LECTURE 2: Supplementary Notes

Example: Comparison of van der Waals Forces for Pure Species

Compare the strength of the dipole–dipole, induction, and dispersion interactions for each of the
following pure species at 298 K: H2O, NH3, CH4, CH3Cl, CCl4. Discuss the results.

In CGS units:
2𝜇 𝜇
C =
3 𝑘𝑇

C = 2𝛼 𝜇

The equation above is multiplied by 2 because each species in two-body interaction can induce a dipole
in its neighbor
3𝛼 𝐼
C =
4

C = C C C

By using the α, μ, and I values of each species and the above equations, the following values are obtained:

• Even though it is nonpolar, CCl4 exhibits the largest intermolecular forces, approximately three
times greater than the strongly polar CH3Cl. The magnitude results from the large polarizability
associated with the four Cl atoms in CCl4.
• However, CH3Cl, which has a similar dipole moment to water, demonstrates much larger van der
Waals interactions (over twice the value for C6) since this larger molecule is much more easily
polarized and, consequently, has a larger dispersion interaction.

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van der Waals Parameters by Corresponding States:
• To use the van der Waals equation, the parameters a and b must be determined for a species of
interest. The most accurate values are obtained by fitting experimental 𝑃𝑉 𝑇 data. If these data
are not available, we can use the principle of corresponding states.
• Using principle of corresponding state which scales property data to that at the critical point, we
can determine van der Waals parameters to the temperature and pressure at the critical point by
noting that there is an inflection point on the critical isotherm.

𝜕𝑃 𝜕 𝑃
= =0 𝐸𝑞. 4.16
𝜕𝑉 𝜕𝑉

At critical point van der Waals EOS becomes:

𝑅𝑇 𝑎
𝑃 = 𝐸𝑞. 4.17
𝑉 𝑏 𝑉

𝜕𝑃 𝑅𝑇 2𝑎
=0= 𝐸𝑞. 4.18 Pc= RTc/2b-(9RTc/8*3b)
𝜕𝑉 𝑉 𝑏 𝑉 =(12RTc-9RTc)/24b=RTc/8b
b=RTc/8Pc
𝜕 𝑃 2𝑅𝑇 6𝑎
=0= 𝐸𝑞. 4.19
𝜕𝑉 𝑉 𝑏 𝑉

Multiply Equation (4.18) by 2 and Equation (4.19) by 𝑉 𝑏 and add them together, we get

27/64*R^2*Tc^2/Pc
= 9/8*3*b*R*Tc
2
In terms of reduced variables:
8𝑇 3
𝑃 =
3𝑉 1 𝑉
Compressibility factor at critical point becomes:

𝑃𝑉 3
𝑍 = = = 0.375 0.29
𝑅𝑇 8
Zc is 0.29 for simple species and usually less for complex species. Thus, the value predicted by the van der
Waals equation is considerably high indicating its limitations in predicting 𝑃𝑉 𝑇 behavior.

Example 3.3. A 1 m3 rigid tank contains 25 kg of propylene at 298 K. Determine the pressure and the state
of propylene in the tank using the Peng-Robinson equation of state. The vapor pressure of propylene at
298 K is 11.53 bar.

From Appendix A

Tc = 365.2 K, Pc = 46.0 bar, ω= 0.144, M = 42.08 g/mol.

The state of a single-phase, single-component system can be specified by two independent intensive
properties. The state of propylene lies on the 298 K isotherm as shown in the figure below. To identify the
exact location, one more independent intensive property must be known besides temperature.

Since the tank volume and the amount of propylene are given, this additional intensive property is the
molar volume, calculated as:

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Procedure to obtain molar volume:

1. Obtain Tc, Pc, and ω from Appendix A.

2. Calculate reduced temperature and reduced pressure.

3. Determine the term α for SRK and PR.

4. Determine the dimensionless parameters A and B

5. Evaluate the parameters p, q, and r appearing in the equation

6. Solve. Z3 + pZ2 + qZ + r = 0.

7. Use 𝑉 = 𝑍𝑅𝑇/𝑃 and determine the molar volume.

Please see Example 3.2 in Tosun’s textbook (pp. 42-45).

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Using thermosolver: Psat = 11.399 bar

Using thermosolver with T = 298 and 𝑉 = 0.001683 𝑚 /𝑘𝑚𝑜𝑙, P can be calculated as: 11.787 bar

Since P > Psat propylene is in liquid phase but EOS solver predicts it in vapor phase as given below.

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Properties of propylene used in thermosolver:

Let’s decrease temperature to 280 K and see what happens in Thermosolver

Thus, the difference is due to differences in experimentally observed Psat and PR-predicted Psat. Also
critical properties given in ThermoSolver and Tosun’s book are slightly different.

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Example 3.1. Calculate the molar volume of ethylene at 350 K and 10 bar if it obeys the virial equation of
state. (Tosun; pp. 38-39).

𝑅𝑇
𝐵= 𝐵 𝜔𝐵
𝑃
0.422
𝐵 = 0.083
𝑇 .
0.172
𝐵 = 0.139
𝑇 .

𝑃𝑉 𝐵𝑃 𝑃
𝑍= =1 =1 𝐵 𝜔𝐵
𝑅𝑇 𝑅𝑇 𝑇

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Example 4.9 Calculate an expression for the second virial coefficient, B, for the hard sphere model
(Koretsky; p. 243).

Hard Sphere Model:

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Example 6.1 A rigid tank contains 3 mol of ethane (1) at 373 K and 4 bar. Estimate the pressure in the tank
when 5 mol of n-butane (2) is added isothermally to the tank. The mixture is described by the virial
equation of state and the following critical properties are provided: (Tosun; pp. 164-166).

Solution: From Appendix A

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Example 6.3 (Tosun): Calculate the molar volume of a gas mixture consisting of 50 mol% propane (1), 20%
n-butane (2), and 30% n-pentane (3) at 393 K and 40 bar using van der Waals equation of state. It is
reported that Zmix found according to Peng Robinson EOS as 0.179. Compare that value with a hypothetical
𝑍 = ∑ 𝑥 𝑍 where xi is mole fraction of pure compounds and Zi is the compressibility factor of
pure compounds found in this case according to Peng-Robinson EOS.

From Appendix A:

To find Zmix:

Using the equations in Table 6.3, the dimensionless parameters are calculated as:

Using:

Amix = 0.482 and Bmix = 0.137

Calculate p, q, and r using Table 6.2, and the EOS becomes:

Using thermosolver software at 393 K and 40 bar individual compressibility factors according to PR-EOS
were calculated as:

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 Component xi Zi xiZi Vi xiVi
Propane 0.5 0.6457 0.32285 527.5 263.8

n-butane 0.2 0.1632 0.03264 133.4 26.7

n-pentane 0.3 0.1667 0.05001 136.1 40.8

Sum: 0.4055 Sum: Vmix 331.3

Vmix = (0.4055)(83.14)(393)/40 = 331.2

Thus, this kind of mixing rule does not apply!

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