Tutorial on Equilibrium Law, Equilibrium constant

Kc and Reaction quotient Qc.

Prepared by
Lawrence Kok
http://lawrencekok.blogspot.com
 Dynamic Equilibrium At Equilibrium

Forward Rate, K1 Reverse Rate, K-1

Conc
Conc vs time Rate vs time

A+B

Reversible (closed system)

C+D
Time

Conc reactants and products remain

CONSTANT/UNCHANGE Forward rate = Backward rate

Equilibrium Constant Kc

K1
coefficient Conc of product and reactant
aA(aq) + bB(aq) cC(aq) + dD(aq) at equilibrium

K-1
Conc represented by [ ]
Solid/liq not included in Kc

Equilibrium Constant Kc
Excellent Notes

C  D
express in
c d
K1
Kc  Kc  K 1 rate..cons tan t.. forward

Aa Bb K 1 K 1 rate..cons tan t..reverse
Click here notes on dynamic equilibrium

Kc = ratio of molar conc of product (raised to power of their respective stoichiometry coefficient)
to molar conc of reactant (raised to power of their respective stoichiometry coefficient)
 Position of equilibrium Magnitude of Kc Extend of reaction

How far rxn shift to right or left?

Not how fast

Kc 
C  D
c d

 Kc 
C  D
c d


Aa Bb Aa Bb
K c  K c 
1
K c  3 10 92 K c  8.7  10 2 K c  3 10 81

2CO2(g) ↔ 2CO(g) + O2(g) H2(g) + I2(g) ↔ 2HI(g) 2H2(g) + O2(g) ↔ 2H2O(g)

Small Kc Kc Large Kc
• Position equilibrium shift to left • Position equilibrium lies slightly right • Position equilibrium shift to right
• More reactants > products • Reactants and products equal amount • More products > reactants

Reaction completion

Kc
Temp Extend
dependent of rxn
Reactant favoured Reactant/Product equal Product favoured
Not how fast
 Equilibrium Constant Kc

aA(aq) + bB(aq) cC(aq) + dD(aq)

Kc 
C  D
c d

Aa Bb
Conc of product and reactant at equilibrium

Equilibrium expression HOMOGENEOUS gaseous rxn

4NH3(g) + 5O2(g) ↔ 4NO(g) + 6H2O(g) N2(g) + 3H2(g) ↔ 2NH3(g) 2SO2(g) + O2(g) ↔ 2SO3(g)

NO  H 2O
4 6
NH 3 
2
Kc 
SO3 
2

Kc  Kc 
NH 3 4 O2 5 N 2 1H 2 3 SO2 2 O2 1
Equilibrium expression HOMOGENEOUS liquid rxn Reactant/product same phase

CH3COOH(l) + C2H5OH(l) ↔ CH3COOC2H5(l) + H2O(l)

Kc 
CH 3COOC2 H 5  H 2 O
1 1

CH 3COOH 1 C2 H 5OH 1

Equilibrium expression HETEROGENOUS rxn Reactant/product diff phase

NH4CI(s) ↔ NH3(g) + HCI(g) CaCO3(s) ↔ CaO(g) + CO2(g) Cu2+(aq) + 4NH3(aq) ↔ [Cu(NH3)4]2+

Kc 
NH 3  HCI 
1 1
CaO  CO2 
1 1
 Cu ( NH 3 ) 4 2 
Kc  Kc 
NH 4CI 0 CaCO3 0 Cu 2 1 NH 3 4
Kc  NH3  HCI  K c  CaO CO2 
1 1 1 1
 Equilibrium Constant Kc Equilibrium Constant Kc Effect on Kc

inverse
aA bB bB aA Inverse Kc

Kc 
B
b
Kc
'

 A
a
Kc 
' 1
Aa Bb Kc
X2 coefficient
aA bB 2aA 2bB Square Kc

Kc 
B
b
Kc
'

B
2b
Kc  Kc
' 2

Aa A2a
1
2 coefficient 1 1
aA bB 2
aA 2
bB Square root Kc

Kc 
B
b
B  1
2b 1
Kc  Kc  Kc  Kc
' '

Aa
2

A12a
+ 2 reactions
aA bB + bB cC aA cC Multiply both Kc

B
b
C
c
C  B C 
c b
 b a  a
c
K c  K cii  K ci
'
K ci  K cii 
'
Kc
Aa Bb B A A
K cii K ci
 Kc for diff rxn
Adding 2 rxns Adding 2 rxns

