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STATE

WHAT IS VIRIAL EXPANSION?

ഥ −1 ) or the pressure

expansion in either the density (𝑉

ഥ

𝑃𝑉 𝐵2𝑣 (𝑇) 𝐵3𝑣 (𝑇) 𝐵4𝑣 (𝑇)

𝑍= =1+ ഥ

+ ഥ2

+ ഥ3

+⋯

𝑅𝑇 𝑉 𝑉 𝑉

ഥ

𝑃𝑉

𝑍= = 1 + 𝐵2𝑃 𝑇 𝑃 + 𝐵3𝑃 𝑇 𝑃 2 + 𝐵3𝑃 𝑇 𝑃 3 + ⋯ .

𝑅𝑇

𝑃𝑉ത

𝑍=

𝑅𝑇

𝐵2𝑣 (𝑇) 𝐵3𝑣 (𝑇) 𝐵4𝑣 (𝑇)

=1+ + + +⋯

𝑉ത 𝑉ത 2 𝑉ത 3

𝑃𝑉ത

𝑍=

𝑅𝑇

= 1 + 𝐵2𝑃 𝑇 𝑃 + 𝐵3𝑃 𝑇 𝑃2 + 𝐵3𝑃 𝑇 𝑃2 + ⋯ .

coefficient).

molar volumes) Z → 1, reflecting ideal gas behavior.

For a truncated virial equation with two terms we have:

𝐵2𝑣 (𝑇)

1+ ഥ

𝑉

equations:

𝑅𝑇𝑐

𝐵2𝑣 𝑇 = 𝐵0 + 𝜔𝐵1

𝑃𝑐

0.422 0.172

B0 = 0.083 − 1.6 𝐵1 = 0.139 −

𝑇𝑅 𝑇𝑅 4.2

geometry and polarity of a molecule.

In the limiting case where there are no interactions

between the molecules, all the virial coefficients are

equal to zero becomes:

ഥ

𝑃𝑉

𝑍= =1

𝑅𝑇

Table 1.1

Second virial Coefficients, B at 298.15K

GAS 𝑩/𝟏𝟎−𝟔 𝒎𝟑 𝒎𝒐𝒍−𝟏

𝐻2 14.1

He 11.8

𝑁2 -4.5

02 -16.1

Ar -15.8

CO -8.6

Table 1.2

Second Virial Coefficients, B(10−6 𝑚3 𝑚𝑜𝑙−1 )

GAS 𝑻𝒆𝒎𝒑𝒆𝒓𝒂𝒕𝒖𝒓𝒆

273K 600K

Ar -21.7 11.9

𝐻2 13.7

He 12.0 10.4

𝑁2 -10.5 21.7

02 -22.0 12.9

Ne 10.4 13.8

Xe -153.7 -19.6

Table 1.3

Third virial Coefficients, C at 298.15K

GAS 𝑪/𝟏𝟎−𝟏𝟐 𝒎𝟔 𝒎𝒐𝒍−𝟐

𝐻2 350

He 121

𝑁2 1100

02 1200

Ar 1160

CO 1550

SAMPLE PROBLEMS

Solution ---------------------------------------------------------------------------

𝐵𝑃 (0.0217𝐿𝑚𝑜𝑙−1 )(600𝑏𝑎𝑟)

𝑍 =1+ =1+ = 1.261

𝑅𝑇 (8.315 L𝑚𝑜𝑙 −1 )(600𝐾)

𝑍𝑅𝑇

𝑉𝑚 =

𝑃

= 1.261 8.3145𝑥10−2 𝐿𝑚𝑜𝑙 −1

= 𝟎. 𝟏𝟎𝟒𝟖𝑳𝒎𝒐𝒍−𝟏

Use the virial equation to determine the pressure in

atm of 1 mole of carbon dioxide gas contained in a

volume of 5.0 L at 300 K.

