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Solution Thermodynamics:
Theory
3.0 The Notations for Solution
Thermodynamics
M = the properties of the solution
(h, s, v)
Mi = partial properties (e.g., hi , si )
(e.g., gi , si )
188
(2.13)
(3.1)
P T ,n
T P ,n
189
(3.2)
and
( ng )
P = nv
T ,n
(3.3)
( ng )
T = ns
P ,n
(3.4)
where
n = total # of moles or # of moles
of all chemical species in the
solution
= n1 + n2 + n3 + ... + nn
(for n species)
Accordingly,
ng = f ( T , P, n1, n2 , n3 , .... )
190
P T ,n
T P ,n
( ng )
dni
+
ni P ,T ,n
i =1
j
n
(3.5)
ni P,T ,nj
CHEMICAL POTENTIAL, i
( ng )
i =
P , T , nj
i
191
(3.6)
d ( ng ) = ( nv ) dP ( ns ) dT + i dni (3.7)
i =1
(3.8)
i =1
and
g
=v
P T ,x
(3.9)
g
= s
T P,x
(3.10)
192
193
d ( ng ) = ( nv ) dP ( ns ) dT + i dni
(3.11)
i =1
n
d ( ng ) = ( nv ) dP ( ns ) dT + i dni
i =1
194
(3.12)
(3.13)
d ( ng ) = ( nv ) dP ( ns ) dT + i dni + i dni
i =1
i =1
(3.14)
From Eq. 3.1, we knew that
d ( ng ) = ( nv ) dP ( ns ) dT
195
(3.1)
d ( ng ) = d ( ng ) + i dni + i dni
i =1
i =1
i =1
i =1
dn
+
dn
i i i i =0
(3.15)
(3.16)
dn
+
dn
i i i ( i )=0
i =1
i =1
(
i =1
i )dni = 0
and, eventually
i = i
(3.17)
197
P , T , nj
i
where
(3.18)
P ,T ,n j
i
(3.19)
199
P T ,n
T P ,n
( nM)
dni
+
ni P,T ,n
i =1
j
(3.20)
P T ,n
T P ,n
n
+ Mdn
i
i
i =1
200
(3.21)
dT
P T ,n
T P ,n
(3.22)
+ Mdn
i
i
i =1
P
P
T ,n
T ,x
M
M
T
T
P ,n
P ,x
and
dT
P T ,x
T P,x
n
+ Mdn
i
i
i =1
201
(3.23)
Mdn
i =1
in Eq. 3.23
ni
Since xi = ni = xi n
n
Thus,
dni = d ( xi n) = xi dn + ndxi
Accordingly,
n
Mdn = M ( x dn + ndx )
i =1
i =1
(3.24)
(3.25)
202
M
M
ndM + Mdn = n
dP + n
dT
P T ,x
T P ,x
n
+ Mi ( xi dn + ndxi )
i =1
M
M
i
in
dM P dP T dT Mdx
T ,x
P ,x
+ M xi Mi dn = 0
(3.26)
Eq. 3.26 will be true only if
M
M
i
i = 0
dM P dP T dT Mdx
T ,x
P ,x
and
M xi Mi = 0
203
Hence,
M
M
dM =
dP
+
dT + Mdx
i
i
P
T
T ,x
P ,x
M = xi Mi
(3.27)
(3.28)
(3.29)
(3.30)
x dM + Mdx
i
M
M
dP
+
dT + Mdx
i
i
T ,x
P ,x
dP +
dT xi dMi = 0
P T ,x
T P,x
(3.31)
Note that Eq. 3.31 is called a Gibbs/
Duhem equation
In the case where T & P are constant, a
Gibbs/Duhem equation (Eq. 3.31) becomes
x dM = 0
i
205
(3.32)
(3.28)
(3.33)
(3.34)
206
x dM = 0
i
(3.32)
(3.35)
207
(3.36)
208
(3.37)
(3.38)
209
(3.39)
( x2 + x1 ) M1 = M + x2
dM
dx1
(3.40)
(3.41)
210
(3.42)
211
I1
M
I2
x1
and
dM M I2 M I2
=
=
dx1 x1 0
x1
(3.43)
dM I1 I2
=
= I1 I2
dx1 1 0
(3.44)
212
(3.45)
(3.46)
but x1 + x2 = 1 x2 = 1 x1
213
Hence,
dM
I1 = M + x2
dx1
(3.47)
214
dM
Lets consider the value of
when
dx1
M1
M2
x1
215
216
M1
M2
M2
x1
(3.48)
Determine the values of h1, h2 , h1 , &
h2
