Solution

thermodynamics theory
Part I
Chapter 11

topics
Fundamental equations for mixtures
Chemical potential
Properties of individual species in
solution (partial properties)
Mixtures of real gases
Mixtures of real liquids

A few equations
For a closed system
G H TS
d (nG ) d (nH ) Td (nS ) (nS )dT
from
H U PV
obtain d(nH)
d (nG ) (nV )dP (nS )dT
Total differential form, what are (nV) and (nS)
Which are the main variables for G??
What are the main variables for G in an open system of
k components?

G in a mixture (open
system)
(nG )
d (nG )

(nG )
dP

T ,n

dT
P ,n

G in a mixture of k components at T
and P
k

d (nG ) (nV )dP (nS )dT i dni

i 1

How is this equation reduced if n =1

2 phases (each at T and P) in a closed

system
Apply this equation to each phase

d (nG ) (nV )dP (nS )dT i dni

i 1

Sum the equations for each phase, take into account that

(nM ) (nM ) (nM )

In a closed system:

d (nG ) (nV )dP (nS )dT

We end up with

dn dn 0

How are dni and dni related at constant n?

For 2 phases, k components at

equilibrium

T T

P P

For all i = 1, 2,k

Thermal equilibrium

Mechanical equilibrium

Chemical equilibrium

In order to solve the PE

problem
Need models for i in each phase
Examples of models of i in the vapor
phase
Examples of models of i in the liquid
phase

Now we are going to learn

about
Partial molar properties
Because the chemical potential is a partial
molar property
At the end of this section think about this
What is the chemical potential in physical terms
What are the units of the chemical potential
How do we use the chemical potential to solve a
PE (phase equilibrium) problem

Partial molar property

(nM )
Mi

n
i

Solution property
Partial property
Pure-species property

P ,T , n j i

example
(nV )
Vi

ni
(nV ) Vw nw
~
(nV ) Vw nw
lim nw 0

Open beaker: ethanol + water, equimolar

Total volume nV
T and P

P ,T , n j i

Add a drop of pure water, nw

Mix, allow for heat exchange, until temp T

Change in volume ?

Total vs. partial properties

M xi M i
i

nM ni M i
i

See derivation page 384

Derivation of Gibbs-Duhem
equation
M
dM

P
M xi M i
i

M
dP

T
T ,x

P,x

dT M i dxi
i

Gibbs-Duhem at constant
T&P

x dM
i

constant T & P

Useful for thermodynamic consistency tests

Binary solutions
See derivation page 386

dM
M 1 M x2
dx1
dM
M 2 M x1
dx1

Obtain dM/dx1 from (a)

Example 11.3
We need 2,000 cm3 of antifreeze
solution: 30 mol% methanol in water.
What volumes of methanol and water
(at 25oC) need to be mixed to obtain
2,000 cm3 of antifreeze solution at 25oC
Data:

V1 38.63cm / mol

V1 40.73cm / mol methanol

V2 17.77cm / mol

V1 18.07cm / mol water

solution
Calculate total molar volume

We know the total volume, calculate the

number of moles required, n
Calculate n1 and n2
Calculate the volume of each pure species

Note curves for partial molar volumes

From Gibbs-Duhem:

x dM
i

constant T & P

x1dV1 x2 dV2 0
Divide by dx1, what do you conclude respect to the slopes?

Read and work example

11.4
Given H=400x1+600x2+x1x2(40x1+20x2)
determine partial molar enthalpies as
functions of x1, numerical values for purespecies enthalpies, and numerical values
for partial enthalpies at infinite dilution
Also show that the expressions for the
partial molar enthalpies satisfy GibbsDuhem equation, and they result in the
same expression given for total H.

Now we are going to start looking

at models for the chemical
potential of a given component in a
mixture

The first model is the ideal gas mixture

The second model is the ideal solution
As you study this, think about the
differences, not only mathematical but
also the physical differences of these
models

The ideal-gas mixture

model
EOS for an ideal gas

Calculate the partial molar volume

for an ideal gas in an ideal gas
mixture

For an ideal gas mixture

Vi (T , P) Vi (T , P ) V (T , P)
ig

ig

and
RT
pi yi P yi ig
V

ig

For any partial molar property other

than volume, in an ideal gas
mixture:
M (T , P ) M (T , pi )
ig
i

ig
i

H iig (T , P) H iig (T , pi )
dS Rd ln P
ig
i

at constant T

integrate from pi to P

Partial molar entropy (igm)

S (T , pi ) S (T , P ) R ln yi
ig
i

ig
i

S (T , P) S (T , pi ) S (T , P ) R ln yi
ig
i

ig
i

ig
i

Partial molar Gibbs energy

Gi ig H iig TSiig H iig TS iig RT ln yi

iig Gi ig Giig RT ln yi

Chemical potential of
component i in an
ideal gas mixture

*******************************************************************************

RT
dG Vi dP
dP RTd ln P at constant T
P
integrating between P 1atm and P
ig
i

ig

Giig i (T ) RT ln P

This is for a pure component !!!

i (T ) RT ln P RT ln yi i (T ) RT ln yi P
ig
i

Problem
What is the change in entropy when 0.7
m3 of CO2 and 0.3 m3 of N2, each at 1 bar
and 25oC blend to form a gas mixture at
the same conditions? Assume ideal gases.
We showed that:

Siig Siig R ln yi
S yi S
ig

ig
i

yi S R yi ln yi
ig
i

S yi S R yi ln yi
ig

ig
i

solution
S nR yi ln yi
i

n = PV/RT= 1 bar 1 m3/ [R x 278 K]