Solution ---------------------------------------------------------------------------

𝑧= =1+ + 2 +⋯

𝑅𝑇 𝑉𝑚 𝑉𝑚

Using this equation but only including terms up

to the second virial coefficient B. we can solve for the

pressure,

𝑃𝑉𝑚 𝐵2𝑣 𝑇

z= 𝑅𝑇

= 1+

𝑉𝑚

𝑃𝑉𝑚

z= 𝑅𝑇

𝐵2𝑣 (𝑇)

z= (1 + )

𝑉𝑚

= 1−

(5.0𝐿 𝑚𝑜𝑙 −1 ) 5.0𝐿 𝑚𝑜𝑙 −1

P=4.80 atm

Solution ---------------------------------------------------------------------------

𝐵2𝑣 (𝑇)

𝑃𝑉

𝑅𝑇

=1+ ഥ

𝑉

+ 𝐵3𝑣𝑉ഥ 2(𝑇)

3

Let us assume 𝑉ത = 0.219𝑥10−3 𝑚 ൗ𝑚𝑜𝑙

ഥ

𝑃𝑉 (8𝑥106 )(0.219𝑥10−3 )

L.H.S of eqn gives: = = 0.4215

𝑅𝑇 (8.314)(500)

R.H.S of eqn gives: 1 + ഥ

+ ഥ2

𝑉 𝑉

0.265𝑥10−3 0.3025𝑥10−7

=1− +

0.219𝑥10−3 0.219𝑥10−3 2

= 0.4206

ത −3 𝑚3ൗ

Therefore, 𝑉 = 0.219𝑥10 𝑚𝑜𝑙

Solution ------------------------------------------------------------------------

3𝐿

𝑉ത = = 1.5 𝐿ൗ𝑚𝑜𝑙 𝑇 = −150.8℃ + 273.2 = 122.4𝐾

2𝑚𝑜𝑙

𝑎𝑡𝑚

ത

𝑅𝑇 (0.08206𝐿 ∙ )(122.4𝐾)

𝑃𝑖𝑑𝑒𝑎𝑙 = = 𝑚𝑜𝑙 ∙ 𝐾 = 6.696𝑎𝑡𝑚

𝑣ҧ 1.50𝐿/𝑚𝑜𝑙

From the truncated virial equation,

𝑝𝑣ത 𝐵(𝑇)

ത

=1+

𝑅𝑇 𝑣ത

122.4

𝑇𝑅 = = 0.970

126.2

0.422 0.422

𝐵0 = 0.083 − = 0.084 − = −0.360

𝑇𝑅 1.6 0.971.6

0.172 0.172

𝑩1 = 0.139 − = 𝐵1 = 0.139 − = −0.0566

𝑇𝑅 4.2 0.974.2

ത 𝑐

𝑅𝑇

𝐵 𝑇 = 𝐵0 + 𝜔𝐵1

𝑃𝑐

(0.08206 𝐿∙𝑎𝑡𝑚/𝑚𝑜𝑙∙𝐾)(126.2 𝐾)

𝐵 𝑇 = −0.36 + 0.04 −0.0566

33.5 𝑎𝑡𝑚

𝐿

= −0.112

𝑚𝑜𝑙

𝑎𝑡𝑚

ത

𝑅𝑇 0.112 0.08206 𝐿 ∙ ∙𝐾 122.4 𝐾

𝑝= 1− = 𝑚𝑜𝑙 0.9253

𝑣ҧ 1.5 𝐿

1.50

𝑚𝑜𝑙

𝒑 = 𝟔. 𝟏𝟗𝟔 𝒂𝒕𝒎

Solution ------------------------------------------------------------------------

bar:= 100kPa

cm3

kJ=1000J B≔ −110 T = 273.15 + 40 K

mol

dm3

v ≔ 2.5

mol

𝑃𝑐 = 73.773bar 𝑇𝑐 = 304.128𝐾

𝑃𝑉 𝐵2𝑣 (𝑇)