218
(3.49)
(3.50)
(3.41)
dM
dx1
(3.42)
M2 = M x1
dh
h1 = h + (1 x1 )
dx1
(3.51)
dh
h2 = h x1
dx1
(3.52)
+ (1 x1 ) ( 180 60 x12 )
(3.53)
h2 = 600 + 40 x13
(3.54)
220
and when x1 1:
M1 = M1 and M2 = M2
h2 = h2 ( x1 = 0 ) = 600 + 40 ( 0 ) = 600
3
h1 = h1 ( x1 = 0 ) = 420 60 ( 0 ) + 40 ( 0 ) = 420
2
221
700
h2
600
h1
h2
500
400
h1
300
200
100
0
0
0.2
0.4
0.6
x1
222
0.8
P ,T ,n j
i
(3.19)
results in
d ( ng ) = ( nv ) dP ( ns ) dT + gi dni (3.55)
223
( nv )
( ns )
T = P
P ,n
T ,n
and
v
s
=
T P,n
P T ,n
(3.56)
( ns )
gi
T = n
P ,n
i P ,T ,n j
(3.57)
( nv )
gi
P = n
T ,n
P ,T ,n j
i
(3.58)
P , T , nj
i
(3.18)
gi
T = si
P ,n
(3.59)
gi
P = vi
T ,n
(3.60)
224
(3.10)
g
=v
P T ,n
(3.9)
225
Hence,
gi
gi
dgi =
dT +
dP
T P,n
P T ,n
(3.61)
226
(2.13)
227
(3.62)
(3.63)/(3.62) gives
ni RT
t
Pi
ni
V
=
= = xi
P nRT n
Vt
or
Pi = xi P
228
(3.63)
ig
nv ig
=
i T ,P ,nj
RT
n P
=
ni
T ,P,nj
=
RT n
P ni T ,P,n
ni
i T ,P,nj
T ,P,nj
( nj )
ni
=
+
=1
ni T ,P,nj ni T ,P,nj
229
Thus,
vi
ig
RT
=
= viig
P
(3.64)
230
(3.65)
meaning that
hi ig = hi ig
231
(3.66)
(3.28)
to enthalpy, yields
hig = xi hiig = xi hiig
(3.67)
232
dsi ig = cp
dT
dP
R
T
P
dP
P
= Rd ln P
dsi ig = R
233
Pi
Pi
ig
ds
i = Rd ln P
P
= R d ln P
Pi
si ig ( T , P ) si ig ( T , Pi ) = R [ln P ln Pi ]
P
si ( T , P ) si ( T , Pi ) = R ln
Pi
ig
ig
Pi
but xi = Pi = xi P
P
Accordingly,
P
1
= R ln
si ( T , P ) si ( T , Pi ) = R ln
xi P
xi
ig
ig
si ig ( T , P ) si ig ( T , Pi ) = R ln xi
234
(3.68)
(3.69)
(3.70)
(3.71)
(3.72)
sig = xi si ig ( T , P ) R xi ln xi
235
(3.73)
ig
(3.74)
236
(3.75)
gi ig = hi ig Tsi ig
(3.76)
gives
(3.77)
gi ig = i = giig + RT ln xi
237
(3.78)
(2.13)
becomes
dgiig = vdP
RT
=
dP
P
dP
= RT
P
dgiig = RTd ln P
(3.79)
where
(3.80)
i ( T ) = integration constant
= f(T)
238
(3.81)
(3.82)
239
(3.80)
(3.83)
240
fi
P
Note that
fi
= i = FUGACITY
P
COEFFICIENT
Hence,
giR = RT lni
241
(3.84)
fi
= 1 giR = RT ln (1) = 0
P
(3.85)
gR
dP
= ( Z 1)
RT 0
P
(2.67)
yields
P
giR
dP
lni =
= ( Zi 1)
RT 0
P
242
(3.86)
(2.85a)
(3.85)
gives
gi R
lni =
= ln (1 b ) Zi qI + ( Zi 1)
RT
243
(3.87)
(2.95)
(2.95a)
244
(3.88)
(3.89)
gil = RT ln fi l + i ( T )
(3.90)
245
At equilibrium,
giv = gil
or
giv gil = 0
or
fi v = fi l = fi sat
(3.92)
246
iv = il = isat
(3.93)
247
Example
(3.83)
(3.94)
fi gi gi*
ln * =
RT
fi
248
(3.95)
gi = hi Tsi
(3.98)
RT
RT
R
*
h
h
( i i)
RT
249
*
s
s
( i i)
(3.99)
250
kJ
kmol
fi
ln * =
kJ
fi
8.314
([ 300 + 273 ] K )
kmol-K
kJ
(18.02 [6.3561 9.5162]) kmol-K
kJ
8.314
kmol-K
= 6.395
(note that we have to multiply the values of h
& s obtained from the steam table with MW of water