N2(g) + O2(g) ↔ 2NO(g) K ci  2.3  10 19 HF(ag) ↔ H+(aq) + F -(aq) K ci  6.8  10 4

+ 2NO(g) + O2(g) ↔ 2NO2(g) K cii  3 10 6 + H2C2O4(ag) ↔ 2H+(aq) + C2O42 -(aq) K cii  3.8  10 6

N2(g) + 2O2(g) ↔ 2NO2(g) K c  K ci  K cii 2HF(ag) + C2O42- ↔ 2F -(aq) + H2C2O4(aq)

K c  2.3 1019  3  106
1 x2 coefficient
K c  7 1013
HF(ag) ↔ H+(aq) + F -(aq) K ci  6.8  10 4
Inverse rxn

N2(g) + 2O2(g) ↔ 2NO2(g)

K c  7  10 13 2HF(ag) ↔ 2H+(aq) + 2F -(aq) K c  K ci  6.8  104
' 2
 
2
 4.6  107

1 1 Square Kc
Kc  
' 2 Inverse rxn
2NO2(g) ↔ N2(g) + 2O2(g)
K c 7  10 13
H2C2O4(ag) ↔ 2H+(aq) + C2O42 - K cii  3.8  10 6
K c  1.42  1012
'

1 1
2H+(ag) + C2O42- ↔ H2C2O4(aq) K c    2.6  10 5
''
6
Effect on Kc Effect on Kc K cii 3.8  10

1 3 Add 2 rxn
Inverse rxn Inverts expression Invert Kc
Kc
K c  4.6 107
'
Doubling rxn coefficient Squares expression 2 2HF(ag) ↔ 2H+(aq) + 2F -(aq)
Kc
K c  2.6 105
''
Tripling rxn coefficient Cubes expression
Kc
3
+ 2H+(ag) + C2O42- ↔ H2C2O4(aq)

Halving rxn coefficient Square root expression Kc 2HF(ag) + C2O42- ↔ 2F -(aq) + H2C2O4(aq)
Adding 2 reactions Multiplies 2 expression Kc  Kc
i ii
K c  K c'  K c'' Multiply Kc

K c  4.6  10 7  2.6  105  0.12

 IB Questions

1 Determine Kc for inversing rxn 2 Determine Kc for halving rxn

inverse halving 1
H2 + I2 ↔ 2HI 2HI ↔ H2 + I2 2SO2 + O2 ↔ 2SO3 SO2 + 2 O2 ↔ SO3

HI 
1

Kc 
2
H 2  I 2 
1 1
Kc 
SO3  2
 SO3 
Kc  

2 2
Kc 
'
1
H 2 1 I 2 1 HI 2 SO2 2 O2 1  SO2  O2  
2

K c  50 1 1
Kc    0.02
'

K c 50
K c  200 K c  K c  200  14.1
'

4 Kc is 170 at 500K 3 Determine Kc for doubling rxn

Determine if rxn is at equilibrium when conc are at:
[N2] =1.50, [H2] = 1.00, [NH3] = 8.00
doubling
N2(g) + 3H2(g) ↔ 2NH3(g) 2SO2 + O2 ↔ 2SO3 4SO2 + 2O2 ↔ 4SO3

 NH 3 
2
Kc 
NH 3 
2
SO3  2
 SO3 2 
2

Qc  Kc  Kc   1
N 2 1 H 2 3 N 2 1H 2 3 SO2 2 O2 1  SO2  O2  
2

Qc 
8.00
1.501.00
K c  K c   200
' 2 2
K c  200
K c  40000
,
Qc  42 .7 K c  170

Qc  K c
• Rxn not at equilibrium
• Shift to right, favour product
• Qc must increase, till equal to Kc
 Kc and Qc

Initial conc of H2 , I2 and HI At equilibrium

Expt Initial Initial Initial Expt Equilibrium Equilibrium Equilibrium

Conc H2 Conc I2 Conc HI Conc H2 Conc I2 Conc HI
1 2.40 x 10-2 1.38 x 10-2 0 1 1.14 x 10-2 0.12 x 10-2 2.52 x 10-2

H2(g) + I2(g) ↔ 2HI(g) HI  2


2.52  10  2 2
 46.4 K c  46 .4
Kc  Kc
H 2 1 I 2 1 1.14  10  0.12  10 
2 1 2 1

At equilibrium conc

Initial conc of H2 , I2 and HI Not at equilibrium

Expt Initial Initial Initial

Conc H2 Conc I2 Conc HI
1 0.0500 0.0500 0.100

HI 
2

0.100
2
 4.00
H2(g) + I2(g) ↔ 2HI(g) Qc  Qc Qc  4.00
H 2 1 I 2 1 0.0500.050
Difference between