=1+

𝑅𝑇 𝑉ത

1

1 + 𝐵2𝑝 𝑇 ത 𝑅𝑇

𝑃= 𝑉

𝑉ത

cm3

1 + (−110 )(8.31433 J/K.mol)(304.128𝐾

= mol

dm3

2.5

mol

𝑃 = 9.956𝑏𝑎𝑟

Solution ------------------------------------------------------------------

0.211.Thus,

(250 + 273.15𝐾)

𝑇𝑟 = = 0.931

562.2𝐾

4𝑏𝑎𝑟

𝑃𝑟 = = 0.0817

48.98 𝑏𝑎𝑟

0

0.422 1

0.172

𝐵 = 0.083 − 1.6 𝐵 = 0.139 −

𝑇𝑟 𝑇𝑟 4.2

0.422 0.172

= 0.083 − = 0.139 −

0.931 1.6 0.931 4.2

= −0.390 = −0.093

𝐵′𝑃𝑐

= 𝐵0 + 𝜔𝐵1 = −0.390 + 0.211 −0.093

𝑅𝑇𝑐

= −0.410

𝐵′𝑃𝑐 𝑃𝑟

𝑍 =1+

𝑅𝑇𝑐 𝑇𝑟

0.0817

= 1 + −0.410

0.931

𝑍 = 0.964

Solution ------------------------------------------------------------------

𝑃𝑉𝑚 𝐵 𝐶

𝑧= =1+ + +⋯

𝑅𝑇 𝑉𝑚 𝑉𝑚 2

𝑃𝑉𝑚 𝐵

𝑧= ≈1+

𝑅𝑇 𝑉𝑚

At room temperature (300 K) and standard pressure (1 atm), the

molar volume is

𝑅𝑇

𝑉𝑚 =

𝑃

−1

(0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 )(300𝐾)

=

(1𝑎𝑡𝑚)

𝐿

= 24.62

𝑚𝑜𝑙

B = −3.91cm3/mol = −0.00391L/mol,

𝐵

z≈1+

𝑉𝑚

0.00391𝐿

= 1 − 𝑚𝑜𝑙

24.62𝐿

𝑚𝑜𝑙

= 1 − 0.00016

𝑍 = 0.99984

ideal case by about 0.02% at 300K and 1 atm pressure.

Solution --------------------------------------------------------------------

𝑉𝑖𝑑𝑒𝑎𝑙 = =

𝑃 400𝑏𝑎𝑟

= 9.83𝑥10 𝐿𝑚𝑜𝑙 −1

−2

𝐵𝑃

Z = 1 + BV = 1 +

𝑅𝑇

−1

(−0.417𝐿𝑚𝑜𝑙 )(400𝑏𝑎𝑟)

=1+ = 0.9965

(8.314𝐿𝑏𝑎𝑟𝐾 −1 𝑚𝑜𝑙 −1 )(573𝐾)

𝑉ത𝑟𝑒𝑎𝑙 = 𝑉ത𝑖𝑑𝑒𝑎𝑙 𝑍 = 9.83𝑥10−2 𝑚𝑜𝑙−1 0.9965

= 9.79𝑥10−2 𝐿𝑚𝑜𝑙−1

9.83𝑥10−2 −(9.79𝑥10−2 )

Deviation = 𝑥 100

9.83𝑥10−2

= 0.4%

Solution -------------------------------------------------------------------------------------

Constants:

kPA=1000Pa R=8.31433 J/Kmol bar=1000kPa dm=0.1m

Given:

T= 300K M= 10kg V=0.1m^3 Mw= 28.054 gm/mol B= -138cm^3/mol

𝑀 10𝑘𝑔

𝑛= = 𝑔𝑚 = 356.455 𝑚𝑜𝑙

𝑀𝑤 28.054 ൗ𝑚𝑜𝑙

𝑃𝑉 1

=1+𝐵

𝑛𝑅𝑇 𝑉

𝑉 + 𝐵𝑛

P = nRT

𝑉2

= 356.455𝑚𝑜𝑙 8.31433 𝐽Τ𝐾𝑚𝑜𝑙 300𝐾

(0.1𝑚3 )2

𝑃 = 45.175 𝑏𝑎𝑟

EXERCISES

𝑏𝑒𝑛𝑧𝑒𝑛𝑒 ℎ𝑎𝑠 𝑇𝑐 =

562.2𝐾, 𝑃𝑐 = 48.98𝑏𝑎𝑟, 𝑎𝑛𝑑 𝜔 = 0.211

SOLUTION:

