mole of propane gas, model as an
ideal gas mixture? Assume the pressure and temperature of the system are constant during the process.

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 13

Solution:
𝑱 𝑱
∆𝑺𝒊𝒈 = −𝑹 ∑ 𝒚𝒊 𝒍𝒏 𝒚𝒊 = − (𝟖. 𝟑𝟏𝟒 ) (𝟎. 𝟓 𝒍𝒏 𝟎. 𝟓 + 𝟎. 𝟓 𝒍𝒏 𝟎. 𝟓) = 𝟓. 𝟕𝟔𝟐𝟖
𝒎𝒐𝒍 − 𝑲 𝒎𝒐𝒍 − 𝑲
𝒊

𝑱 𝑱 𝑱
∆𝑺𝒊𝒈 𝒊𝒏 = (𝟐 𝒎𝒐𝒍) (𝟓. 𝟕𝟔𝟐𝟖 ) = 𝟏𝟏. 𝟓𝟐𝟓𝟕
𝑲 𝒎𝒐𝒍 − 𝑲 𝑲
or
𝑱 𝑱 𝑱
∆𝑺𝒊𝒈 = − [(𝟏 𝒎𝒐𝒍) (𝟖. 𝟑𝟏𝟒 ) 𝒍𝒏(𝟎. 𝟓) + (𝟏 𝒎𝒐𝒍) (𝟖. 𝟑𝟏𝟒 ) (𝒍𝒏 𝟎. 𝟓)] = 𝟏𝟏. 𝟓𝟐
𝒎𝒐𝒍 − 𝑲 𝒎𝒐𝒍 − 𝑲 𝑲

∆𝑺𝒊𝒈 𝒇𝒐𝒓 𝒃𝒖𝒕𝒂𝒏𝒆 ∆𝑺𝒊𝒈 𝒇𝒐𝒓 𝒑𝒓𝒐𝒑𝒂𝒏𝒆

Problem 11.2 (7th Edition Smith & Van Ness):

A vessel divided into two parts by partition, contains 4 mol of nitrogen gas at 75℃ (348.15 K) and 30 bar on one
side and 2.5 mol og argon gas at 130℃ (403.15 K) and 20 bar on the other. If the partition is removed and the
gases mix adiabatically and completely, what is the change in entropy? Assume nitrogen to be an ideal gas with
Cv = (5/2)R and argon to be an ideal gas with Cv = (3/2)R.
Analysis:

Solution:
Volume occupied by N2 at 30 bar and 348.15 K:
𝐽
𝑛𝑅𝑇 (4 𝑚𝑜𝑙)(8.314 )(348.15𝐾)
𝑉𝑁2 = = 𝑚𝑜𝑙 −𝐾 = 3.8593 𝑥 10−3 𝑚3
𝑃 30𝑥105 𝑃𝑎
Volume occupied by Ar at 20 bar and 403.15 K:
𝐽
𝑛𝑅𝑇 (2.5 𝑚𝑜𝑙)(8.314 )(403.15𝐾)
𝑉𝐴𝑟 = = 𝑚𝑜𝑙 −𝐾 = 4.1897 𝑥 10−3 𝑚3
𝑃 20𝑥105 𝑃𝑎
Volume of mixture at T and P:

𝑉𝑚𝑖𝑥𝑡𝑢𝑟𝑒 = 3.8593 𝑥 10−3 + 4.1897 𝑥 10−3 = 8.049 𝑥 10−3 𝑚3

Determination of T and P:

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 14

For a closed system ∆𝑈 = 𝑄 + 𝑊 𝑄 = 0 (𝑎𝑑𝑖𝑎𝑏𝑎𝑡𝑖𝑐 𝑝𝑟𝑜𝑐𝑒𝑠𝑠) 𝑎𝑛𝑑 𝑊 = 0

∆𝑈 = ∆𝑈𝑁2 + ∆𝑈𝐴𝑟 = 0 (𝑛𝐶𝑣∆𝑇)𝑁2 + (𝑛𝐶𝑣∆𝑇)𝐴𝑟 = 0
5 𝐽 3 𝐽
(4 𝑚𝑜𝑙) ( × 8.314 ) (𝑇 − 348.15)𝐾 + (2.5 𝑚𝑜𝑙) ( × 8.314 ) (𝑇 − 403.15)𝐾 = 0
2 𝑚𝑜𝑙−𝐾 2 𝑚𝑜𝑙−𝐾