Qc Kc
Constant at Independent of Conc of
Reaction quotient Not at equilibrium Predict the
fixed Temp initial conc product/reactant
at particular time conc direction of rxn
at equilibruim conc

Varies NOT constant

 Kc and Qc

HI 
2

2.52  10  2 2
 46.4 K c  46 .4
Kc  Kc
H2(g) + I2(g) ↔ 2HI(g)
H 2 1 I 2 1 1.14  10  0.12  10 
2 1 2 1

At equilibrium conc

Qc  K c
Qc  K c Qc  K c
Initial conc of H2 , I2 and HI Initial conc of H2 , I2 and HI
Reaction at
Expt Initial Initial Initial equilibrium Expt Initial Initial Initial
Conc H2 Conc I2 Conc HI Conc H2 Conc I2 Conc HI
1 0.0500 0.0500 0.100 1 0.0250 0.0350 0.300

Qc 
HI 
2
0.100
2
HI 
2
0.300
2
Qc   4.00 Qc  Qc   103
H 2 1 I 2 1 0.0500.050 H 2 1 I 2 1 0.02500.0350
More reactant > product Qc  More product > reactant Qc 

→
Rxn shift right → more product Rxn shift left more reactant

Bring Qc up Qc 
Click here to view notes
Bring Qc down Qc 

Qc  K c Qc  K c
 Kc from reaction stoichiometry

4 diff initial conc of H2 , I2 and HI At equilibrium Kc = 46.4 ( 730K)

same

H2(g) + I2(g) ↔ 2HI(g) Kc 

HI 
2
Kc 
2.52  10 
2 2
 46.4
H 2 1 I 2 1 1.14  10  0.12  10 
Rxn 1
2 1 2 1

Rxn 2, 3, 4  HI 
2
H2(g) + I2(g) ↔ 2HI(g) Kc  K c  same  46 .4
diff initial conc
H 2 1 I 2 1

Rxn shift to right

more products Qc 
 product
reac tan t 
Qc  Qc 
Qc 
 product
reac tan t  more reactants Rxn shift to left

Qc  K c Qc  K c
Qc  K c
Qc = Kc - rxn at equilibrium, no side/shift occur
Qc < Kc – rxn shift right, favour product
Qc > Kc – rxn shift left, favour reactant
 How dynamic equilibrium is shifted when H2 is added ?

N2(g) + 3H2(g) ↔ 2NH3(g) K c  4.07

• Add H2 , Qc decrease
• Position equilibrium shift to right
• Rate forward and reverse increase
• New equilibrium conc achieved when
Rate forward Kf = Rate reverse Kr
• More product NH3 ,but Kc unchanged

At equilibrium Equilibrium disturbed At new equilibrium

Conc reactant/product no change H2 added. More reactant Conc reactant/product no change

Equilibrium Conc H2 = 0.82M New Conc H2 = 1.00M New Equilibrium Conc H2 = 0.90M
Equilibrium Conc N2 = 0.20M Conc N2 = 0.20M New Equilibrium Conc N2 = 0.19M
Equilibrium Conc NH3 = 0.67M Conc NH3 = 0.67M New Equilibrium Conc NH3 = 0.75M

Kc 
NH 3 
2

Qc 
NH 3 
2
Kc 
NH 3 
2

N 2 1H 2 3 N 2 1 H 2 3 N 2 1H 2 3

0.67
2
0.67
2
Qc  K c Kc 
0.75
2

Kc  Qc 
0.201 0.823 0.201 1.003 Shift to the right
0.191 0.903
- Increase product
- New Conc achieve
K c  4.07 Qc  2.24 - Qc = Kc again
K c  4.07
 How dynamic equilibrium shift when H2 added ?

N2(g) + 3H2(g) ↔ 2NH3(g) K c  4.07

• Add H2 , Qc decrease
• Position equilibrium shift to right
• Rate forward and reverse increase
• New equilibrium conc achieved when
Rate forward Kf = Rate reverse Kr
• More product NH3 ,but Kc unchanged

At equilibrium Equilibrium disturbed At new equilibrium

Conc reactant/product no change H2 added. More reactant Conc reactant/product no change

Qc  K c Qc  Qc 

Qc  K c  4.07
Qc increase until Qc = Kc

Equilibrium shift to right

Rate forward Kf = Rate reverse Kr Rate forward Kf = Rate reverse Kr
Rate forward Kf > Rate reverse Kr

