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WHAT IS VIRIAL EXPANSION?
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 + ⋯ .
0.422 0.172
B0 = 0.083 − 1.6 𝐵1 = 0.139 −
𝑇𝑅 𝑇𝑅 4.2
ഥ
𝑃𝑉
𝑍= =1
𝑅𝑇
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 ---------------------------------------------------------------------------
𝑃𝑉𝑚 𝐵2𝑣 𝑇
z= 𝑅𝑇
= 1+
𝑉𝑚
𝑃𝑉𝑚
z= 𝑅𝑇
𝐵2𝑣 (𝑇)
z= (1 + )
𝑉𝑚
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)
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 ------------------------------------------------------------------------
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 ------------------------------------------------------------------
(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
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
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
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
= 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