𝑻 = 𝟑𝟔𝟑. 𝟏𝟓𝑲

Dalton’s Law of Partial Pressures: 𝑃 = 𝑃𝑁2 + 𝑃𝐴𝑟

𝐽
(4 𝑚𝑜𝑙)(8.314𝑚𝑜𝑙−𝐾)(363.15𝐾)
𝑃𝑁2 = = 1500424.45 𝑃𝑎 = 15.0042 𝑏𝑎𝑟
8.094×10−3 𝑚3
𝐽
(2.5 𝑚𝑜𝑙)(8.314𝑚𝑜𝑙−𝐾)(363.15𝐾)
𝑃𝐴𝑟 = = 937765.2814 𝑃𝑎 = 9.3777 𝑏𝑎𝑟
8.094×10−3 𝑚3

𝑃 = 15.0042 + 9.3777 = 24.3819 𝑏𝑎𝑟

∆𝑆 = ∆𝑆𝑁2 + ∆𝑆𝐴𝑟 +Smixing 𝐶𝑝 = 𝐶𝑣 + 𝑅

𝑑𝑇 𝑑𝑃 5 363.15 𝐾 𝐽 24.3819 𝑏𝑎𝑟

∆𝑆𝑁2 = 𝑛𝐶𝑝 − 𝑛𝑅 = (4.0𝑚𝑜𝑙) ( 𝑅 + 𝑅) 𝑙𝑛 − (4.0𝑚𝑜𝑙) (8.314 ) 𝑙𝑛
𝑇 𝑃 2 348.15 𝐾 𝑚𝑜𝑙 − 𝐾 30 𝑏𝑎𝑟
𝐽
= 11.8057
𝐾

𝑑𝑇 𝑑𝑃 3 363.15 𝐾 𝐽 24.3819 𝑏𝑎𝑟

∆𝑆𝐴𝑟 = 𝑛𝐶𝑝 − 𝑛𝑅 = (2.5 𝑚𝑜𝑙) ( 𝑅 + 𝑅) 𝑙𝑛 − (2.5𝑚𝑜𝑙) (8.314 ) 𝑙𝑛
𝑇 𝑃 2 403.15 𝐾 𝑚𝑜𝑙 − 𝐾 20 𝑏𝑎𝑟
𝐽
= −9.5474
𝐾

∆𝑺𝒎𝒊𝒙𝒊𝒏𝒈 :

𝜟𝑺𝒊𝒈 = −𝑹 ∑ 𝒚𝒊 𝒍𝒏 𝒚𝒊
𝒊

𝐽 4.0 4.0 2.5 2.5 𝐽

∆𝑆𝑚𝑖𝑥𝑖𝑛𝑔 = −(4.0 𝑚𝑜𝑙 + 2.5 𝑚𝑜𝑙)(8.314 ) ( 𝑙𝑛 + 𝑙𝑛 ) = 36.0061
𝑚𝑜𝑙−𝐾 6.5 6.5 6.5 6.5 𝐾

𝑱
∆𝑺 = ∆𝑺𝑵𝟐 + ∆𝑺𝑨𝒓 + ∆𝑺𝒎𝒊𝒙𝒊𝒏𝒈 = 𝟏𝟏. 𝟖𝟎𝟓𝟕 − 𝟗. 𝟓𝟒𝟕𝟒 + 𝟑𝟔. 𝟎𝟎𝟔𝟏 = 𝟑𝟖. 𝟐𝟔𝟒𝟒 (Ans)
𝑲

Problem 11.3 (7th Edition Smith & Van Ness):