Qc  K c Qc  K c Qc  K c
 Equilibrium Law (Using ICE Method)

Reactants species present Product species present

Mol ratio 2 ↔ 1:1 2HI ↔ H2 + I2 Mol ratio 2 ↔ 2:1 2NO2 ↔ 2NO + 1O2

2HI ↔ 1H2 1I2 Change 2NO2 ↔ 2NO 1O2

Initial 0.8 0.0 0.0 Initial 0 1 1

React and Produce

Change -2x +x +x Change +2x -2x -x

Equilibrium 0.8 – 2x +x +x Equilibrium +2x 1 – 2x 1-x

x amt x amt
react produce
Mol ratio 2 ↔ 1:1 2HI ↔ 1H2 + 1I2
Mol ratio 1:1 ↔ 1:1 CO + H2O ↔ CO2 + H2

CO H2O ↔ I2 H2 2HI ↔ 1H2 1I2

3 3 0 0 Initial 0 3 1
Initial
-x -x +x +x Change +4x -2x -2x
Change
3-x 3-x +x +x Equilibrium +4x 3 – 2x 1 - 2x
Equilibrium

Mol ratio 2:1 ↔ 1 2NO + 1O2 ↔ 2CO2 Mol ratio 2:1 ↔ 2 2NO + 1O2 ↔ 2CO2

2NO 1O2 ↔ 2CO2 2NO 1O2 ↔ 2CO2

Initial 0.3 0.3 0.0 Initial 0 0 1

Change -x -1/2x +x Change +2x +1x -2x

Equilibrium 0.3 - x 0.3 – 1/2x +x Equilibrium +2x +1x 1 - 2x

ICE method
"I" - initial conc for each species rxn mixture.
"C" – change in conc for each species as system move toward eq.
"E" - equilibrium conc of each species in equilibrium.
 Equilibrium Law (Using ICE Method)

At equilibrium H2 added to system Rxn shift to left

Qc  K c Qc  K c Qc  K c  Qc
Mol ratio 2 ↔ 1:1 2HI ↔ 1H2 + 1I2 2HI ↔ 1H2 1I2
H2 
2HI ↔ 1H2 1I2 Initial 0.8 1.0 0.8

Equilibrium 0.8 0.6 0.8 Change +2x -x -x

Equilibrium 0.8 + 2x 1-x 0.8 - x

At equilibrium NO added to system Rxn shift to left

Qc  K c Qc  K c  Qc
Mol ratio 2 ↔ 2:1 2NO2 ↔ 2NO + 1O2
2NO2 ↔ 2NO 1O2
2NO2 ↔ 2NO 1O2 NO 
Initial 3 1.5 2
Equilibrium 3 1 2
Change +2x -2x -x

Equilibrium 3 + 2x 1.5 – 2x 2-x

At equilibrium CO added to system Rxn shift to right

Qc  K c Qc  K c  Qc
Mol ratio 1:1 ↔ 1:1 CO + H2O ↔ I2 + H2
1CO 1H2O ↔ 1I2 1H2
CO H2O ↔ I2 H2 CO 
Initial 4 3 2 2
Equilibrium 3 3 2 2
Change -x -x +x +x

Equilibrium 4-x 3-x 2+x 2+x

 Equilibrium Law Expression - Law of Mass Action Equilibrium Constant Kc

aA(aq) + bB(aq) cC(aq) + dD(aq) Eq Conc = Moles/Vol

All homogeneous gaseous

Kc 
C  D
c d
Conc of product and reactant at equilibrium
Cal Kc Aa Bb
CO + Br2 ↔ COBr2
Ex 1 CO + Br2 ↔ COBr2 Eq conc 8.78 x 10-3 4.90 x 10-3 3.40 x 10-3

3.40  10 
Cal Kc. (Vol vessel - 1 dm3 )
Eq Conc : [CO] = 8.78 x 10-3 M COBr2 
1

3

Kc  Kc K c  79
8.78  10  4.90  10 
[Br2] = 4.90 x 10-3M
[COBr2] = 3.40 x 10-3M CO1 Br2 1 3 1 3 1

Cal Eq Conc
PCI5 ↔ PCI3 + CI2
Ex 2
PCI5 ↔ PCI3 + CI2 Eq conc 0.20 0.01 x
Cal eq conc CI2
Kc = 0.19. (Vol vessel - 1 dm3 )
PCI 3  CI 2 
1 1
0.19 
0.01 x
1 1

