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3/30/2015
OVERVIEW
The purpose of this chapter is to express the theoretical foundation for
applications of thermodynamics to gas mixtures and liquid solutions.
Separation processes of multicomponent gases and liquids in chemical,
petroleum and pharmaceutical industries commonly undergo composition
changes, transfer of species from one phase to another and chemical reaction.
Thus compositions become essential variables, along with temperature and
pressure.
This chapter introduce new property, i.e. chemical potential which facilitate
treatment of phase and chemical reaction equilibria; partial properties which
are properties of individual species as they exist in solution; and fugacity which
provide treatment for real gas mixtures through mathematical formulation.
Another solution properties known as excess properties, is the deviation from
ideal solution property.
(2.11a)
(6.1)
(6.4)
(6.6)
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(6.6)
d nG nV dP nS dT
Equation (6.6) relates the total Gibbs energy of any closed system to
temperature and pressure.
An appropriate application is to a single phase fluid in a closed system
wherein no chemical reactions occur. For such a system the composition is
necessarily constant, and therefore
nG
P nV
T ,n
nG
T nS
P ,n
and
Total differential of nG is
nG
nG
nG
d nG
dni
dP T dT n
i
P T ,n
P ,n
i P ,T ,nj
(B)
The summation is over all species present, and subscript nj indicates that all
mole numbers except the ith are held constant.
The derivative in the final term is called the chemical potential of species i in
the mixture. It is define as
(A)
nG
ni P ,T ,nj
The subscript n indicates that the numbers of moles of all chemical species are
held constant.
For more general case of a single phase, open system, material may pass
into and out of the system, and nG becomes a function of the numbers of
moles of the chemical species present, and still a function of T and P.
nG g P , T , n1, n2 ,..., ni ,...
(11.1)
With this definition and with the first two partial derivatives [eqn. (A)]
replaced by (nV) and (nS), the preceding equation [eqn. (B)] becomes
d nG nV dP nS dT i dni
(11.2)
Equation (11.2) is the fundamental property relation for single phase fluid
systems of variable mass and composition.
dG VdP SdT i dx i
i
(11.3)
d nG nV dP nS dT i dni
dG VdP SdT
d nG nV dP nS dT i dni
(6.10)
Although the mole numbers ni of eq. (11.2) are independent variables, the
mole fractions xi in eq. (11.3) are not, because ixi = 1. Eq. (11.3) does
imply
G
G
S
V
(11.5)
(11.4)
T P , x
P T , x
Other solution properties come from definitions; e.g., the enthalpy, from
H = G + TS. Thus, by eq. (11.5),
G
H G T
T P , x
d nG d nG nV nV dP nS nS dT i dni i dni
i
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d nG d nG nV nV dP nS nS dT i dni i dni
i
Quantities dni are independent; therefore the only way the left side of the
second equation can in general be zero is for each term in parentheses
separately to be zero. Hence,
nM nM nM
i i
the sum is
d nG nV dP nS dT i dni i dni
i
i i ... i
Because the two phase system is closed, eq. (6.6) is also valid. Comparison of
the two equations shows that at equilibrium,
i dni i dni 0
i
d nG nV dP nS dT
and
(6.6)
(11.6)
Example: A glass of liquid water with ice cubes in it. When the chemical
potential of ice is larger than water, the ice melts. When chemical potential
of water is larger than ice, the water freezes. Water and ice are in
equilibrium when their chemical potential are the same.
dn 0
i
i 1,2,..., N
Multiple phases at the same T and P are in equilibrium when the chemical
potential of each species is the same in all phases.
The changes dni and dni result from mass transfer between the phases; mass
conservation therefore requires
dni dni
i 1,2,..., N
PARTIAL PROPERTIES
Example
A species exhibits its pure property when no other species exist with it, i.e.
pure component exhibits pure properties.
Species exhibits its partial property when it co-exists with other species in a
mixture or solution.
ni P ,T ,nj
When one mole of water is added to a large volume of water at 25C, the
volume increases by 18 cm3.
However, addition of one mole of water to a large volume of pure ethanol
results in an increase in volume of only 14 cm 3.
* The increase in volume is different due to intermolecular forces between
molecules, size and shape of molecules are different in mixture rather than pure
species.
(11.7)
10
_
nV
Vi
ni P ,T ,nj
M,
for example: V, U, H, S, G
M i , for example: Vi , U i , Hi , Si , G i
Mi , for example: Vi , Ui , Hi , Si , Gi
11
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Because ni = xin,
Moreover,
d nM ndM Mdn
M
M dT M x dn ndx
ndM Mdn n
dP n
i i i
i
P T , x
T P , x
nM
nM
nM
d nM
dP T dT n dni
P T ,n
P ,n
i
i
P ,T ,nj
The terms containing n are collected and separated from those containing dn
to yield
where subscript n indicates that all mole numbers are held constant, and subscript
nj that all mole numbers except ni are held constant.
Because the first two partial derivatives on the right are evaluated at constant n
and because the partial derivative of the last term is given by eq. (11.7), this
equation has the simpler form:
M
M
d nM n
dP n T dT Mi dni
P T , x
P , x
i
dni x i dn ndx i
M dP M dT M dx n M x M dn 0
i i i i i i
dM
P T , x
T P , x
The left side of this equation can be zero if each term in brackets be zero
too. Therefore,
(11.9)
M
M dT M dx
dM
dP
i i i
T , x
T P , x
(11.10) M x i Mi
i
(11.11)
13
14
nM ni Mi
(11.12)
Equations (11.11) and (11.12) are known as summability relations, they allow
calculation of mixture properties from partial properties.