A stream of Nitrogen flowing at the rate of 2 kg/s and a stream of Hydrogen flowing at the rate of 0.5 kg/s mix
adiabatically in a steady-flow process. If the gases are assumed ideal, what is the rate of entropy increase as a
result of the process?
𝑘𝑔 1 𝑘𝑔 − 𝑚𝑜𝑙 𝑘𝑔 1 𝑘𝑔 − 𝑚𝑜𝑙 𝑘𝑔 − 𝑚𝑜𝑙 𝑚𝑜𝑙
𝑛 = (2 )( ) + (0.5 ) ( ) = 0.3214286 = 321.4286
𝑠 28 𝑘𝑔 𝑁2 𝑠 2 𝑘𝑔 𝐻2 𝑠 𝑠
𝑘𝑔 1 𝑘𝑔 − 𝑚𝑜𝑙 1000 𝑚𝑜𝑙
(2 )( )( )
𝑠 28 𝑘𝑔 𝑁2 1 𝑘𝑔 − 𝑚𝑜𝑙
𝑦𝑁2 = = 0.2222
𝑚𝑜𝑙
321.4286
𝑠
𝑘𝑔 1 𝑘𝑔 − 𝑚𝑜𝑙 1000 𝑚𝑜𝑙
(0.5 )( )( )
𝑠 2 𝑘𝑔 𝑁2 1 𝑘𝑔 − 𝑚𝑜𝑙
𝑦𝐻2 = = 0.7778
𝑚𝑜𝑙
321.4286
𝑠

𝛥𝑆 𝑖𝑔 = −𝑅𝑛 ∑ 𝑦𝑖 𝑙𝑛 𝑦𝑖 = 𝛥𝑆 𝑖𝑔 = −𝑅𝑛[(𝑦𝑁2 ln 𝑦𝑁2 ) + (𝑦𝐻2 ln 𝑦𝐻2 )]

𝑖

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 15

𝐽 𝑚𝑜𝑙
𝛥𝑆 𝑖𝑔 = − (8.314 ) (321.4286 ) [(0.2222 ln 0.2222) + (0.7778 ln 0.7778)]
𝑚𝑜𝑙 − 𝐾 𝑠
𝐽
𝛥𝑆 𝑖𝑔 = 1415.4899
𝑠−𝐾

Problem 11.4 (7th Edition Smith & Van Ness):

What is the ideal work for the separation of an equimolar mixture of methane and ethane at 175 OC and 3 bar in
a steady-flow process into product streams of pure gases at 35 OC and 1 bar if Tσ = 300K?

Gas A B C D
Methane 1.702 0.009081 -0.000002164 0
Ethane 1.131 0.019225 -0.000005561 0
*Taken from Appendix C1 (Smith and Van Ness, 7 th Edition)

Solution 1 (Following the Solutions Manual):

𝐵𝑎𝑠𝑖𝑠: 1 𝑚𝑜𝑙 𝑚𝑖𝑥𝑡𝑢𝑟𝑒
𝑇1 = 448.15 𝐾 𝑇2 = 308.15 𝐾

𝑖𝑔 𝐽 𝐽
∆𝑆𝑚𝑖𝑥𝑖𝑛𝑔 = −𝑅𝑛 ∑ 𝑦𝑖 𝑙𝑛 𝑦𝑖 = − (8.314 ) (1 𝑚𝑜𝑙)[(0.5 ln 0.5) + (0.5 ln 0.5)] = 5.7628
𝑚𝑜𝑙 − 𝐾 𝐾
𝑖

𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 = 𝐶𝑝 𝑖𝑔 −𝑅
𝑇 𝑃
𝑖𝑔 𝑇2 𝑃2
∆𝑆 𝑖𝑔 = 〈𝐶𝑃 〉𝑆 ln − 𝑅 ln (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 5.18)
𝑇1 𝑃1

𝐷 𝜏+1 𝜏−1
〈𝐶𝑃𝑖𝑔 〉𝑆 = 𝑅 [𝐴 + (𝐵𝑇1 + (𝐶𝑇12 + )( )) ∗ ( )] (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 5.17)
𝜏 2 𝑇12 2 ln 𝜏

𝑖𝑔
∆𝐻𝑚𝑖𝑥𝑖𝑛𝑔 = 0

𝑑𝐻 𝑖𝑔 = 𝐶𝑝 𝑖𝑔 𝑑𝑇
𝑖𝑔
∆𝐻 𝑖𝑔 = 〈𝐶𝑃 〉𝐻 (𝑇2 − 𝑇1 ) (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 4.9)

