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• Integration of eq. (13.3) from an initial unreacted state where
ε = 0 and ni = nio to a state reached after an amount of
reaction gives n ε
∫ dni = ν i ∫ d ε
i
ni 0 0
or
ni 0 + ν i ε
ni = (i =
1, 2, ..., N ) (13.4)
n0 = ∑n
i
i0 = 2 + 1+ 1+ 4 = 8
7
Equation (13.5) yields
ni ni 0 + ν i ε
y= =
n0 + νε
i
n
2−ε 1− ε
=y CH4 = y H2O
8 + 2ε 8 + 2ε
1+ ε 4 + 3ε
=y CO = y H2
8 + 2ε 8 + 2ε
8
Example 13.2
Consider a vessel which initially contains only n0 mol of
water vapor. If decomposition occurs according to the
reaction,
H2O → H2 + 21 O2
9
=
ni ni 0 + ν i ε (13.4)
ni ni 0 + ν i ε
y= = (13.5)
n0 + νε
i
n
n0 − ε ε 2ε
1
=y H2O = y H2 = y O2
n0 + 2 ε
1
n0 + 2 ε
1
n0 + 21 ε
The fractional decomposition of water vapor is
n0 − nH O n0 − ( n0 − ε ) ε
= = 2
n0 n0 n0
10
Multireaction Stoichiometry
• For multireaction, νi,j designates the stoichiometric number of
species i in reaction j.
• The general relation, eq. (13.3) becomes
=dni ∑
=ν dε ( i
j
i, j j 1, 2, ..., N )
11
• The definition of a total stoichiometric number ν ( ≡ ∑ i ν i ) for
a single reaction has its counterpart here in the definition:
ν j ≡ ∑ν i , j whence n0 + ∑ν j ε j
n=
i j
12
Example 13.3
Consider a system in which the following reactions occur:
CH 4 + H2O → CO + 3H2 (1)
CH 4 + 2H2O → CO2 + 4H2 ( 2)
where the numbers (1) and (2) indicate the value of j, the
reaction index.
If there are present initially 2 mol CH4 and 3 mol H2O,
determine expressions for the yi as functions of ε1 and ε2.
Solution:
The stoichiometric numbers νi,j can be arrayed as follows:
i= CH4 H2O CO CO2 H2
j νj
1 -1 -1 1 0 3 2
2 -1 -2 0 1 4 2 13
ni 0 + ∑ j ν i , j ε j
=yi = ( i 1, 2, ..., N ) (13.7)
n0 + ∑ j ν j ε j
Application of eq. (13.7) gives
2 − ε1 − ε 2 ε1
=y CH4 = y CO
5 + 2ε1 + 2ε 2 5 + 2ε1 + 2ε 2
3 − ε1 − 2ε 2 ε2
=y H2O = y CO2
5 + 2ε1 + 2ε 2 5 + 2ε1 + 2ε 2
3ε1 + 4ε 2
y H2 =
5 + 2ε1 + 2ε 2
14
APPLICATION OF EQUILIBRIUM
CRITERIA TO CHEMICAL REACTIONS
• Total Gibbs energy of a closed system at constant T and P
must decrease during an irreversible process and equilibrium
is reached when Gt attains its minimum value.
16
THE STANDARD GIBBS-ENERGY CHANGE
AND THE EQUILIBRIUM CONSTANT
• Equation (11.2) provides an expression for the total
differential of the Gibbs energy:
d ( nG ) = (nV )dP − (nS )dT + ∑ µi dni (11.2)
i
• If changes in the mole numbers ni occur as the result of a
single chemical reaction in a closed system, then by eq. (13.3)
each dni may be replaced by the product νi dε .
• Eq. (11.2) then becomes
d ( nG ) = (nV )dP − (nS )dT + ∑ν i µi d ε
i
( ) ∑
νi ν Go
ln ∏ fˆi fi
−
o
= RTi i i
i
where Πi signifies the product over all species i.
19
• In exponential form, this equation becomes
∏( )
νi
fˆi fi o =K (13.10)
i
20
K is called the equilibrium constant for the reaction;
∑iνi Gio, represented by ∆Go, is called the standard
Gibbs-energy change of reaction.
• The function ∆Go ≡ ∑iνiGio in eq. (13.12) is the difference
between the Gibbs energies of the products and reactants
when each is in its standard state as a pure substance at the
standard state pressure, but at the system temperature.
21
• For example, the relation between the standard heat of
reaction and the standard Gibbs energy change of reaction is
developed from Eq. (6.39) written for species i in its standard
state: o
d (Gi / RT )
H = − RT
i
o 2
dT
dT
• Therefore, using Eq.4.14 and Eq. 13.12, relation written as
Eq.(4.14)
∆H =
o
−RT 2
d ∆(
G o
RT ) (13.13)
∆H = ∑ vi H
o
i
o
dT
i
EFFECT OF TEMPERATURE ON THE
EQUILIBRIUM CONSTANT
• Because the standard state temperature is that of the
equilibrium mixture, the standard property changes of
reaction, such as ∆Go and ∆Ho, vary with the equilibrium
temperature.