(= 18.02) to convert the units of h & s to be kJ/kmol
& kJ/kmol-K, respectively)
Thus,
fi
= exp(6.395) = 598.84
*
fi
8.314
([ 300 + 273 ] K )
kmol-K
kJ
18.02
3.2519
9.5162
[
]) kmol-K
(
kJ
8.314
kmol-K
= 7.057
252
Hence,
fi
= exp(7.057) = 1,160.96
*
fi
fi = 1,160.96fi * = 1,160.96 ( 6 kPa) = 6,966 kPa
and
fi 6,966 kPa
i = =
= 0.697
P 10,000 kPa
(3.78)
(3.80)
254
(3.100)
(3.101)
where
fi = fugacity of species i in a solution
255
256
(2.55)
fi
g = RT ln
x
P
i
R
i
Let
(3.102)
fi
fi
i =
=
xi P Pi
Thus,
giR = RT lni
(3.103)
lni = ( Zi 1)
0
258
dP
P
(3.104)
dP
lni = ( Zi 1)
P
0
(3.86)
Pr =
Pc
P = PcPr
dP = d ( PcPr )
= PcdPr
results in
259
(3.105)
(3.106)
Pr
lni = ( Zi 1)
0
PcdPr
PcPr
Pr
dPr
lni = ( Zi 1)
Pr
0
(3.107)
(1.21)
260
(3.108)
Zi 1 = Zi0 1+ Z1i
dPr
lni = ( Zi 1)
Pr
0
Pr
dPr
= ( Z 1+ Z )
Pr
0
Pr
0
i
1
i
lni = ( Zi0 1)
0
Pr
dPr
dP
+ Z1i r
Pr
Pr
0
261
Let
Pr
dPr
ln = ( Z 1)
Pr
0
0
i
and
Pr
0
i
dPr
ln = Z
Pr
0
1
i
1
i
Thus,
lni = lni0 + lni1
1
i
0
1
= ln (i )(i )
i = (
0
i
)( )
262
1
i
(3.110)
Example
For R-134a:
Tc = 374.26 K
Pc = 40.59 bar
= 0.326
263
(a)
Pr =
P
80 bar
=
= 1.97
Pc 40.59 bar
T [ 300 + 273 ] K
= 1.53
Tr = =
374.26 K
Tc
Hence,
i = ( 0.8495 )(1.1828 )
0.326
= 0.897
and
(b)
P
284 bar
Pr =
=
= 7.0
Pc 40.59 bar
T [ 300 + 273 ] K
= 1.53
Tr = =
374.26 K
Tc
i( 0) = 0.6866
i(1) = 1.5817
Hence,
i = ( 0.6866 )(1.5817 )
0.326
= 0.797
and
fi = i P = ( 0.797 )( 284 bar )
= 226.3 bar
265
(3.78)
(3.111)
P ,x
266
P ,x
(3.59)
results in
g
si id = i + R ln xi
T P,x
and
si
id
gi
=
R ln xi
T P,x
(3.112)
(3.10)
P,x
with Eq. 3.112 gives
267
(3.10a)
si id = ( si ) R ln xi
= si R ln xi
(3.113)
T ,x
(3.114)
T ,x
results in
g
viid = i + 0
P T ,x
(3.60)
T ,x
(3.9a)
viid = vi
(3.115)
we obtain
or
hiid = giid + Tsi id
269
(3.116)
(3.117)
hiid = hi
270
(3.28)
Thus,
gid = xi giid = xi gi + xi RT ln xi
= xi gi + RT xi ln xi
(3.118)
sid = xi si id = xi si R xi ln xi
(3.119)
v id = xi viid = xi vi
(3.120)
hid = xi hiid = xi hi
(3.121)
271
(3.101)
(3.122)
(3.83)
yields
272
(3.111)
i ( T ) + RT ln fi id = i ( T ) + RT ln fi + RT ln xi
fi id = xi fi
(3.123)
273
f
f
iid = i = i
xi P P
274
Since
fi
i =
P
(3.124)
275
MR = M Mig
ME = M Mid
ig
276
(3.126)
(3.118)
(3.127)
277
(3.128)
When combining Eq. 3.128 with
Eq. 3.126, we obtain
ME MR = ( xi MiR )
ME = MR xi MiR
278
(3.129)
279
(3.130)
(3.101)
(3.131)
(3.123)
giid = i ( T ) + RT ln xi fi
(3.132)
gives
280
E
i
(3.133)
fi
Let i =
= activity coefficient of
xi fi
species i in a solution
Thus,
giE = RT ln i
(3.134)
giE
= ln i
RT
(3.135)
and
281
(3.136)
283
284
285
286
287