𝐵 𝐶 𝐷
〈𝐶𝑃𝑖𝑔 〉𝐻 = 𝑅 [𝐴 + 𝑇1 (𝜏 + 1) + 𝑇12 (𝜏 2 + 𝜏 + 1) + 2 ] (𝐸𝑞𝑢𝑎𝑡𝑖𝑜𝑛 4.8)
2 3 𝜏𝑇1
𝑇2
𝜏=
𝑇1
𝐽
〈𝐶𝑃𝑖𝑔 〉𝑆,𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = 39.8283
𝑚𝑜𝑙 − 𝐾
𝐽
〈𝐶𝑃𝑖𝑔 〉𝑆,𝐸𝑡ℎ𝑎𝑛𝑒 = 62.6134
𝑚𝑜𝑙 − 𝐾
𝐽
〈𝐶𝑃𝑖𝑔 〉𝐻,𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = 38.7974
𝑚𝑜𝑙 − 𝐾
𝐽
〈𝐶𝑃𝑖𝑔 〉𝐻,𝐸𝑡ℎ𝑎𝑛𝑒 = 59.8150
𝑚𝑜𝑙 − 𝐾
𝐽 (308.15𝐾) 𝐽 (1 𝑏𝑎𝑟) 𝐽
∆𝑆 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = (39.8283 ) ln − (8.314 ) ln = −5.7835
𝑚𝑜𝑙 − 𝐾 (448.15𝐾) 𝑚𝑜𝑙 − 𝐾 (3 𝑏𝑎𝑟) 𝑚𝑜𝑙 − 𝐾
𝐽 (308.15𝐾) 𝐽 (1 𝑏𝑎𝑟) 𝐽
∆𝑆 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 = (62.6134 ) ln − (8.314 ) ln = −14.3174
𝑚𝑜𝑙 − 𝐾 (448.15𝐾) 𝑚𝑜𝑙 − 𝐾 (3 𝑏𝑎𝑟) 𝑚𝑜𝑙 − 𝐾
𝐽 𝐽
∆𝐻 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = (38.7974 ) (308.15 − 448.15) = −5431.6295
𝑚𝑜𝑙 − 𝐾 𝑚𝑜𝑙
𝐽 𝐽
∆𝐻 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 = (59.8150 ) (308.15 − 448.15) = −8374.1059
𝑚𝑜𝑙 − 𝐾 𝑚𝑜𝑙

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 16

𝑖𝑔
∆𝑆 𝑖𝑔 = (0.5 𝑚𝑜𝑙)∆𝑆 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 + (0.5 𝑚𝑜𝑙)∆𝑆 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 + ∆𝑆𝑢𝑛𝑚𝑖𝑥𝑖𝑛𝑔

𝑖𝑔 𝑖𝑔 𝐽 𝐽
∆𝑆𝑢𝑛𝑚𝑖𝑥𝑖𝑛𝑔 = −∆𝑆𝑚𝑖𝑥𝑖𝑛𝑔 = (−1) (5.7628 ) = −5.7628
𝐾 𝐾
𝐽 𝐽 𝐽
∆𝑆 𝑖𝑔 = (0.5 𝑚𝑜𝑙) (−5.7835 ) + (0.5 𝑚𝑜𝑙) (−14.3174 ) + (−5.7628 )
𝑚𝑜𝑙 − 𝐾 𝑚𝑜𝑙 − 𝐾 𝐾
𝐽
∆𝑆 𝑖𝑔 = −15.8133
𝐾
∆𝐻 𝑖𝑔 = (0.5 𝑚𝑜𝑙)∆𝐻 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 + (0.5 𝑚𝑜𝑙)∆𝐻 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒
𝐽 𝐽
∆𝐻 𝑖𝑔 = (0.5 𝑚𝑜𝑙) (−5431.6295 ) + (0.5 𝑚𝑜𝑙) (−8374.1059 )
𝑚𝑜𝑙 𝑚𝑜𝑙
∆𝐻 𝑖𝑔 = −6902.8677 𝐽
𝐽
𝑊𝑖𝑑𝑒𝑎𝑙 = ∆𝐻 𝑖𝑔 − 𝑇𝜎 ∆𝑆 𝑖𝑔 = (−6902.8677 𝐽) − (300𝐾) (−15.8133 )
𝐾
𝐽
𝑊𝑖𝑑𝑒𝑎𝑙 = −2158.8869 (𝑠𝑖𝑛𝑐𝑒 𝑏𝑎𝑠𝑖𝑠 𝑖𝑠 1 𝑚𝑜𝑙 𝑚𝑖𝑥𝑡𝑢𝑟𝑒)
𝑚𝑜𝑙

Solution 2 (Alternative Approximation of Heat Capacity):