Kc  x  3.8
0.201
Eq Conc : [PCI5] = 0.20M
[PCI3] = 0.01M PCI3 1

Cal Eq Conc
N2O4 ↔ 2NO2
Eq conc x 1.85 x 10-3
Ex 3
N2O4 ↔ 2NO2
Cal eq conc N2O4
Kc = 1.06 x 10-5. (Vol vessel - 1 dm3 ) Kc 
NO2 
2

1.06 10 5

1.8510  3 2
K c  0.323
Eq Conc : [NO2] = 1.85 x 10-3M N 2O4 1 x
1
 Equilibrium Law (Using ICE Method)

1 mol ethanoic acid add to 1 mol ethanol, at equilibrium, 0.67 mol ester produced. Mole ratio 1:1 ↔ 1:1
Cal Kc. (Vol vessel - 1 dm3)
Change = React and Produce
Ex 4
CH3COOH + C2H5OH ↔ CH3COOC2H5 + H2O
Initial mole 1.0 1.0 0 0
I -0.67 +0.67
Change (1 - 0.67) (1 - 0.67) 0.67 0.67
C Mole at eq 0.33 0.33 0.67 0.67
E Eq Conc 0.33/1 0.33/1 0.67/1 0.67/1

CH 3COOC2 H 5  H 2 O
1 1
0.67 0.67
1 1
Eq Conc = Mole/Vol Kc 
CH 3COOH 1 C2 H 5OH 1
Kc  K c  4.12
0.331 0.331
In esterification, 2 mol ethanoic acid, 3 mol ethanol and 2 mol H2O mixed.
Mole ratio 1:1 ↔ 1:1
Cal eq conc, Kc - 4.0 (Vol vessel – 1 dm3 )

Ex 5 CH3COOH + C2H5OH ↔ CH3COOC2H5 + H2O Change = Reacted and Produced

Initial mole 2 3 0 2
I
Change (2 - x ) (3 - x) +x 2+x - x amt reacted + x amt produced
C Mole at eq (2 – x ) (3 – x) +x 2+x
E Eq Conc (2 – x )/1 (3 -x)/1 x/1 (2 + x)/1

CH 3COOC2 H 5  H 2 O
1 1
x 2  x
1 1
Eq Conc = Mole/Vol Kc 
CH 3COOH 1 C2 H 5OH 1
4 x  1.33
2  x1 3  x1
Conc CH3COOC2H5 = 1.33M
Conc H2O = 3.33M
Conc CH3COOH = 0.67M
Conc C2H5OH = 1.67M

Click here notes equilibrium law

 Equilibrium Law (Using ICE Method)

Mole ratio 1:1 ↔ 1

Initial amt X (0.02) and Y (0.01). At eq conc – 0.009 Z produced
Cal Kc. (Vol vessel – 600 cm3 )
Change = React and Produce
Ex 6
X + Y↔ Z
X + Y ↔ Z -0.009 +0.009
Initial mole
Z 0.015
0.02 0.01 0
I 1 1
Change (0.02 – 0.009) (0.01 – 0.009) 0.009 Kc  Kc  K c  491
C
E
Mole at eq 0.011 0.001 0.009 X 1 Y 1 0.01831 0.00161
Eq Conc 0.011/0.6 0.001/0.6 0.009/0.6

Mole ratio 1:1 ↔ 2

Mixture 1.9 mol H2 and 1.9 mol I2 was added to vessel . At eq conc, 3mol HI form
Cal Kc . (Vol vessel – 1 dm3 )
Change = React and Produce
Ex 7
H2 + I2 ↔ 2HI
-1.5 +3
H2 + I2 ↔ 2HI
I Initial mole 1.9 1.9 0
Kc 
HI 
2
3
2
K c  56
C C
Kc 
H 2 1 I 2 1 0.41 0.41
hange (1.9 – 1.5) (1.9 – 1.5) 3
Mole at eq 0.4 0.4 3
E Eq Conc 0.4/1 0.4/1 3/1

Mole ratio 1 ↔ 1:1

0.05 mol SO2CI2 was used, at equilibrium 0.0345 mol CI2 formed
Cal Kc. (Vol vessel – 2 dm3 )
Change = React and Produce

Ex 8
SO2CI2 ↔ SO2 + CI2 -0.0345 +0.0345

SO2CI2 ↔ SO2 + CI2

I Initial mole 0.05 0 0 SO2  CI 2 

1 1
Kc 
0.0173 0.0173
1 1

Kc 
Change
C Mole at eq
(0.05 – 0.0345)
0.0155
0.0345
0.0345
0.0345
0.0345 SO2 CI 2 1 0.007751
E Eq Conc 0.0155/2 0.0345/2 0.0345/2 K c  0.0386
 Equilibrium Law (Using ICE Method)
Mole ratio 1:1 ↔ 1:1
Initial amt, 3 mol CO and H2O were used.
Cal eq conc H2, Kc - 4.0 (Vol vessel - 1 dm3 ) Change = React and Produce

