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This document contains 6 problems related to solution thermodynamics theory. The problems cover topics such as calculating the entropy change of mixing gases, deriving expressions for molar enthalpies of binary liquid mixtures, estimating the fugacity ratio of liquid water at high pressure and temperature, calculating fugacity ratios for steam under isothermal changes in pressure, plotting fugacity and fugacity coefficient curves for carbon dioxide using compressibility factor data, and determining fugacity and Gibbs free energy estimates for sulfur dioxide using correlation equations and reference tables.

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71 views

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This document contains 6 problems related to solution thermodynamics theory. The problems cover topics such as calculating the entropy change of mixing gases, deriving expressions for molar enthalpies of binary liquid mixtures, estimating the fugacity ratio of liquid water at high pressure and temperature, calculating fugacity ratios for steam under isothermal changes in pressure, plotting fugacity and fugacity coefficient curves for carbon dioxide using compressibility factor data, and determining fugacity and Gibbs free energy estimates for sulfur dioxide using correlation equations and reference tables.

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ARYAN_FATHONI_AMRI
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ECHE 311/SPRING 2015

Problem Set #6
Solution Thermodynamics Theory

1. What is the change of entropy when 0.7 m3 of CO2 and 0.3 m3 of N2, each at 1 bar
and 25oC blend to form a homogeneous gas mixture at the same conditions?
Assume ideal gases.
The entropy change of mixing is given by Eq:

S  S ig   xi Si ig   R  xi ln xi
i i

2 For a particular binary liquid solution at constant T and P, the molar enthalpies of
mixtures are represented by the equation

H  x1 (a1  b1x1 )  x2 (a2  b2 x2 )


where a1 and b1 are constants. Since the equation has the form of Eq.


M   xi M i
i

it might be that

_ _
H 1  a1  b1 x 1 and H 2  a2  b2 x 2
 
Derive expression for H1 and H2 to show whether this is true.

1
sat
3 From the data of steam tables, determine an estimate for f / f for liquid
sat
water at 150oC and 150 bar, where f is the fugacity of saturated liquid at
150oC.
Hint: Use Table F.1 150 oC and Eq:

fi V l ( P  Pisat )
ln  i
f sat RT

4 Steam at 9,000 kPa and 400oC undergoes an isothermal change of state to a


pressure of 300 kPa. Determine the ratio of the fugacity in the final state to that in
the initial state.
Hint: Use Table F.2, 9000 kPa & 400oC and get the values of H1 and S1.
Use Table F.2, 300 kPa & 400oC and get the values of H2 and S2
The equation

1 H i  H i*
fi
ln  [  ( S i  S i* ] may be recast for
* R T
fi
this problem.

5 From the following compressibility-factor data for CO2 at 150oC prepare plots of
the fugacity and fugacity coefficient of CO2 vs P for pressures up to 500 bar.
Compare the resulting curves with those found from the generalized correlation
represented by Eq:

Pr o
  exp[ ( B    B1 )
Tr

__________________________________________________

P/bar Z P/bar Z
___________________________________________________

10 0.985 100 0.869


20 0.970 200 0.765
40 0.942 300 0.762
60 0.913 400 0.824
80 0.885 500 0.910
_________________________________________________

2
6 For SO2 at 600oK and 300 bar, determine good estimates of the fugacity and of
G/RT.
Hint: For given conditions the Lee/Kesler correlation is appropriate. Use data
from Tables E.15 & E.16. and Eq.   ( o )( 1 ) .

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