S = 204.89 J/K

Problem
What is the ideal work for the
separation of an equimolar mixture
of methane and ethane at 175oC and
3 bar in a steady-flow process into
product streams of the pure gases at
35oC and 1 bar if the surroundings
temperature
T =of300K?
1)
Read section 5.8 (calculation
ideal work)
2) Think about the process: separation of gases and change of state

First calculate H and S for methane and for ethane changing their state from
P1, T1, to P2T2
Second, calculate H for de-mixing and S for de-mixing from a mixture of ideal
gases

solution
ig

T2

H i Cp (T )dT
ig

T1

Si
ig

T2

T1

dT
P2
Cp (T )
ln
T
P1
ig

H deig mix 0

S deig mix R yi ln yi
i

H yi H i H deig mix

= -7228 J/mol

S yi Si S deig mix

= -15,813 J/mol K

Wideal = H T S = -2484 J/mol

Now we introduce a new concept:

fugacity
When we try to model real
systems, the expression for the
chemical potential that we used for
ideal systems is no longer valid
We introduce the concept of fugacity
that for a pure component is the
analogous (but is not equal) to the
pressure

We showed that:
G i (T ) RT ln P
ig
i

i i (T ) RT ln( yi P )
ig

Pure component i, ideal gas

Component i in a mixture
of ideal gases

Lets define:

Gi i (T ) RT ln f i

For a real fluid, we define

Fugacity of pure species i

Residual Gibbs free energy

fi
G Gi G RT ln
P
R
i

ig
i

G RT ln i
R
i

Valid for species i

in any phase and
any condition

Since we know how to calculate

residual properties

G RT ln i
R
i

R
i

P
G
dP
ln i ( Z i 1)
0
RT
P
Zi from an EOS, Virial, van der Waals, etc

examples
From Virial EOS

Bii P
ln i
RT

From van der Waals

EOS

bi P
ai P
ln i Z i 1 ln Z i
2 2
RT R T Z i

Fugacities of a 2-phase
system

G i (T ) RT ln f i
v
i

G i (T ) RT ln f i
l
i

One component, two phases:

saturated liquid and saturated vapor at Pisat and Tisat
What are the equilibrium conditions for a pure component?

Fugacity of a pure liquid at P

and T
v

sat

sat

f i ( Pi ) f i ( Pi ) f i ( P ) sat
f i ( P)
Pi
sat
v
sat
l
sat
Pi
f i ( Pi ) f i ( Pi )
l

Fugacity of a pure liquid at P

and T

1
l
sat sat
f i ( P) i Pi exp
RT

Pi

sat

Vi dP

example
For water at 300oC and for P up to 10,000 kPa
(100 bar) calculate values of fi and i from
data in the steam tables and plot them vs. P
*

fi
1
1 Hi Hi
*
*
ln *
(Gi Gi )
( Si Si )
RT
R
T
fi

At low P, steam is an ideal gas => fi* =P*

Get Hi* and Si* from the steam tables at 300oC and the lowest P, 1 kPa
Then get values of Hi and Si at 300oC and at other pressure P and calculate fi (P)

Problem
For SO2 at 600 K and 300 bar, determine good
estimates of the fugacity and of GR/RT.
SO2 is a gas, what equations can we use to
calculate f = /P
Find Tc, Pc, and acentric factor, Table B1, p. 680
Calculate reduced properties: Tr, Pr
Tr=1.393 and Pr=3.805

High P, high T, gas: use LeeKessler correlation

From tables E15 and E16 find 0 and 1
0 = 0.672; 1 = 1.354
= 0 1
f = P = 0.724 x 300 bar = 217.14 bar
GR/RT = ln

Problem
Estimate the fugacity of cyclopentane at
110oC and 275 bar. At 110 oC the vapor
pressure of cyclopentane is 5.267 bar.
At those conditions, cyclopentane is a high P liquid

1
l
sat sat
f i ( P ) i Pi exp
RT

Pi

sat

Vi dP

Find Tc, Pc, Zc,, Vc and acentric factor, , Table B1, p.

680
Calculate reduced properties: Tr, Prsat
Tr = 0.7486 and Prsat = 0.117
At P < Prsat we can use the virial EOS to calculate isat

sat
i

Pr 0
1
exp
( B B )
Tr

0.422 1
0.172
B 0.083 1.6 ; B 0.139 4.2
Tr
Tr
0

isat = 0.9
P-correction term:
Get the volume of the saturated liquid phase, Rackett equation

sat

Vc Z

(1Tr )
c

2/7

Vsat = 107.55 cm3/mol

1
l
sat sat
f i ( P ) i Pi exp
RT
f = 11.78 bar

Pi

sat

Vi dP

Generalized correlations: fugacity

coefficient
R
Gi RT ln i
R
i

P
G
dP
ln i ( Z i 1)
0
RT
P
P Pc Pr

ln i

Pr

ln i

Pr

dPr
( Z i 1)
Pr
Pr
dPr
1 dPr
( Z 1)
Z
0
Pr
Pr
0

ln i ln ln
0

0 ( 1 )

Tables E13 to E16

Lee-Kessler

HW # 3, Due Monday,
September 17
Problems 11.2, 11.5, 11.8, 11.12,
11.13

HW # 4, Due Monday, September 24

Problems 11.18, 11.19 (b), 11.21, 11.22
(a), 11.24(a), 11.25