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Molar Volume and Enthalpy Calculations

The document contains exercises related to the calculation of molar volumes and Gibbs energy of mixing for binary mixtures. It provides formulas for determining the molar volume based on composition and the Gibbs energy of mixing for gases in separate compartments. Additionally, it discusses the estimation of pseudo critical temperature and pressure using Kay's rule for a specific gas mixture.

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18 views3 pages

Molar Volume and Enthalpy Calculations

The document contains exercises related to the calculation of molar volumes and Gibbs energy of mixing for binary mixtures. It provides formulas for determining the molar volume based on composition and the Gibbs energy of mixing for gases in separate compartments. Additionally, it discusses the estimation of pseudo critical temperature and pressure using Kay's rule for a specific gas mixture.

Uploaded by

issamoz417
Copyright
© All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
Available Formats
Download as PDF, TXT or read online on Scribd

Exercise 2

The volume of a binary mixture has a molar volume, V, that depends on its composition:
𝑐𝑚3
𝑉𝑚 = 75𝑥1 + 95𝑥2 + 3.7𝑥1 𝑥2 ( )
𝑚𝑜𝑙
For a mixture with x1 = 0.60, determine
a) the molar volume of the mixture
b) the partial molar volume of component 1.

Solution 2

a. (𝑥1 = 0.60 → 𝑥2 = 0.4 𝑡ℎ𝑒𝑛, 𝑉 = 83.9𝑐𝑚3 /𝑚𝑜𝑙)

𝜕𝑉
b. 𝑉̅1 = 𝑉𝑚 + 𝑥2 ( 𝜕𝑥𝑚 )
1 𝑃,𝑇,𝑛1

𝑉𝑚 = 75𝑥1 + 95(1 − 𝑥1 ) + 3.7𝑥1 (1 − 𝑥1 ) = 95 − 16.3𝑥1 − 3.7𝑥12


𝜕𝑉𝑚
( ) = −16.3𝑥1 − 7.4𝑥1 = −16.3𝑥1 − 7.4(0.6) = −20.7
𝜕𝑥1 𝑃,𝑇,𝑛
1

𝑉̅1 = 83.9 + 0.4(−20.7) = 75.6 𝑐𝑚 3 /𝑚𝑜𝑙

Exercise 3

The molar enthalpy of a binary liquid system of species 1 and 2 at fixed T and P is represented by the following
equation:
𝐻 = 400𝑥1 + 600𝑥2 + 𝑥1 𝑥2 (40𝑥1 + 20𝑥2 )
where H is in J/mol
a. determine expressions for ̅𝐻
̅̅1̅ and ̅̅
𝐻̅̅2 as functions of 𝑥1
b. Numerical values for the pure species enthalpies 𝐻1∗ and 𝐻2∗
c. Find the expression of (𝐻𝐸 )
d. Numerical values for the partial enthalpies at infinite dilution ̅𝐻
̅̅1̅ and ̅̅
𝐻̅̅2
Exercise 4

A container is divided into two equal compartments (figure below). One contains 3.0 mol 𝐻2 at 25°𝐶; the other contains
1.0 𝑚𝑜𝑙 𝑁2 𝑎𝑡 250 𝐶. Calculate the Gibbs energy of mixing when the partition is removed. Assume perfect gas behavior. 𝑃0 = 1𝑏𝑎𝑟

Solution

The Gibbs energy of mixing : so we have to consider both states initial and final

Two perfect gases in two identical containers with amounts 𝑛𝐴 and 𝑛𝐵 , both at the same T and P

We first calculate the initial Gibbs energy from chemical potentials. We need the pressure of each gas.
𝑓𝐴 𝑓𝐵 𝑃𝐴 𝑃𝐵
𝐺𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑛𝐴 ̅̅̅
𝐺𝐴 + 𝑛𝐵 ̅̅̅
𝐺𝐵̅ = 𝑛𝐴 𝜇𝐴 + 𝑛𝐵 𝜇𝐵 = 𝑛𝐴 (𝜇𝐴° + 𝑅𝑇𝑙𝑛 ° ) + 𝑛𝐵 (𝜇𝐵° + 𝑅𝑇𝑙𝑛 ° ) = 𝑛𝐴 (𝜇𝐴° + 𝑅𝑇𝑙𝑛 ° ) + 𝑛𝐵 (𝜇𝐵° + 𝑅𝑇𝑙𝑛 ° )
𝑓𝐴 𝑓𝐵 𝑃𝐴 𝑃𝐵