𝐵𝑎𝑠𝑖𝑠: 1 𝑚𝑜𝑙 𝑚𝑖𝑥𝑡𝑢𝑟𝑒

𝑇1 = 448.15 𝐾 𝑇2 = 308.15 𝐾

𝑖𝑔 𝐽 𝐽
∆𝑆𝑚𝑖𝑥𝑖𝑛𝑔 = −𝑅𝑛 ∑ 𝑦𝑖 𝑙𝑛 𝑦𝑖 = − (8.314 ) (1 𝑚𝑜𝑙)[(0.5 ln 0.5) + (0.5 ln 0.5)] = 5.7628
𝑚𝑜𝑙 − 𝐾 𝐾
𝑖

𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 = 𝐶𝑝 𝑖𝑔 −𝑅
𝑇 𝑃
𝑖𝑔
∆𝐻𝑚𝑖𝑥𝑖𝑛𝑔 = 0

𝑑𝐻 𝑖𝑔 = 𝐶𝑝 𝑖𝑔 𝑑𝑇

𝐶𝑝𝑖𝑔 = 𝑅(𝐴 + 𝐵𝑇 + 𝐶𝑇 2 + 𝐷𝑇 −2 )
𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = 𝑅(1.702 + 9.081𝑥10−3 𝑇 − 2.164𝑥10−6 𝑇 2 ) −𝑅
𝑇 𝑃
𝐽
∆𝑆 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = −5.7835
𝑚𝑜𝑙 − 𝐾
𝑑𝑇 𝑑𝑃
𝑑𝑆 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 = 𝑅(1.131 + 19.225𝑥10−3 𝑇 − 5.561𝑥10−6 𝑇 2 ) −𝑅
𝑇 𝑃
𝐽
∆𝑆 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 = −14.3174
𝑚𝑜𝑙 − 𝐾
𝑑𝐻 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = 𝑅(1.702 + 9.081𝑥10−3 𝑇 − 2.164𝑥10−6 𝑇 2 )𝑑𝑇
𝐽
∆𝐻 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 = −5613.7781
𝑚𝑜𝑙
𝑑𝐻 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 = 𝑅(1.131 + 19.225𝑥10−3 𝑇 − 5.561𝑥10−6 𝑇 2 )𝑑𝑇
𝐽
∆𝐻 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 = −8842.1876
𝑚𝑜𝑙
𝑖𝑔
∆𝑆 𝑖𝑔 = (0.5 𝑚𝑜𝑙)∆𝑆 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 + (0.5 𝑚𝑜𝑙)∆𝑆 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒 + ∆𝑆𝑢𝑛𝑚𝑖𝑥𝑖𝑛𝑔

𝑖𝑔 𝑖𝑔 𝐽 𝐽
∆𝑆𝑢𝑛𝑚𝑖𝑥𝑖𝑛𝑔 = −∆𝑆𝑚𝑖𝑥𝑖𝑛𝑔 = (−1) (5.7628 ) = −5.7628
𝐾 𝐾
𝐽 𝐽 𝐽
∆𝑆 𝑖𝑔 = (0.5 𝑚𝑜𝑙) (−5.7835 ) + (0.5 𝑚𝑜𝑙) (−14.3174 ) + (−5.7628 )
𝑚𝑜𝑙 − 𝐾 𝑚𝑜𝑙 − 𝐾 𝐾

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 17

𝐽
∆𝑆 𝑖𝑔 = −15.8133
𝐾
∆𝐻 𝑖𝑔 = (0.5 𝑚𝑜𝑙)∆𝐻 𝑖𝑔 𝑀𝑒𝑡ℎ𝑎𝑛𝑒 + (0.5 𝑚𝑜𝑙)∆𝐻 𝑖𝑔 𝐸𝑡ℎ𝑎𝑛𝑒
𝐽 𝐽
∆𝐻 𝑖𝑔 = (0.5 𝑚𝑜𝑙) (−5613.7781 ) + (0.5 𝑚𝑜𝑙) (−8842.1876 )
𝑚𝑜𝑙 𝑚𝑜𝑙
∆𝐻 𝑖𝑔 = −7227.9829 𝐽
𝐽
𝑊𝑖𝑑𝑒𝑎𝑙 = ∆𝐻 𝑖𝑔 − 𝑇𝜎 ∆𝑆 𝑖𝑔 = (−7227.9829 𝐽) − (300𝐾) (−15.8133 )
𝐾
𝐽
𝑊𝑖𝑑𝑒𝑎𝑙 = −2483.9923 (𝑠𝑖𝑛𝑐𝑒 𝑏𝑎𝑠𝑖𝑠 𝑖𝑠 1 𝑚𝑜𝑙 𝑚𝑖𝑥𝑡𝑢𝑟𝑒)
𝑚𝑜𝑙