Ex 9
CO + H2O ↔ CO2 + H2
- x amt reacted + x amt produced
CO + H2O ↔ CO2 + H2
I
C
Initial mole
Change
3
(3 - x)
3
(3 - x)
0
+x
0
+x Kc 
CO2  H 2 
1 1

4
x x
1 1

x  2M
E Eq Conc (3 - x)/1 (3 - x)/1 x/1 x/1 CO1 H 2 O1 3  x1 3  x1
Mole ratio 2 ↔ 1:1 Quadratic eqn
1 mol HI was used initially, and 0.78 mol of HI remain at equilibrium.
Cal Kc. (Vol - 1 dm3 )
Change = React and Produce
Ex 10
2HI ↔ H2 + I2
-0.22 +0.11
2HI ↔ H2 + I2
I Initial mole 1 0 0
H 2  I 2 
1 1
Kc 
0.11 0.11
1 1
K c  0.02
C Change (1 - 0. 22) 0.11 0.11 Kc 
E Eq Conc 0.78/1 0.11/1 0.11/1 HI 2 0.782
Initial amt PCI5 - 0.01 mol. Kc = 0.19. (Vol vessel - 0.5 dm3 )
Cal eq conc PCI5, PCI3 and CI2
2 2
Ex 11
PCI5 ↔ PCI3 + CI2  x   x 
PCI5 ↔ PCI3 + CI2 Kc 
PCI 3  CI 2 
1 1  0 .5 
Kc    1
 0 .5 
0.19    1
I Initial mole 0.01 0 0 PCI5 1  0.01  x 
 0.5 
 0.01  x 
 0.5 
C Change 0.01 - x +x +x

E Eq Conc (0.01 – x)/0.5 x/0.5 x/0.5

x  0.0091
[PCI5] = (0.01 – 0.0091)/0.5 = 0.0018M
[PCI3] = 0.0091/0.5 = 0.018M
[CI2] = 0.0091/0.5 = 0.018M Quadratic eqn
 Equilibrium Law (Using ICE Method) Using approximation and assumption

Eq conc reactant/product given. Eq amt used instead of eq conc

Ex 12 Cal Kc using vol vessel - 1 dm3 /2 dm3

1 dm3 2 dm3
H2 + I2 ↔ 2HI H2 + I2 ↔ 2HI
H2 + I2 ↔ 2HI H2 + I2 ↔ 2HI
Mole at eq 0.4 0.4 3 Mole at eq 0.4 0.4 3
Eq Conc 0.4/1 0.4 /1 3/1 Eq Conc 0.4/2 0.4 /2 3/2

HI  2
Kc 
3
2
Kc 
HI 
2
3 
2
2

Kc  
H 2 1 I 2 1 0.4 2  0.4 2 
Kc
H 2 1 I 2 1 0.41 0.41 1 1

Eqn with equal number molecule both side

K c  56 Eq expression – Independent of volume K c  56
Eq amt used instead of eq conc

Eq conc reactant/product given.

Ex 13 Cal Kc using vol vessel - 1 dm3 /2 dm3

SO2CI2 ↔ SO2 + CI2 2 dm3

1 dm3 SO2CI2 ↔ SO2 + CI2
SO2CI2 ↔ SO2 + CI2 SO2CI2 ↔ SO2 + CI2
Mole at eq 0.011 0.001 0.009 Mole at eq 0.011 0.001 0.009
Eq Conc 0.011/1 0.001/1 0.009/1 Eq Conc 0.011/2 0.001/2 0.009/2

Kc 
SO2  CI 2 
1 1

Kc 
0.001 0.009
1 1


0.001  0.009 
2
1

2
1

Kc 
0.0005 0.00045
1 1

SO2 CI 2 1 0.0111 0.0112 

Kc 1
0.00551
K c  8.18  10 4 Eqn with diff number molecule both side K c  4.09  10 5
Eq expression – Dependent of volume
 Equilibrium Law (Using ICE Method) Using approximation and assumption

K c  BIG
- Lots product form

K c  SMALL
- Little product form
- Initial Conc reactant
- Initial Conc reactant
changed
unchanged
Eq conc reactant/product given.
Eq conc reactant/product given.
Cal eq conc, Kc - 1. Vol vessel - 1 dm3
Cal eq conc, Kc - 4 x 10-5. Vol vessel - 1 dm3