• The dependence of ∆Go on T is given by eq. (13.13),
(
d ∆G o RT ) = −∆H o
dT RT 2
• In view of eq. (13.11b), this becomes
d ln K ∆H o (13.14)
=
dT RT 2
• If ∆Ho is negative, i.e., if the reaction is exothermic, the
equilibrium constant decreases as the temperature increases.
K increases with T for endothermic reaction.
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• If ∆Ho is assumed independent of T, integration of eq. (13.14)
from T’ to T leads to the simple result:
K ∆H o 1 1 (13.15)
ln ' =
− − '
K R T T
24
A plot of ln K vs. (1/T) for a number of common reactions
25
• The rigorous development of the effect of temperature on
equilibrium constant is based on the definition of the Gibbs
energy at standard state:
G=
i
o
H i
o
− TSi
o
26
• The temperature dependence of the standard entropy
change of reaction is:
dT
dSio = C Poi
T
• Multiply by νi and summation over all species gives
dT
d ∆S o = ∆CPo
T
• Integration gives
∆CPo dT
T
∆S + R ∫
∆S = o o
0 (13.17)
T0 R T
where ∆So and ∆S0o are the standard entropy changes of
reaction at temperature T and at reference temperature T0.
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• Eqs. (13.16), (4.18) and (13.17) are combined to yield
∆CP oT T ∆C
o
∆G =∆H + R ∫
o o
0 dT − T ∆S0 − RT ∫
o P
dT
T0 R T 0 R
• However,
∆H o
− ∆G o
∆S0o = 0 0
T0
• Hence,
T ∆C T ∆C
o o
∆G o =
∆H0o −
T
T0
( )
∆H0o − ∆G0o + R ∫
T 0 R
P
dT − RT ∫
T 0 R
P
dT
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• The first integral of eq. (13.18) is
∆CPo ∆B 2 2 ∆C 3 3 ∆D τ − 1
( ) ( ) ( ) ( )
T
∫T0 R dT = ∆A T0 τ − 1 +
2
T0 τ − 1 +
3
T0 τ − 1 +
T0 τ
(4.19)
• The second integral is
∆CPo dT ∆D τ + 1
∫T0 R T =∆A lnτ + ∆BT0 + ∆CT0 + τ 2T0 2 (τ − 1) (13.19)
T
2
where
T
τ≡
T0
29
• ∆Go/RT(= - ln K) as given in eq. (13.18) is readily calculated at
any temperature from the standard heat of reaction and the
standard Gibbs energy change of reaction at a reference
temperature (usually 298.15 K).
• Factor K may be organized into three terms:
K = K 0K1K 2 (13.20)
−∆G0o (13.21)
K 0 ≡ exp
RT 0
∆H0o T0
K1 ≡ exp 1− (13.22)
RT0 T
1 T ∆CPo T ∆C dT
o
K 2 ≡ exp − ∫ dT + ∫ P
(13.23)
T T0 R T0 R T
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• Temperature dependence of the heat capacity (eq. 4.4):
CP
=A + BT + CT 2 + DT −2
R
• The expression for K2 becomes:
(τ ) (τ ) (τ ) (τ )
2 2 2
τ − 1 1 − 1 1 − 1 + 2 1 ∆D − 1
K= exp ∆A lnτ − + ∆BT0 + ∆CT02
+
2
τ 2 τ 6 τ 2 T0
2
τ 2
(13.24)
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EVALUATION OF EQUILIBRIUM
CONSTANTS
• Values of ∆Go for many formation reactions are tabulated in
standard references.
• The reported values of ∆Gof are not measured experimentally,
but are calculated by Eq. 13.16.
∆G o =∆H o − T ∆S o
• Values of ∆Gof298 and ∆Hof298 for a limited number of chemical
compounds are listed in Table C.4 of App. C. These for a
temperature of 298.15K.
• Values of ∆Go for other reactions are calculated from
formation-reaction values.
• In more extensive compilations of data, values of ∆Gof and
∆Hof are given for a wide range of temperature. When data is
lacking, methods of estimation are available.
Example 13.4
Calculate the equilibrium constant for the vapor phase
hydration of ethylene at 145oC (418.15 K) and at 320oC
(593.15 K) from data given in App. C.
Solution:
First determine the values for ∆A, ∆B, ∆C and ∆D for the
reaction
C2H 4 ( g ) + H 2O ( g ) → C2H5OH ( g )
∆G298
o
=−168490 − 68460 − ( −228572 ) =−8378 Jmol-1
• For T = 418.15 K, values of integrals in eq. (13.18) are
T ∆CPo
∫T0 R dT = −23.121
T ∆C dT
o
∫T0 R P T = −0.0692
• Substitute into eq. (13.18) for a reference temperature of
298.15 K gives:
∆G418
o
−8378 + 45792 −45792 −23.121
= + + +=
0.0692 1.9356
RT ( 8.314 )( 298.15 ) ( 8.314 )( 418.15 ) 418.15
34
• For T = 593.15 K,
T ∆CPo
∫T0 R dT = 22.632
T ∆C dT
o
∫T0 R P T = 0.0173
∆G593
o
−8378 + 45792 −45792 22.632
= + + −=
0.0173 5.8286
RT ( 8.314 )( 298.15 ) ( 8.314 )( 593.15 ) 593.15
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