Problem 11.5 (7th Edition Smith & Van Ness):

What is the work required for the separation of air (21% mol O 2 and 79% mol N2) at 25 OC and 1 bar in a steady-
flow process into product streams of pure oxygen and nitrogen, also at 25 OC and 1 bar if the thermodynamic
efficiency of the process is 5% and if Tσ = 300K

𝐵𝑎𝑠𝑖𝑠: 1 𝑚𝑜𝑙 𝑚𝑖𝑥𝑡𝑢𝑟𝑒

𝑆 𝑖𝑔 = −𝑅 ∑ 𝑦𝑖 𝑙𝑛 𝑦𝑖 = 𝛥𝑆 𝑖𝑔 = −𝑅[(𝑦𝑁2 ln 𝑦𝑁2 ) + (𝑦𝑂2 ln 𝑦𝑂2 )]

𝑖

𝐽
𝑆 𝑖𝑔 = −𝑅 ∑ 𝑦𝑖 𝑙𝑛 𝑦𝑖 = 𝛥𝑆 𝑖𝑔 = − (8.314 ) [(0.79 ln 0.79) + (0.21 ln 0.21)]
𝑚𝑜𝑙 − 𝐾
𝑖

𝐽 𝐽
𝛥𝑆 𝑖𝑔 𝑚𝑖𝑥𝑖𝑛𝑔 = − (8.314 ) [(0.79 ln 0.79) + (0.21 ln 0.21)] = 4.2730
𝑚𝑜𝑙 − 𝐾 𝑚𝑜𝑙 − 𝐾
𝐽
𝛥𝑆 𝑖𝑔 𝑢𝑛𝑚𝑖𝑥𝑖𝑛𝑔 = −𝛥𝑆 𝑖𝑔 𝑚𝑖𝑥𝑖𝑛𝑔 = −4.2730
𝑚𝑜𝑙 − 𝐾
𝐽 𝐽
𝑊𝑖𝑑𝑒𝑎𝑙 = ∆𝐻 𝑖𝑔 − 𝑇𝜎 ∆𝑆 𝑖𝑔 = (0) − (300𝐾) (−4.2730 ) = 1281.9107
𝑚𝑜𝑙 − 𝐾 𝑚𝑜𝑙
𝑊𝑖𝑑𝑒𝑎𝑙
𝜂= = 0.05
𝑊𝑎𝑐𝑡𝑢𝑎𝑙
𝐽
𝑊𝑎𝑐𝑡𝑢𝑎𝑙 = 25638.2146
𝑚𝑜𝑙

CHE 2112 PE Module 3 Problem (AY 2020-2021):

Consider a container divided into three equal compartments containing 3.0 mol of H2(g), 2.0 mol of N 2(g) and
1.0 mol of O2(g) as shown in the figure below. The pressure (p) and temperature of each compartment are also
given in the illustration. Assuming all gases are perfect, Calculate the partial pressures and the gibbs energy of
mixing

Solution (Following Physical Chemistry):

a. If the left partition is removed
If the left partition is removed then the volume of the compartment will be twice as big as it was originally.
Therefore the partial pressure will be divided by 2.
3 3 5
𝑝𝐻2 = 𝑝 ; 𝑝𝑁2 = 𝑝 ; 𝑝𝑡𝑜𝑡𝑎𝑙 = 𝑝 + 𝑝 = 𝑝
2 2 2
Gibbs Energy of Mixing:

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 18

𝐺𝑖 = 𝑛𝐻2 (𝜇 ∗ 𝐻2 + 𝑅𝑇𝑙𝑛𝑝𝐻2 ) + 𝑛𝑁2 (𝜇 ∗ 𝑁2 + 𝑅𝑇𝑙𝑛𝑝𝑁2 )

𝐺𝑖 = (3 𝑚𝑜𝑙) (𝜇 ∗ 𝐻2 + 𝑅𝑇𝑙𝑛3𝑝) + (1 𝑚𝑜𝑙) (𝜇 ∗ 𝑁2 + 𝑅𝑇𝑙𝑛2𝑝)