2H2O ↔ 2H2 + O2 PCI5 ↔ PCI3 + CI2

2H2O ↔ 2H2 + O2 PCI5 ↔ PCI3 + CI2
Initial mole 0.1 0 0 Initial mole 1 0 0
Change -x +x +x/2 Change 1-x +x +x
Eq Conc 0.1 - x +x +x/2 Eq Conc 1–x x x

H 2  O2 
2 1
Kc 
PCI 3  CI 2 
1 1

Kc  PCI5 1 Cannot use

H 2 O2 Using
approximation
0.1 – x ≈ 0.1 approximation

x x / 2 1
x2 1–x≠1

x  x / 2
2 1
2 1
4  10 5 
0.1  x2 4  10 5
 1  x1
0.12
x2  x 1  0
x 3  20.1  4  10 5
2

x  20.1  x   4  10 5
3 2

x  0.62
x  0.0093 Solve quadratic eqn difficult !
Solve cubic eqn difficult !
Kc very small < 10-3 Kc very BIG > 10-3
Not much change in reactant conc Change in reactant conc
Approximation is VALID Approximation NOT VALID

[reactant]initial ≈[reactant]eq [reactant]initial ≠ [reactant]eq

 Equilibrium Law (Using ICE Method) Using approximation and assumption

K c  BIG
- Lots product form

K c  SMALL
- Little product form
- Initial conc reactant
- Initial conc reactant
changed
unchanged
Eq conc reactant/product given. Eq conc reactant/product given.
Cal eq conc, Kc - 1 x 10-10. Vol vessel - 1 dm3 Cal eq conc, Kc - 1. Vol vessel - 1 dm3

PCI5 ↔ PCI3 + CI2 PCI5 ↔ PCI3 + CI2

PCI5 ↔ PCI3 + CI2 PCI5 ↔ PCI3 + CI2
Initial mole 1 0 0 Initial mole 1 0 0
Change 1-x +x +x Change 1-x +x +x
Eq Conc 1–x x x Eq Conc 1–x x x

PCI 3  CI 2 
1 1
10 x2 Using
Kc 
PCI 3  CI 2 
1 1

1
x2 Cannot use

1  10 
approximation
Kc  approximation

PCI5 1 1  x 1 1–x≈1 PCI5 1 1  x1 1–x≠1

10
1  10  1
x
2

x2  x 1  0
1
Solve quadratic eqn
Kc very small < 10-3
Not much change reactant conc Kc very BIG > 10-3 Change in x - big
5
Approximation is VALID x  1  10 Change in reactant conc, BIG
x  0.62
[PCI5] = (1 – 0.00001) [PCI5] = (1 – 0.62) = 0.38M
= 0.99999M [PCI3] = 0.62M
[PCI3] = 0.00001M [CI2] = 0.62M
[CI2] = 0.00001M

[reactant]initial ≈ [reactant]eq [reactant]initial ≠ [reactant]eq

[ 1 ]initial ≈ [0.99999]eq [ 1 ]initial ≠ [ 0.38 ]eq
 Equilibrium Law (Using ICE Method)
Using approximation and assumption
Initial amt, 1 mol CO and H2O were used. 1 dm3
Cal eq conc all component, Kc - 4.0 (Vol vessel - 1 dm3 ) Eqn with equal number molecule both side
Eq expression – Independent of volume
Ex 14
CO + H2O ↔ CO2 + H2
Eq amt used instead of eq conc
CO + H2O ↔ CO2 + H2
I Initial mole 1 1 0 0
K c  BIG
C Change -x -x +x +x
Cannot use
E Eq Amt (1 - x) (1 - x) x x approximation
[1 – x] ≠ 1

Kc 
CO2  H 2 
1 1

4
x x 1 1
4
x2

x  0.667
[CO]
[H2O]
= 1 – 0.667 = 0.333
= 1 – 0.667 = 0.333

CO1 H 2 O1 1  x1 1  x1 1  x 2

[CO2]
[H2O]
= 0.667
= 0.667

Using square root method

2 dm3

0.05 mol SO2CI2 added to 2 dm3 vessel.

