Question

Express the van der Waals equation of state as a virial expansion in powers of 1/Vm and obtain expressions for B and C in terms of the parameters a and b. The expansion you will need is (1 − x)−1 = 1 + x + x2 + … . Measurements on argon gave B = −21.7 cm3 mol−1 and C = 1200 cm6 mol−2 for the virial coefficients at 273 K. What are the values of a and b in the corresponding van der Waals equation of state?

Answer 1

Answer:

$PV_{m} = RT[1 + (b-\frac{a}{RT})\frac{1}{V_{m} } + \frac{b^{2} }{V^{2} _{m} } + ...]$

B = b -a/RT

C = b^2

a = 1.263 atm*L^2/mol^2

b = 0.03464 L/mol

Explanation:

In the given question, we need to express the van der Waals equation of state as a virial expansion in powers of 1/Vm and obtain expressions for B and C in terms of the parameters a and b. Therefore:

Using the van deer Waals equation of state:

$P = \frac{RT}{V_{m}-b } - \frac{a}{V_{m} ^{2} }$

With further simplification, we have:

$P = RT[\frac{1}{V_{m}-b } - \frac{a}{RTV_{m} ^{2} }]$

Then, we have:

$P = \frac{RT}{V_{m} } [\frac{1}{1-\frac{b}{V_{m} } } - \frac{a}{RTV_{m} }]$

Therefore,

$PV_{m} = RT[(1-\frac{b}{V_{m} }) ^{-1} - \frac{a}{RTV_{m} }]$

Using the expansion:

$(1-x)^{-1} = 1 + x + x^{2} + ....$

Therefore,

$PV_{m} = RT[1+\frac{b}{V_{m} }+\frac{b^{2} }{V_{m} ^{2} } + ... -\frac{a}{RTV_{m} }]$

Thus:

$PV_{m} = RT[1 + (b-\frac{a}{RT})\frac{1}{V_{m} } + \frac{b^{2} }{V^{2} _{m} } + ...]$           equation (1)

Using the virial equation of state:

$P = RT[\frac{1}{V_{m} }+ \frac{B}{V_{m} ^{2}}+\frac{C}{V_{m} ^{3} }+ ...]$

Thus:

$PV_{m} = RT[1+ \frac{B}{V_{m} }+ \frac{C}{V_{m} ^{2} } + ...]$     equation (2)

Comparing equations (1) and (2), we have:

B = b -a/RT

C = b^2

Using the measurements on argon gave B = −21.7 cm3 mol−1 and C = 1200 cm6 mol−2 for the virial coefficients at 273 K.

$b = \sqrt{C} = \sqrt{1200} = 34.64[tex]cm^{3}/mol$[/tex] = 0.03464 L/mol

a = (b-B)*RT = (34.64+21.7)*(1L/1000cm^3)*(0.0821)*(273) = 1.263 atm*L^2/mol^2