𝑓𝐴 𝑓𝐵 𝑃𝐴𝑖 𝑃𝐵𝑖
𝐺𝑖𝑛𝑖𝑡𝑖𝑎𝑙 = 𝑛𝐴 ̅̅̅
𝐺𝐴 + 𝑛𝐵 ̅̅̅
𝐺𝐵̅ = 𝑛𝐴 𝜇𝐴 + 𝑛𝐵 𝜇𝐵 = 𝑛𝐴 (𝜇𝐴° + 𝑅𝑇𝑙𝑛 ° ° °
° ) + 𝑛𝐵 (𝜇𝐵 + 𝑅𝑇𝑙𝑛 ° ) = 𝑛𝐴 (𝜇𝐴 + 𝑅𝑇𝑙𝑛 ° ) + 𝑛𝐵 (𝜇𝐵 + 𝑅𝑇𝑙𝑛 ° )
𝑓𝐴 𝑓𝐵 𝑃𝐴 𝑃𝐵
= 𝑛𝐴 (𝜇𝐴° + 𝑅𝑇𝑙𝑛3𝑃) + 𝑛𝐵 (𝜇𝐵° + 𝑅𝑇𝑙𝑛𝑃) =

𝑃1 𝑉2 3𝑃 𝑃
𝑃1 𝑉1 = 𝑃2 𝑉2 → = = 2 → 𝑃𝐴𝑓 = 𝑎𝑛𝑑 𝑃𝐵 =
𝑃2 𝑉1 2 2
𝑃𝐴𝑓 𝑃𝐵𝑓
𝐺𝑓𝑖𝑛𝑎𝑙 = 𝑛𝐴 ̅̅̅
𝐺𝐴 + 𝑛𝐵 ̅̅̅
𝐺𝐵̅ = 𝑛𝐴 𝜇𝐴 + 𝑛𝐵 𝜇𝐵 = 𝑛𝐴 (𝜇𝐴 + 𝑅𝑇𝑙𝑛 ° ) + 𝑛𝐵 (𝜇𝐵 + 𝑅𝑇𝑙𝑛 ° )
° °
𝑃𝐴 𝑃𝐵
𝑃 𝐴𝑓 𝑃 𝐵𝑓 3𝑃 𝑃
= 𝑛𝐴 (𝜇𝐴° + 𝑅𝑇𝑙𝑛 ° ) + 𝑛𝐵 (𝜇𝐵° + 𝑅𝑇𝑙𝑛 ° ) = 𝑛𝐴 (𝜇𝐴° + 𝑅𝑇𝑙𝑛 ) + 𝑛𝐵 (𝜇𝐵° + 𝑅𝑇𝑙𝑛 )
𝑃𝐴 𝑃𝐵 2 2
1 1 1
∆𝐺 = 𝐺𝑓 − 𝐺𝑖 = 𝑛𝐴 𝑅𝑇𝑙𝑛 + 𝑛𝐵 𝑅𝑇𝑙𝑛 = 4(8.314𝐽𝐾 −1 𝑚𝑜𝑙 −1 )(298𝐾) ln = −6900𝑗. 𝑚𝑜𝑙−1
2 2 2
Exercise 5

[Link]

For a mixture contains 75% 𝐻2 and 25% 𝑁2 (molar basis) estimate the pseudo critical Temperature and
pressure (𝑃𝑝𝑐 𝑎𝑛𝑑 𝑇𝑝𝑐 ) using Kay’s rule.

We give:
For 𝑁2 : 𝑇𝐶 = 126.2𝐾 𝑎𝑛𝑑 𝑃𝐶 = 33.5𝑎𝑡𝑚
For 𝐻2 𝑇𝐶 = 33 + 8 = 41𝐾 𝑎𝑛𝑑 𝑃𝐶 = 12.8 + 8 = 20.8 𝑎𝑡𝑚
Solution

𝑇𝑝𝑐 = 𝑦𝐻2 𝑇𝑐𝐻2 + 𝑦𝑁2 𝑇𝑐𝑁2 = 62.3𝐾 𝑃𝑝𝑐 = 24𝑎𝑡𝑚

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