RG-010. The compressibility factor Z=PV/RT for CO is 0.9920 at 25C and 75.0 atm and 1.

7412
at 25C and 800 atm. Calculate the percentage errors introduced at these two conditions if (a) the
ideal gas law and (b) van der Waals equation is used to calculate the volume of 1 mole of CO.
Van der Waals constants: a = 1.505 L2atm mol-2 and b = 3.985 x 10-2 L mol-1

If Z=0.9920, T=25C, P=75.0 atm:

, =

(0.9920)(0.08206

)(25+273.15)

75.0

= 0.3236061265 0.324

If Z=1.7412, T=25C, P=800 atm:

, =

(1.7412)(0.08206

)(25+273.15)

= 0.05325066036 0.0533

800

a.) IDG
=

If T=25C, P=75.0 atm:

% =

(0.08206

)(25+273.15)

75.0

= 0.3262158533 0.326

|. |

100 =

0.326
|

0.324

|0.324

100 = 0.617 %

If T=25C, P=800 atm:

=

% =

(0.08206

)(25+273.15)

800
|. |

= 0.03058273625
100 =

0.0306

0.0306
|

0.0533

|0.0533

100 = 42.6 %

b.) VDW equation

2 +

3 2

2 = 2 +
( + )2 + =

2 =

3
3
0
If T=25C, P=75.0 atm:
753 [(3.985 102 )(75) + (0.08206)(298.15)]2 + 1.505 (1.505)(3.985 102 ) = 0
753 27.4549392 + 1.505 0.05997425 = 0

1 = 0.3095924729 0.310 (2 3 )
% =

|. |

100 =

0.310
|

0.324

|0.324

100 = 4.32 %

If T=25C, P=800 atm:

8003 [(3.985 102 )(800) + (0.08206)(298.15)]2 + 1.505 (1.505)(3.985
102 ) = 0
8003 56.3461892 + 1.505 0.05997425 = 0

1 = 0.0599172238 0.0600 (2 3 )
% =

|. |

100 =

0.0600
|

0.0533

|0.0533

100 = 12.6 %

RG-019. One mole of gas at 100 K is compressed isothermally from an initial volume of 20 dm 3
to a final volume of 5 dm3. Calculate the work done on the system if (a) the gas ideal (b) the
equation of state is

( + 2 ) = = 0.384 6 1

Account for the difference between the values in (a) and (b).
a.) IDG

= = (

20 3

= ln ( ) = (1 ) (8.3145 ) (100 ) ln ( 5 3 ) =

1152.634447 1.15
b.)
1

,
( 2 )
,

= 0.384 6 1 (101325 ) (0.0013 ) (0.0013 ) = 3.789785344

= , = , (
,

ln (

) + (

3.789785344

1
,

1
)
,

2
1
( 5 3

2 )

= (8.3145
1

20 3
) (100 ) ln (
)+

5 3

) = 1152.634447

20 3

8.3145
0.5684678016
(
)
0.08206

= , ( ) +

= 1095.036037

(1

) = 1095.036037 1.10

The values obtained in (a) and (b) are different since different equations of state were
used. The pressure between the ideal gas law and the equation of state of (b) has the difference
of the term -a/Vm2, hence the work calculated for (b) will deviate from the ideal gas law.

RG-026. By measuring the equilibrium between liquid and vapor phases of an acetone-methanol
solution at 57.2C at 1.00 atm, it was found that Xacetone = 0.400 (mol in fraction liquid) when Yacetone
= 0.516 (mol fraction in vapor). Calculate the activities and activity coefficients of both
components at this temperature are: p(acetone) = 786 torr and p(methanol) = 551 torr.
=

(0.516)(760 )

= (0.400)(786 ) = 1.247328244 1.25

)
(1

(0.484)(760 )
= (0.600)(551 ) =
)
(1

760
= = 786 = 0.9669211196 0.967

760
= = 551 = 1.379310345 1.38

1.112643678 1.11

RG-031. Compare the values obtained for the pressure of 3.00 mol CO2 at 298.15 K held in an
8.25-dm3 bulb using the ideal gas, van der Waals, Dieterici, and Beattie-Bridgeman equations. For
CO2 the Dieterici equation constants are a = 0.462 Pa m6 mol-2 and b = 4.63 x 10-5 m3 mol-1.
6
1
1
1
(
) (0.0013 ) (0.0013 ) =
2 101325
3
1

4.63 105 = (0.001 3 ) = 0.0463

= 0.462
=

a.) IDG
=

)(298.15 )

1
3
8.25 dm (
)
1 dm3

(3.00 )(0.08206

b.) VDW
=

)(298.15 )

8.25

(
)0.0463
3.00

(0.08206

(0.08206

2
2

= 8.896796 8.90
4.559585492
(

c.) Dieterici
( ) = /
/

4.559585492

2
2
2

8.25
)
3.00

= 8.446230398 8.45

2

8.25
)(298.15 )exp(4.559585492
/(0.08206
)(298.15 )(
))


3.00
2
8.25

(
)0.0463
3.00

8.456223313 8.46
d.) Beattie-Bridgeman
a
1.62129 x103 m3/kg
A0
262.07 Nm4/kg2
b
1.6444 x103 m3/kg
B0
2.3811 x103 m3/kg
c
1.4997 x104 m3K3/kg
Source: Klein, S. A., Nellis, G. F., Cambrifge University Press. 2011, 1.
=

(1

)
3

3 3
4
1.499710

(0.08206
)(298.15 )(1
)

8.25 3
(
)(298.15 )3
3.00
8.25 3
m3
1.6444103
kg
8.25 3
3.00

[ + 0 (1 )] 20 (1 ) =

)]

3.00
N m4
262.07 2
kg
3
8.25 3

3.00

(1

1.62129103
8.25 3
3.00

8.25 3

[( 3.00 ) + (2.3811 103

m3
kg

)=

m3
) (1
kg

RG-093. One mole of a gas at 300 K is compressed isothermally and reversibly from an initial
volume of 10 dm3 to a final volume of 0.2 dm3. Calculate the work done on the system if (a) the
gas is ideal, (b) the equation of state of the gas is P(Vm b) = RT, with b = 0.03 dm3 mol-1. Account
for the difference between the two values.
a.) IDG

= = (

10 3

= ln ( ) = (1 ) (8.3145 ) (300 ) ln (0.2 3 ) =

9757.954584 9.76
b.)

= , = , (
,

) = , (
,

10 3 0.03

(8.3145 ) (300 ) ln (
)
3
0.2 3 0.03

) = ln ( , ) =
,

= 10155.83938 10.2

The values obtained in (a) and (b) are different since different equations of state were
used. The molar volume between the ideal gas law and the equation of state of (b) has the
difference of the term b, hence the work calculated for (b) will deviate from the ideal gas law.