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G
G1
0 =
T1
T0
G = H S
S P
Cp dT ) dT
(5)
(6)
1
T
G
T
G1
1
0 = H0 + aln 1 + 0 1
T1
T0
T0
T1
T1
T0
2
2
T2
T3
b
c T 3T0
T1 2T0 + 0 + 1
+ 0
2
T1
3
2
T1
3
3
T 4
d T1 4T0
+ 0
4
3
T1
(7)
(4)
(2)
H
G
= 2
T T
T
1
(H 0 +
T2
Cp = a + bT + cT 2 + dT 3
d G = V dP S d T
T1
(1)
G = H TS
Article
Hrxn
Grxn
=
T RT
RT 2
Grxn,1
RT1
Grxn,0
K
ln 1 = +
K0
RT0
T1
T1
Hrxn(T )
RT 2
Hrxn(T )
RT 2
dT
(9)
dT
(10)
o
Grxn,0
RT0
d 3
T0
+
12R
H =
S =
T1
T1
Cp
dT = Cp ln
T1
(constant P)
T0
(18)
(19)
(11b)
Cp =
T 1 Cp dT
o
T1 T0
b
(11c)
Cp =
T 1 Tp dT
o
ln
(12)
T1
T0
( ) + b(T T ) + (T
ln( )
a ln
T1
T0
c
2
2
1
T1
T0
(21)
T1
T0
(22)
PROPOSED METHODS
dG = dH d(TS)
(17)
J
a
b
c 2
ln T0 +
T0 +
T0
+
2R
6R
RT0
R
K
Hrxn 1
1
ln 1 =
R T1
T0
K0
(16)
= H S0T T1S
where
I=
(15)
(11a)
b 2 c 3 d 4
T0
T0
T0
2
3
4
G = H (TS
1 1 T0S0)
G = H (TS
1 1 T0S0 + TS
1 0 TS
1 0)
J
a
b
c 2
d 3
T1 I
T1 +
T1 +
+
ln T1 +
RT1
R
2R
6R
12R
o
J = Hrxn,0
aT0
(14)
where subscripts 0 and 1 stand for the initial and nal states,
respectively.
It is possible to manipulate the expression algebraically, by
introducing a new term, T1S0, to get
where Grxn and Hrxn are the Gibbs energy and enthalpy of
reaction, respectively, and K0 and K1 are the chemical equilibrium
constants at temperatures T0 and T1, respectively.
For the most accurate calculations, the enthalpy of reaction
should be considered a function of the temperature by using the
polynomial expressions for the heat capacities of reactants and
products as shown in eq 6.
Elliot and Lira2 show that the solution for eq 10 can be
expressed as
ln K1 =
G = H (TS)
(13)
397
Article
iRT1 ln
P0
(T1 T0) + TC
1 p , i ln
T1
T0
(27)
P0
i
1
o
{Grxn,0
RT1
(23)
i(Gi)P }
(28)
(29a)
T1
T0
(29b)
(30)
In this case,
yC P1
K1 =
yD P1
( )( )
( )( )
P0
P0
yA P1
yB P1
P0
(31)
P0
because P0 = 1 bar,
(24)
K1 =
(32)
(25)
o
Grxn,0
=
(33)
APPLICATION EXAMPLES
The following examples explain the procedure to calculate the
temperature dependence of the Gibbs energy and the chemical
equilibrium constants, using dierent methods.
T1
T0
TC
+ RT1 ln A
1 P ,A ln
T0
P0
with
(T1 T0) TC
1 p , i ln
ln K1 =
T
G = (Cp S0)(T1 T0) CpT1 ln 1
T0
i(Cp ,i Si ,0)
(26)
398
Article
Hof /
1
Gof /
1
So/
J mol1 K1
C p at 400 K/
J mol1 K1
C p at 400 K/
J mol1 K1
191.61
130.68
192.45
31.15
27.14
27.31
1.357 102
9.274 103
2.383 102
2.680 105
1.381 105
1.707 105
1.168 108
7.645 109
1.185 108
29.19
29.01
37.21
29.19
29.01
37.13
Species
kJ mol
kJ mol
N2 (g)
H2 (g)
NH3 (g)
0
0
46.11
0
0
16.45
Hof , Gof and So are taken from ref 3. The coecients for Cp are taken from ref 2.
(34)
1
G = G1 G0
1
1
= G0 1 1 T1 H0
T0
T0
T1
T
T
T2
b
+ aln 1 + 0 1 + T1 2T0 + 0
T1
T1
2
T0
2
2
T 3 d T 3 4T03
T 4
c T1 3T0
+ 0+ 1
+ 0
3
2
T1
4
3
T1
76,795.7
57.95
+
ln(400)
(8.314)(400)
8.314
3.341 102
4.877 105
+
(400) +
2(8.314)
6(8.314)
3.496 108
2
(400) +
(400)3 + 21.32
12(8.314)
ln K1 =
(35)
(36)
ln K1 = 3.58 K1 = 36.04
(22)
K
Hrxn 1
1
ln 1 =
R T1
T0
K0
o
o
Grxn,0
Hrxn
1
1
ln K1 =
RT0
R T1
T0
o
Hrxn,0
= 92,220 J
ln K1 =
o
Grxn,0
= 32,900 J
32,900
92,220 1
1
(8.314)(298)
8.314 400
298
ln K1 = 3.78 K1 = 44.14
399
Article
Figure 2. Comparison of dierent methods to calculate the temperature dependence of equilibrium constant K1.
ln K1 =
1
{+32,900 [(2)( 20,215.9)
(8.314)(400)
+ 20,003.9 + (3)(13,786.2)]}
ln K1 = 3.60 K1 = 36.56
1
{+32,900 [(2)( 20,206.5)
(8.314)(400)
+ 20,003.9 + (3)(13,786.2)]}
ln K1 = 3.59 K1 = 36.36
ln K1 =
1
{+32,900 [(2)( 20,190.5)
(8.314)(400)
+ 20,004.1 + (3)(13,784.5)]}
400
ln K1 = 3.58 K1 = 36.07
Article
ASSOCIATED CONTENT
* Supporting Information
S
AUTHOR INFORMATION
Corresponding Author
*E-mail: fvargas@rice.edu.
Notes
ACKNOWLEDGMENTS
The author gratefully acknowledges support from Tecnologico de
Monterrey, through Catedra de Energia Solar y Termociencias
(Grant CAT-125). The support of Shyam Benny Kadali and
Sameer Punnapala in early versions of this manuscript is also
greatly appreciated. The author also thanks the anonymous
reviewers for their careful assessment, which helped to improve
this article. In particular, section 4 is largely the result of
addressing the constructive feedback of one of the referees.
REFERENCES
(1) Beegle, B. L.; Modell, M.; Reid, R. C. AIChE J. 1974, 20, 1194
1200.
(2) Elliot, J. R.; Lira, C. T. Introductory Chemical Engineering
Thermodynamics, 2nd ed.; Prentice Hall: New York, 2009; pp 652657.
(3) Atkins, P.; de Paula, J. Physical Chemistry, 9th ed.; W.H. Freeman:
and Co.: New York, 2009; pp 918923.
(4) NIST Chemistry WebBook. http://webbook.nist.gov/chemistry/
(accessed Feb 2014).
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