Differentiate eq. (11.11) yields:
dM x i d Mi Mi dx i
i
lim M lim Mi Mi
xi 1
i i i
P T , x
T P , x
x i 1
For a species that approaches its infinite dilution limit, i.e., the values as its mole
fraction approaches zero, no general statements can be made. Values come
from experiment or from models of solution behavior. By definition,
(11.13)
lim Mi Mi
x i 0
x dM 0
i
(11.14)
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_
nM
Mi
ni P ,T ,nj
Summability:
M x i Mi
(11.11)
x1d M1 x 2 d M2 0
Gibbs/Duhem:
M
M dT
dP
P T , x
T P , x
(B)
dM x1d M1 M1 dx1 x 2 d M2 M2 dx 2
(A)
xdM
M x1 M1 x 2 M2
(11.7)
(C)
Because x1 + x2 = 1, dx1 + dx2 = 0 dx1 = - dx2. Substitute eq. (C) into eq.
(B) to eliminate dx2 gives
(11.13)
dM
M1 M2
dx1
(D)
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Two equivalent forms of eq. (A) result from elimination separately of x 1 and
x 2:
x1 1 x 2
x 2 1 x1
M 1 x 2 M1 x 2 M2
M M1 x 2 M1 M2
x1
M x1 M1 1 x1 M2
M M1 x 2 M1 x 2 M2
18
M x1 M1 M2 x1 M2
M x1 M1 M2 M2
dM
dx1
(11.15)
dM2
x dM1
1
dx1
x2 dx1
dM
dx1
(11.16)
M2 M x1
(E)
dM1
x dM2
2
dx1
x1 dx1
and
M1 M x2
d M1
d M2
x2
0
dx1
dx1
(F)
(G)
When M1 and M2 are plotted vs. x1, the slopes must be of opposite sign.
Thus for binary systems, the partial properties are calculated directly from an
expression for the solution property as a function of composition at constant T
and P.
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EXAMPLE 11.2
Moreover,
d M1
lim
0
x1 1 dx
1
Similarly,
d M2
0
x 2 1 dx
1
lim
d M2
Provided lim
is finite
x1 1 dx
and
I1 I2
dx1
x1
dx1
Solution:
d M1
Provided lim
is finite
x
1
2
dx1
I2 M x1
dM
dx1
and
I1 M 1 x1
dM
dx1
I1 M1
and
I2 M2
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EXAMPLE 11.3
The need arises in a laboratory for 2000 cm 3 of an antifreeze solution
consisting of 30 mole % methanol in water. What volumes of pure methanol
and of pure water at 25oC (298.15K) must be mixed to form the 2000 cm3 of
antifreeze, also at 25oC (298.15K)? Partial molar volumes for methanol and
water in a 30 mole % methanol solution and their pure species molar volumes,
both at 25oC (298.15K), are
opposite intercept, M M
1
opposite intercept, M M
2
-1
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V x i Vi
i
V x1 V1 x 2 V2
0.338.632 0.7 17.765
24.025 cm3 mol-1
Because the required total volume of solution is Vt = 2000 cm3, the total number of
moles required is
Vt
2000
n
83.246 mol
V 24.025
Of this, 30% is methanol, and 70% is water:
ni x i n
V1 and V2
intercept, V1 V1
intercept, V2 V2
EXAMPLE 11.4
26
Solution:
Replace x2 by 1 x1 in the given equation for H and simplify:
(A)
dH
180 60 x12
dx1
Solution:
Equation (11.11) is written for the molar volume of the binary antifreeze solution, and
known values are substituted for the mole fractions and partial volumes:
By equation (11.15),
H1 H x 2
dH
dx1
By eq. (11.16),
or
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H2 H x1
H2 600 40 x13
(B)
dH
600 180 x1 20 x13 180 x1 60 x13
dx1
(C)
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The infinite dilutionH1 and H2 are found from eq. (B) and (C) when x 1 = 0 in
eq. (B) and x1 = 1 in eq. (C). The results are:
-1
H = 420 Jmol
and
By eq. (11.8),
i G i
and eq. (11.2) may be written as
(11.8)
d nG nV dP nS dT i dni
d nG nV dP nS dT G i dni
i
-1
H = 640 Jmol
(11.2)
(11.17)
Exercise: Show that the partial properties as given by eqs. (B) and (C) combine
by summability to give eq. (A), and conform to all requirements of the
Gibbs/Duhem equation.
dz Mdx Ndy
M N
y x x y
(6.12)
V S
T P ,n
P T ,n
(6.16)
29
G
nV
i
P
ni P ,T ,n
j
T ,n
G
nS
i
T
ni P ,T ,n j
P ,n
nH nU P nV
where subscript n indicates constancy of all ni, and subscript nj indicates that
all mole numbers except the ith are held constant.
In view of eq. (11.7), the last two equations are most simply expressed:
G
i
P
Vi
T , x
(11.18)
G
i
T
Si
P , x
30
nH
nU
nV
ni P ,T ,n j ni P ,T ,n j
ni P ,T ,n j
By eq. (11.7) this becomes
(11.19)
Hi Ui P Vi
d Gi i
P
G
dP i
T
T , x
dT
P , x
d G i Vi dP Si dT
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REFERENCES
Smith, J.M., Van Ness, H.C., and Abbott, M.M. 2005. Introduction to Chemical
Engineering Thermodynamics. Seventh Edition. Mc Graw-Hill.
http://www.chem1.com/acad/webtext/thermeq/TE4.html
http://mpdc.mae.cornell.edu/Courses/ENGRD221/LECTURES/lec26.pdf
http://science.csustan.edu/perona/4012/partmolvolsalt_lab2010.pdf
PREPARED BY:
MDM. NORASMAH MOHAMMED MANSHOR
FACULTY OF CHEMICAL ENGINEERING,
UiTM SHAH ALAM.
norasmah@salam.uitm.edu.my
03-55436333/019-2368303
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