(250 + 273.15𝐾) 0.422

𝑇𝑟 = = 0.931 𝐵0 = 0.083 −

562.2𝐾 𝑇𝑟 1.6

0.422

= 0.083 −

0.931 1.6

= −0.390

0.172

𝐵1 = 0.139 − 4.2 𝐵′𝑃𝑐

𝑇𝑟 = 𝐵0 + 𝜔𝐵1

0.172 𝑅𝑇𝑐

= 0.139 − = −0.390 + 0.211 −0.093 = −0.410

0.931 4.2

= −0.093

𝐵′𝑃𝑐 𝑃𝑟

𝑍 =1+

𝑅𝑇𝑐 𝑇𝑟

0.572

= 1 + −0.410

0.931

𝑍 = 0.748

Solution: At room temperature (300 K) and

𝑃𝑉𝑚 𝐵 𝐶

𝑧= =1+ + +⋯ standard pressure (1 atm), the molar

𝑅𝑇 𝑉𝑚 𝑉𝑚 2

volume is

𝑃𝑉𝑚 𝐵 𝑅𝑇

𝑧= ≈1+ 𝑉𝑚 =

𝑅𝑇 𝑉𝑚 𝑃

=

𝑅𝑇 (0.08205 𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 )(300𝐾)

𝑉𝑚 = (1𝑎𝑡𝑚)

𝑃 𝐿

= 24.62 𝑚𝑜𝑙

B = −3.91cm3/mol = −0.00391L/mol,

𝐵

z≈1+

𝑉𝑚

1.126𝐿

= 1 − 𝑚𝑜𝑙

24.62𝐿

𝑚𝑜𝑙

= 1 − 0.0457

𝑍 = 0.9543

So our estimate is that diatomic nitrogen only deviates from the ideal case by

about 4.6% at 300K and 1 atm pressure.

(R = 0.08205𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙−1, 𝐵 = 0.126 𝐿 𝑚𝑜𝑙−1)

𝑃𝑉𝑚 𝐵2𝑣 (𝑇) 𝐵3𝑣 (𝑇)

𝑧= =1+ + 2 +⋯

𝑅𝑇 𝑉𝑚 𝑉𝑚

𝑃𝑉𝑚 𝐵2𝑣 𝑇

z= 𝑅𝑇

= 1 +

𝑉𝑚

𝑃𝑉𝑚

z= 𝑅𝑇

𝐵2𝑣 (𝑇)

z= (1 + )

𝑉𝑚

= 1−

(6.0𝐿 𝑚𝑜𝑙 −1 ) 6.0𝐿 𝑚𝑜𝑙 −1

P=4.02 atm

(The virial coefficient B of N2(g) at 600 K is 0.0217 L mol-1., R = 8.315 L𝑚𝑜𝑙−1)

𝐵𝑃 (0.0217𝐿𝑚𝑜𝑙 −1 )(300𝑏𝑎𝑟)

𝑍 =1+ =1+

𝑅𝑇 (8.315x10−2 L𝑚𝑜𝑙 −1 )(600𝐾)

= 1.1304

𝑍𝑅𝑇

𝑉𝑚 =

𝑃

=

(300𝑏𝑎𝑟)

= 𝟎. 𝟏𝟖𝟕𝟖𝑳𝒎𝒐𝒍−𝟏

𝑅𝑇 (8.314𝑥10−2 𝐿𝑏𝑎𝑟𝐾 −1 𝑚𝑜𝑙 −1 )

