CHAPTER VI SUMMARY
CHEMICAL EQUILIBRIUM
BASIC KNOWLEDGE ABOUT CHEMICAL EQUILIBRIUM CONSTANT
I. Type of equilibrium constant
N Consider a reaction which occurs in an ideal system at constant temperature and
constant pressure:
a A + b B = cC + d D
Type Calculation Depend on
pi is the partial pressure of
Partial pcC pdD
K P = a b
component i at equilibrium time: T
pressure pA pB eq pi = x i ptotal
C i is the molarity of component
Molar C C
c d
i at equilibrium time:
K C = C
D
n ( mol )
T
C C eq
a b
concentration A B
Ci = i
Vtotal ( L )
xi is the mole fraction of
( ) ( )
xcC xdD
Kx = a
component i at equilibrium time:
Mole fraction
( ) ( )
x A x Bb
eq xi = i
n
T, P
n total
The number n c ndD n i is the number of moles of T, P,
K n = aC d ( n )
i eq
of moles n A n D eq component i at equilibrium time.
II. The relationship between K P , K C , K x , K n :
P
K P = K C ( RT )
n
= K xP n = K n
n
i eq
N Where:
The change in gas moles: n = ( c + d ) − ( a + b ) (Only calculate the
n : coefficient of gases)
Ex: N 2 ( g ) + 3H 2 ( g ) = 2NH 3 ( g ) → n = 2 − (1 + 3 ) = −2
( n ) i eq
: The total moles of gases at equilibrium time
The gas constant
R: J atm L cal
R = 8,314 = 0,082 = 1,987
mol K mol K mol K
T: The temperature which the reaction occurs at (K)
III. Predict the direction of chemical reaction based on equilibrium constant
N Van’t Hoff isotherm:
GT = GT + RT ln P
o
o → GT = RT ln P
GT = −RT ln K P
KP
Where:
K K
pc pdD
P = Ca
pc pdD
K P = Ca ( ) ( )
xcC xdD ( ) ( )
xcC xdD
Kx = a
b
b
x = a
pA p B pA pB eq ( ) ( )
x A x Bb
( ) ( )
x A x Bb
eq
Cc CdD CcC CdD n c ndD n cC ndD
C = Ca b
K C = a b
n = aC d
K n = a d
CA CB CA C B eq nA nD n A n D eq
→ is calculated at each time in the reaction.
→ At equilibrium time, @ = K @ (@ can be replaced for P, C, x or n).
N The direction of a reaction which occurs at constant temperature and constant
pressure:
K@ @ Forward direction
K@ @ Reverse direction
K@ = @ Equilibrium
CHEMICAL EQUILIBRIUM IN VARIOUS SYSTEM
I. Ideal gas system
G = G o + RT ln = G o + RT ln
T T,P p T,P X
GoT , P = −RT ln K p = −RT ln K X
II. Ideal solution
N Equilibrium constant
GT = G T + RT ln X
*
*
GT = −RT ln K X
Where: G *T is the standard Gibbs free energy of liquid
K n = K X ( n i )eq = K C V n ⎯⎯⎯
n n = 0
N → Kn = KX = KC
III. Heterogeneous system
1. Equilibrium constants
⎯⎯
→ d Pure solid(s) + e Pure liquid(s) + f Gas(es)
a Pure solid(s) + b Pure liquid(s) + c Gas(es) ⎯
⎯
N Partial pressure of pure solids and pure liquids are not included:
pgas
f
pgas
f
( es ) ( es )
→ KP = c → P = c
pgas ( es ) pgas ( es)
eq
3
pCO
Ex: Fe 2 O 3 ( s ) + 3CO(g ) = 2Fe( s ) + 3CO 2 (g ) K P = 3
2
pCO
N The number of moles of pure solids and pure liquids are not included when we
calculate ( n )i eq
and n :
( n ) = ( n ) + n
Ex: Fe 2 O 3 ( s ) + 3CO(g ) = 2Fe ( s ) + 3CO 2 (g )
i eq CO eq (
CO2 ) eq
n = 3 − 3 = 0
2. Dissociation pressure
⎯⎯
→ b Pure solid + c Gas
a Pure solid ⎯
⎯
( )
c
N At equilibrium time: K P = pgas = const → pgas = Dissociation Pr essure
→ Dissociation pressure of a substance A is the property of A at the given
temperature
N T increases → pdissociation increases:
Temperature Increases ( )
Dissociation Temperature Decomposition Temperature
(p ) = (p )
gas eq gas atmosphere (p )
gas eq
= patmosphere
(p ) gas atmosphere
= xgas / atm patm
patm = 1 atm
( )
Ex: pO2
atm
= 20% 1 atm = 0,2 atm
Dissociation
pressure
( )
(p )
Increases
gas eq
FACTORS AFFECT CHEMICAL EQUILIBRIUM
Group 1 Group 2
Can change the components of
equilibrium mixture (change the
Property Can change the value of K P
value of K X , K n but cannot change
KP
Changes in temperature (T)
Changes in Pressure
Huge change in pressure
Include Changes in initial composition
Change in the surface area of phase
Addition of an inert component
separation
1. Temperature
N Van’t Hoff isobaric equation:
d ln K P H d log K P H H
= 2
or = → ln K P = dT + I
dT RT dT 4,575T 2
RT 2 intergrate constant
N The determination of I can be done by below methods
a. Approximate method for a small temperature change:
K P, T2 H 1 1
ln =− −
K P, T1 R T2 T1
Where: H : Assume that HT2 = HT1 = H
R = 8,314 → H : J
R : Gas constant.
R = 1,987 → H : cal
b. Using reduced Gibbs free energy
1 Hoo
ln K P , T = − + g rx ( T )
R T
Where: g rx = g ( Products) − g ( Reactants ) ( g i can be got from handbook)
Hoo : Can be calculated by equation Hoo = Go298 + 298g rx ( 298 )
c. Using Nernst’s Law
N Condensation system (includes only solid(s) and liquid(s):
H
Ignore I → ln K P = dT
RT 2
N Gas system:
H
I = j → ln K P = dT + j
RT 2
Where j: the real chemical constant of a substance and can be got from handbook
(page 51)
j = j( Products ) − j( Reactants )
N Heterogeneous system:
Similar to gas system but pure solids and liquids have j = 0
N Other system: Approximate equation
Ho298
log K P = − + 1,75n log T + i
4,575T
Where i: the conventional chemical constant of a substance and can be got from
handbook (page 51)
i = i( Products ) − i( Reactants )
2. Total pressure / Volume / Addition of inert component(s)
N Condensation system:
Total pressure Increase of volume Inert components
Remain
Equilibrium Shift to the side that involves larger moles of gas
unchanged
N Gas system:
Total Inert Equilibrium
Volume
pressure components n 0 n = 0
Shift to the side that
Increases Decreases involves fewer moles of
gas Remain
Shift to the side that unchanged
Decreases Increases x involves larger moles of
gas
3. Change in initial composition
a. Basic definition
- Yield / Efficiency (h%): Mole fraction of products in the equilibrium mixture
n A reacted
- Conversion ( ) : A =
n A initial
b. Effect of initial composition
- Maximum equilibrium yield → Stoichiometric initial compositions
- Increase of equilibrium conversion of A → Need to increase the
concentration of other reactants