3
𝐺𝑓 = (3 𝑚𝑜𝑙) (𝜇 ∗ 𝐻2 + 𝑅𝑇𝑙𝑛 𝑝) + (1 𝑚𝑜𝑙) (𝜇 ∗ 𝑁2 + 𝑅𝑇𝑙𝑛𝑝)
2
∆𝑚𝑖𝑥 𝐺 = 𝐺𝑓 − 𝐺𝑖
3
∆𝑚𝑖𝑥 𝐺 = [(3 𝑚𝑜𝑙) (𝜇∗ 𝐻 + 𝑅𝑇𝑙𝑛 𝑝) + (1 𝑚𝑜𝑙) (𝜇 ∗ 𝑁 + 𝑅𝑇𝑙𝑛𝑝)] − [(3 𝑚𝑜𝑙) (𝜇∗ 𝐻 + 𝑅𝑇𝑙𝑛3𝑝) + (1 𝑚𝑜𝑙) (𝜇∗ 𝑁 + 𝑅𝑇𝑙𝑛2𝑝)]
2 2 2 2 2

1 1
∆𝑚𝑖𝑥 𝐺 = (3𝑅𝑇𝑙𝑛 ) + (2𝑅𝑇𝑙𝑛 )
2 2
∆𝑚𝑖𝑥 𝐺 = −8586.61 𝐽
b. If the right partition is also removed
If the right partition is also removed then the volume of the compartment will be thrice as big as it was
originally. Therefore the partial pressure will be divided by 3.
2 1 2 1 13
𝑝𝐻2 = 𝑝 ; 𝑝𝑁2 = 𝑝 ; 𝑝𝑂2 = 𝑝 ; 𝑝𝑡𝑜𝑡𝑎𝑙 = 𝑝 + 𝑝 + 𝑝 = 𝑝
3 3 3 3 6

𝐺𝑖 = 𝑛𝐻2 (𝜇 ∗ 𝐻2 + 𝑅𝑇𝑙𝑛𝑝𝐻2 ) + 𝑛𝑁2 (𝜇 ∗ 𝑁2 + 𝑅𝑇𝑙𝑛𝑝𝑁2 ) + 𝑛𝑂2 (𝜇 ∗ 𝑂2 + 𝑅𝑇𝑙𝑛𝑝𝑂2 )

𝐺𝑖 = (3) (𝜇 ∗ 𝐻 + 𝑅𝑇𝑙𝑛(3𝑝)) + (2) (𝜇 ∗ 𝑁 + 𝑅𝑇𝑙𝑛(2𝑝)) + (𝜇 ∗ 𝑂 + 𝑅𝑇𝑙𝑛(𝑝))

2 2 2

2 1
𝐺𝑓 = (3) (𝜇 ∗ 𝐻2 + 𝑅𝑇𝑙𝑛(𝑝)) + (2) (𝜇 ∗ 𝑁2 + 𝑅𝑇𝑙𝑛 ( 𝑝)) + (𝜇 ∗ 𝑂2 + 𝑅𝑇𝑙𝑛 ( 𝑝))
3 3

∆𝑚𝑖𝑥 𝐺 = 𝐺𝑓 − 𝐺𝑖
2 2 1
∆𝑚𝑖𝑥 𝐺 = (3𝑅𝑇𝑙𝑛 ) + (2𝑅𝑇𝑙𝑛 ) + (𝑅𝑇𝑙𝑛 )
3 3 3
∆𝑚𝑖𝑥 𝐺 = −7744.74𝐽

Solution (Following Solutions Thermodynamics):

a. If the Left Partition is Removed

𝐽 𝐽
(3 𝑚𝑜𝑙)(8.314 )(298𝐾) (2 𝑚𝑜𝑙)(8.314 )(298𝐾)
𝑉𝐻2 = 𝑚𝑜𝑙−𝐾
= 2477.572 𝑝 −1 𝑉𝑁2 = 𝑚𝑜𝑙−𝐾
= 2477.572 𝑝 −1
(3𝑝) (2𝑝)

𝑉 = 2477.572 𝑝 −1 + 2477.572 𝑝 −1 = 4955.144 𝑝 −1

𝐽 𝐽
(3 𝑚𝑜𝑙)(8.314𝑚𝑜𝑙−𝐾)(298𝐾) (1 𝑚𝑜𝑙)(8.314𝑚𝑜𝑙−𝐾)(298𝐾)
𝑃𝐻2 = = 1.5𝑝 𝑃𝑁2 = = 1𝑝
4955.144 𝑝−1 4955.144 𝑝−1

