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You are on page 1of 35

THE STANDARD GIBBS-ENERGY CHANGE AND THE EQUILIBRIUM CONSTANT

EFFECT OF TEMPERATURE ON THE EQUILIBRIUM CONSTANT

EVALUATION OF EQUILIBRIUM CONSTANTS

Course Learning Outcomes

The student should be able to :

• Describe the chemical reaction equilibria and it’s

importance in chemical engineering.

• Derive excess Gibbs energy equation to evaluate

equilibrium constant (K) for a given reaction and

conditions.

• Evaluate the equilibrium constant from diagram or excess

Gibbs energy for given reaction and conditions

• Apply the equilibrium constant to determine equilibrium

conversion and to calculate reaction mixture equilibrium

compositions.

• Calculate the equilibrium conversions for single reactions

THE REACTION COORDINATE

• General chemical reaction:

v1 A1 + v2 A2 + ... → v3 A3 + v4 A4 + ...

where;

vi = stoichiometric coefficient

Ai = chemical formula

vi = stoichiometric number

By the sign convention:

Positive (+) for a product Negative (-) for a reactant

• For reaction:

CH 4 + H2O → CO + 3H2

ν CH =

4

−1 νH O =

−12

ν CO =

1 νH =

3 2

numbers of moles of species present are in direct

proportion to the stoichiometric numbers. This

principle provides the equations:

dn2 dn1 dn3 dn1

= = etc.

ν2 ν1 ν3 ν1

• The list continues to include all species.

dn1 dn2 dn3 dn4

= = = = ...

ν1 ν 2 ν3 ν4 4

• All terms being equal, they can be identified collectively by a

single quantity representing an amount of reaction.

• A definition of dε is given by the equation:

dn1 dn2 dn3 dn4

= = = = ... ≡ d ε (13.2)

ν1 ν2 ν3 ν4

• The general relation connecting the differential change dni

with dε is therefore

=dni ν=

i dε ( i 1, 2, ..., N) (13.3)

degree to which a reaction has taken place.

5

• 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)

=n ∑

= n ∑n

i

i

i

i0 + ε ∑ν i

i

or n n0 + νε

=

where

n ≡ ∑ ni n0 ≡ ∑ ni 0 ν ≡ ∑ν i

i i i

ε by ni ni 0 + ν i ε

y= = (13.5)

n0 + νε

i

n 6

Example 13.1

For a system in which the following reaction occurs,

CH 4 + H2O → CO + 3H2

assume there are present initially 2 mol CH4, 1 mol H2O,

1 mol CO and 4 mol H2. Determine expressions for the

mole fractions yi as functions of ε.

Solution:

For the reaction,

For the given numbers of moles of species initially

present,

ν =∑ν i =−1 − 1 + 1 + 3 =2

i

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

are seen to be functions of the single variable ε .

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

the mole fraction of each chemical species to the

reaction coordinate ε.

Solution:

For the reaction,

ν =−1 + 1 + 1

2

=21

9

=

ni ni 0 + ν i ε (13.4)

ni ni 0 + ν i ε

y= = (13.5)

n0 + νε

i

n

nH O =

2

n0 − ε nH = ε nO =

2

1

2

ε2

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

fractional decomposition of the water vapor.

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 )

ni 0 + ∑ν i , j ε j

ni = (i =

1, 2, ..., N ) (13.6)

j

∑i i 0 ∑∑

n= n +

i j

ν ε

i, j j =

n0 + ∑ ∑ i , j ε j

j i

ν

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

mole fraction

ni 0 + ∑ j ν i , j ε j

=yi = ( i 1, 2, ..., N ) (13.7)

n0 + ∑ j ν j ε 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

variables ε1 and ε2 .

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.

( dG t )

T ,P

=0

and P must lead to a decrease in the total Gibbs energy of the

system.

• Fig. 13.1 shows the relation of Gt and ε. The arrows along the

curve indicate the directions of changes in (Gt)T,P. The reaction

coordinate, ε has its equilibrium value, εe at the minimum of

the curve.

This figure indicates two distinctive

features of the equilibrium state for given

T and P,

b) Its differential is zero.

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

is an exact differential expression,

∂ ( nG ) ∂ Gt( )

∑i i i =

= ν µ

∂ ε

∂ε

T ,P T ,P

• In general, the quantity ∑i

ν i µi represents, the rate of change

of total Gibbs energy of the system with respect to the

reaction coordinate at constant T and P.

• Fig. 13.1 shows that this quantity is zero at the equilibrium

state. A criterion of chemical reaction equilibrium is therefore

∑ν µ

i

i i =0 (13.8)

Γ i (T ) + RT ln fˆi

µi = (11.46)

standard state at the same temperature:

Γ i (T ) + RT ln fi o

Gio =

A standard state is a particular state of a species at temperature T and at specified

conditions of pressure, composition and physical condition e.g. gas, liquid or solid.

18

• The difference between these two equations is

fˆi

µi − G = o

RT ln o

i

(13.9)

fi

for the equilibrium state of a chemical reaction:

∑ i i

ν

i

G o

+

RT ln fˆ fo =

i i 0 ( )

or

( )

νi

∑ i

ν G + RT

i

o

∑ i i

ln fˆ fo =

0

or

i 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

−∆G o (13.11a)

K ≡ exp

RT

−∆G o (13.11b)

ln K =

RT

• Also by definition,

∆G o ≡ ∑ i ν i Gio (13.12)

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.

defined. For general property M:

∆M o ≡ ∑ν i Mio

i

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

summation over all species gives

d (∑i vi Gio / RT )

∑i i

v

i

H o

= − RT 2

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.

23

• 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

is a straight line.

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

∑i i

=ν

i

G o

∑i i ∑i i

i

ν H o

− T ν S o

reaction, this reduces to

∆G o =∆H o − T ∆S o (13.16)

• The standard heat of reaction is related to temperature:

T ∆Cpo

∆H0o + R ∫

∆H o = dT (4.18)

T0 R

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.

27

• 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

∆G0o − ∆H 0o

o

∆G o

∆H0 1 ∆CP o

T T ∆C

o

P dT

=

RT RT0

+

RT T

+ ∫T0 R dT − ∫T0 R T

(13.18)

28

• 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

30

• 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)

31

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 )

From Table C.1:

∆A = 3.518 – 1.424 – 3.470 = -1.376

∆B = (20.001 – 14.394 – 1.450) x 10-3 = 4.157 x 10-3

∆C = (-6.002 +4.392 – 0) x 10-6 = -1.610 x 10-6

∆D = (-0 – 0 – 0.121) x 105 = -0.121 x 105

33

• Values of ∆Ho298 and ∆Go298 at 25oC (298.15 K) for the

hydration reaction are found from Table C.4:

∆H298

o

=−235100 − 52510 − ( −241818 ) =−45792 Jmol-1

∆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

− ∆G o

ln K =

RT

At 418.15 K, ln K = -1.9356 and K = 1.443 x 10-1

At 593.15 K, ln K = -5.8286 and K = 2.942 x 10-3

• Alternative solution by using eq. (13.21), (13.22) and (13.24).

35

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