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VIRIAL EQUATION OF

STATE
WHAT IS VIRIAL EXPANSION?

• The compressibility is expressed as an infinite series


ഥ −1 ) or the pressure
expansion in either the density (𝑉

𝑃𝑉 𝐵2𝑣 (𝑇) 𝐵3𝑣 (𝑇) 𝐵4𝑣 (𝑇)
𝑍= =1+ ഥ
+ ഥ2
+ ഥ3
+⋯
𝑅𝑇 𝑉 𝑉 𝑉


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 + ⋯ .

𝐵𝑛𝑥 are virial coefficients (𝐵2𝑣 is a “second” virial


coefficient).

Note that at very low pressures or densities (large


molar volumes) Z → 1, reflecting ideal gas behavior.
For a truncated virial equation with two terms we have:
𝐵2𝑣 (𝑇)
1+ ഥ
𝑉

In this equation, B(T) can be estimated from the following


equations:
𝑅𝑇𝑐
𝐵2𝑣 𝑇 = 𝐵0 + 𝜔𝐵1
𝑃𝑐

0.422 0.172
B0 = 0.083 − 1.6 𝐵1 = 0.139 −
𝑇𝑅 𝑇𝑅 4.2

ω is the Pitzer acentric factor, which is a parameter reflecting the


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:


𝑃𝑉
𝑍= =1
𝑅𝑇

is the ideal gas equation of state.


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 ---------------------------------------------------------------------------

• The virial coefficient B of N2(g) at 600 K is 0.0217 L mol-1.

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 ---------------------------------------------------------------------------

The virial equation is

𝑃𝑉𝑚 𝐵2𝑣 (𝑇) 𝐵3𝑣 (𝑇)


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

(0.08205𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 )(300𝑘) 0.126 𝐿 𝑚𝑜𝑙 −1


= 1−
(5.0𝐿 𝑚𝑜𝑙 −1 ) 5.0𝐿 𝑚𝑜𝑙 −1

P=4.80 atm
Solution ---------------------------------------------------------------------------

The virial equation of state is given by

𝐵2𝑣 (𝑇)
𝑃𝑉
𝑅𝑇
=1+ ഥ
𝑉
+ 𝐵3𝑣𝑉ഥ 2(𝑇)

3
Let us assume 𝑉ത = 0.219𝑥10−3 𝑚 ൗ𝑚𝑜𝑙

𝑃𝑉 (8𝑥106 )(0.219𝑥10−3 )
L.H.S of eqn gives: = = 0.4215
𝑅𝑇 (8.314)(500)

𝐵2𝑣 (𝑇) 𝐵3𝑣 (𝑇)


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

From the ideal gas law,

𝑎𝑡𝑚

𝑅𝑇 (0.08206𝐿 ∙ )(122.4𝐾)
𝑃𝑖𝑑𝑒𝑎𝑙 = = 𝑚𝑜𝑙 ∙ 𝐾 = 6.696𝑎𝑡𝑚
𝑣ҧ 1.50𝐿/𝑚𝑜𝑙
From the truncated virial equation,

𝑝𝑣ത 𝐵(𝑇)

=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

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 ------------------------------------------------------------------------

kPa:= 1000Pa dm:= 0.1m R:= 8.31433 J/K.mol


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

Solving for P results in

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 ------------------------------------------------------------------

Benzene has 𝑇𝑐 = 562.2𝐾, 𝑃𝑐 = 48.98𝑏𝑎𝑟, 𝑎𝑛𝑑 𝜔 =


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

So our estimate is that diatomic nitrogen only deviates from the


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

𝑅𝑇 (8.314𝑥10−2 𝐿𝑏𝑎𝑟𝐾 −1 𝑚𝑜𝑙 −1 )


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

0.1𝑚3 + (138 𝑐𝑚3 Τ𝑚𝑜𝑙)( 356.455𝑚𝑜𝑙)


= 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

(0.08205𝐿 𝑎𝑡𝑚 𝑚𝑜𝑙 −1 𝐾 −1 )(300𝑘) 0.126 𝐿 𝑚𝑜𝑙 −1


= 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

1.0131 8.3145𝑥10−2 𝐿𝑚𝑜𝑙 −1 (600𝐾)


=
(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)

𝑉ത𝑟𝑒𝑎𝑙 = 𝑉ത𝑖𝑑𝑒𝑎𝑙 𝑍 = 9.83𝑥10−2 𝑚𝑜𝑙 −1 0.9562

= 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

From the ideal gas law,

𝑎𝑡𝑚

𝑅𝑇 (0.08206𝐿 ∙ )(122.4𝐾)
𝑃𝑖𝑑𝑒𝑎𝑙 = = 𝑚𝑜𝑙 ∙ 𝐾
𝑣ҧ 3.0𝐿/𝑚𝑜𝑙
= 3.348𝑎𝑡𝑚
From the truncated virial equation,

𝑝𝑣ത 𝐵(𝑇)

=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

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