2.5𝑝 2.5𝑝 3 3 2 2
Δ𝐺 𝑖𝑔 = 3(8.314)(298) ln ( ) + 2(8.314)(298) ln ( ) + (5)(8.314)(298) [( ) ln ( ) + ( ) ln ( )]
3𝑝 2𝑝 5 5 5 5

Δ𝐺 𝑖𝑔 = −8586.6102 𝐽

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda
 P a g e | 19

b. If the Right Partition is also Removed

𝐽
(3 𝑚𝑜𝑙) (8.314 ) (298𝐾)
𝑃𝐻2 = 𝑚𝑜𝑙 −𝐾 = 1𝑝
7432.716 𝑝 −1
𝐽
(2 𝑚𝑜𝑙) (8.314 ) (298𝐾) 2
𝑃𝑁2 = 𝑚𝑜𝑙 −𝐾 = 𝑝
7432.716 𝑝 −1 3
𝐽
(1 𝑚𝑜𝑙) (8.314 ) (298𝐾) 1
𝑃𝑂2 = 𝑚𝑜𝑙 − 𝐾 = 𝑝
7432.716 𝑝 −1 3
𝑃𝑇 = 2𝑝
2𝑝 2𝑝 2𝑝
Δ𝐺 𝑖𝑔 = (3)(8.314)(298) ln ( ) + (2)(8.314)(298) ln ( ) + (1)(8.314)(298) ln ( )
1.5𝑝 𝑝 𝑝
3 2 1
+ (3)(8.314)(298) ln ( ) + (2)(8.314)(298) ln ( ) + (1)(8.314)(298) ( )
6 6 6
Δ𝐺 𝑖𝑔 = −7744.73603 𝐽

Summary of Useful Equations

Fundamental Property Relations Partial Molar Properties
𝒅(𝒏𝑼) = 𝑻𝒅(𝒏𝑺) − 𝑷𝒅(𝒏𝑽) 𝒅(𝒏𝑯) = 𝑻𝒅(𝒏𝑺) + (𝒏𝑽) 𝒅𝑷 𝜕(𝑛𝑀)
̅𝑖 ≡ [ ̅𝑖
𝑀 = ∑ 𝑥𝑖 𝑀
𝑀 ]
𝜕𝑛𝑖 𝑃,𝑇,𝑛 𝑖 𝑗
𝒅(𝒏𝑮) = (𝒏𝑽) 𝒅𝑷 − (𝒏𝑺)(𝒅 𝑻) 𝒅(𝒏𝑨) = −𝑷𝒅(𝒏𝑽) − (𝒏𝑺)(𝒅 𝑻) Binary Solutions
Mixing ̅ 𝟏 + 𝒙𝟐 𝑴
𝑴 = 𝒙𝟏 𝑴 ̅𝟐 ̅ 𝟏 + 𝒙𝟐 𝒅𝑴
𝒙𝟏 𝒅𝑴 ̅ 𝟐 = 𝟎*
𝚫𝑯𝒊𝒈 = 𝚫𝑼𝒊𝒈 = 𝚫𝑽𝒊𝒈 = 𝟎 𝒅𝑴 𝒅𝑴
=𝑴 ̅𝟏 − 𝑴̅𝟐 ̅ 𝟏 = 𝑴 + 𝒙𝟐
𝑴
𝒅𝒙𝟏 𝒅𝒙𝟏
̅
𝒅𝑴 ̅
𝒅𝑴
𝚫𝑮𝒊𝒈 = 𝑹𝑻 ∑ 𝒚𝒊 𝒍𝒏 𝒚𝒊 𝚫𝑺𝒊𝒈 = −𝑹 ∑ 𝒚𝒊 𝒍𝒏 𝒚𝒊 lim 𝟏 = 0* lim 𝟐 = 0*
𝑥1→1 𝒅𝒙𝟏 𝑥2→1 𝒅𝒙𝟏
𝒊 𝒊
*Conditions are at Constant Temperature and Pressure

LECTURE BY: ASSOC. PROF. BERNADETTE M. DURAN, MENGG, MA | Prepared by: Kenneth Albelda