𝑉𝑖𝑑𝑒𝑎𝑙 = =

𝑃 500𝑏𝑎𝑟

= 7.87𝑥10 𝐿𝑚𝑜𝑙 −1

−2

𝐵𝑃

Z = 1 + BV = 1 +

𝑅𝑇

−1

(−0.417𝐿𝑚𝑜𝑙 )(500𝑏𝑎𝑟)

= 1+ = 0.9562

(8.314𝐿𝑏𝑎𝑟𝐾 −1 𝑚𝑜𝑙 −1 )(573𝐾)

= 9.40𝑥10−2 𝐿𝑚𝑜𝑙 −1

7.87𝑥10−2 −(9.40𝑥10−2 )

Deviation = 𝑥 100 = 19.4%

7.87𝑥10−2

SOLUTION:

6𝐿

𝑉ത = = 3 𝐿ൗ𝑚𝑜𝑙 𝑇 = −150.8℃ + 273.2

2𝑚𝑜𝑙

= 122.4𝐾

𝑎𝑡𝑚

ത

𝑅𝑇 (0.08206𝐿 ∙ )(122.4𝐾)

𝑃𝑖𝑑𝑒𝑎𝑙 = = 𝑚𝑜𝑙 ∙ 𝐾

𝑣ҧ 3.0𝐿/𝑚𝑜𝑙

= 3.348𝑎𝑡𝑚

From the truncated virial equation,

𝑝𝑣ത 𝐵(𝑇)

ത

=1+

𝑅𝑇 𝑣ത

122.4

𝑇𝑅 = 126.2 = 0.970

0.422 0.422

𝐵0 = 0.083 − 𝑇 1.6 = 0.084 − 0.971.6 = −0.360

𝑅

0.172 0.172

𝑩1 = 0.139 − 𝑇 4.2 = 𝐵1 = 0.139 − 0.974.2 = −0.0566

𝑅

ത 𝑐

𝑅𝑇

𝐵 𝑇 = 𝐵0 + 𝜔𝐵1

𝑃𝑐

(0.08206 𝐿∙𝑎𝑡𝑚/𝑚𝑜𝑙∙𝐾)(126.2 𝐾)

𝐵 𝑇 = ሾ−0.36 +

33.5 𝑎𝑡𝑚

ത

𝑅𝑇 0.112

= 1−

𝑣ҧ 1.5

𝑎𝑡𝑚

0.08206 𝐿 ∙ ∙ 𝐾 122.4 𝐾

= 𝑚𝑜𝑙 0.9253

𝐿

3.0

𝑚𝑜𝑙

𝒑 = 𝟑. 𝟎𝟗𝟖 𝒂𝒕𝒎

Solution ----------------------------------------------------------------------------------

𝑅𝑇 𝐵

𝑃= 1+

𝑣ҧ 𝑣ҧ

𝐽

8.314 105 + 273.15 𝐾

= 𝑚𝑜𝑙𝑒 ∙ 𝐾 (1

𝑚 3

0.02814

𝑚𝑜𝑙𝑒

4.0𝑥10−4 𝑚3 /𝑚𝑜𝑙𝑒

− 3

)

0.02814𝑚 /𝑚𝑜𝑙𝑒

= 𝟏. 𝟏𝟎𝟏𝒙𝟏𝟎𝟓 𝑷𝒂 = 𝟏𝟏𝟎. 𝟏 𝒌𝑷𝒂

8. Calculate the pressure of water whose

temperature is 105𝑜 𝐶 and speciific

volume is 1561.6 𝑐𝑚3 /𝑔 using the virial

equation.

(water has a molecular mass of 18.02 𝑔/𝑚𝑜𝑙)

𝑐𝑚3 𝑔

𝑣ҧ = 𝑣𝑀 = 1561.6 18.02 = 2.814 𝑥104 𝑐𝑚3 /𝑚𝑜𝑙

𝑔 𝑚𝑜𝑙

= 0.02814 𝑚3 /𝑚𝑜𝑙

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