At equilibrium, 0.0345 mol CI2 form. Cal Kc

Ex 15
SO2CI2 ↔ SO2 + CI2
SO2CI2 ↔ SO2 + CI2

I Initial mole 0.05 0 0 Eq amt cannot be used

Change -0.0345 +0.0345 + 0.0345
C Mole at eq (0.05 – 0.0345) 0.0345 0.0345 Eqn with diff number molecule both side
E Eq Conc 0.0155/2 0.0345/2 0.0345/2 Eq expression – Dependent of volume

Kc 
SO2  CI 2 
1 1
0.0173 0.0173
1 1
Kc  K c  0.0386
SO2 CI 2 1 0.007751
 Equilibrium Law (Using ICE Method)

Initial amt, 2 mol H2 and I2 were used.

Cal eq conc all component, Kc - 49 (Vol vessel - 2 dm3 )
Ex 16
H2 + I2 ↔ 2HI
H2 + I2 ↔ 2HI

I Initial mole 2 2 0 Click here simulation equilibrium Click here simulation

Change -x -x +2x
C Mole at eq 2-x 2-x +2x Eqn with equal number molecule both side
E Eq Conc 2–x 2–x +2x Eq expression – Independent of volume

HI 
2
2 x
2
2x x  1.56
49 
[H2] = (2 – 1.56) = 0.44M
Kc  49 
H 2 1 I 2 1 2  x1 2  x1 2 x
[I2] = (2 – 1.56) = 0.44M
[HI] = 2 x 1.56 = 3.12M

Equilibrium was investigated in two expt at diff temp

Result shown table below. Cal Kc for expt 1 and 2.

EXPT 1 EXPT 2
2HI ↔ H2 + I2
2HI ↔ H2 + I2 2HI ↔ H2 + I2
Initial mole 0.06 0 0 Initial mole 0 0.04 0.04
Change -0.02 +0.01 +0.01
Kc 
H 2  I 2 
1 1
Change +0.04 -0.02 - 0.02

HI 2
Mole at eq (0.06 – 0.02) +0.01 +0.01 Mole at eq +0.04 0.04 – 0.02 0.04 - 0.02
Eq Conc 0.04 0.01 0.01 Eq Conc 0.04 0.02 0.02


0.01 0.01
1 1

0.02 0.02
1 1

K c  6.25  10 2 Kc Kc K c  0.25
0.042 0.042
 Equilibrium Law)

Ex 17 Initial amt -2 mol SO2 and O2 were used. Ex 18 Initial amt, 2 mol SO2 and O2 were used.
Cal eq amt, if 90% of SO3 formed . Change Cal eq amt, if 20% of SO2 react.

2SO2 + 1O2 ↔ 2SO3 2SO2 + 1O2 ↔ 2SO3

Initial mole 2 2 0 React and Produce Initial mole 2 2 0
Change - 1.8 -0.9 +1.8 Change -0.4 -0.2 +0.4
Eq Amt (2 – 1.8) (2 – 0.9) +1.8 x amt x amt Eq Amt (2 – 0.4) (2 – 0.2) +0.4
Eq Amt 0.2 1.1 1.8 react produce Eq Amt 1.6 1.8 0.4

90% SO3 produce 20% SO3 react

Mol ratio SO2 : SO3, = 1 : 1 Mol ratio SO2 : SO3, = 1 : 1
90% SO2 react – 90% SO3 produced 20% SO2 react – 20% SO3 produced
90% SO2 react - 90% x 2 = 1.8 mol SO3 produced 20% SO2 react - 20% x 2 = 0.4 molSO3 produced
Amt SO2 = (2 – 1.8) = 0.2 mol left Amt SO2 left = 2 – 0.4 = 1.6 mol left
Mol ratio SO2 : O2. = 2 : 1 Mol ratio SO2 : O2. = 2 : 1
1.8 mol SO2 react with 0.9 mol O2 0.4 mol SO2 react with 0.2 mol O2
Amt O2 = (2 – 0.9) = 1.1 mol left Amt O2 left = 2 – 0.2 = 1.8 mol

Ex 20 N2 + H2 react ratio 1 : 3 to produce NH3.

Ex 19 Initial amt, 1 mol N2O4 used. 66% dissociated.
Equilibrium mixture contain 15% NH3.
Cal eq amt.
Cal eq amt for each species.

1N2O4 ↔ 2NO2 Let x N2 reacted N2 + 3H2 ↔ 2NH3

Initial mole 1 0
Initial mole 1 3 0
Change -0.66 +1.32
Change -x -3x 2x
Eq Amt (1 – 0.66) +1.32
Eq Amt 1–x 3 – 3x 2x
Eq Amt 0.34 1.32
Eq Amt 0.74 2.22 0.52

66% N2O4 reacted 2x

% Nitrogen   100  15
Mol ratio N2O4 : NO2, = 1 : 2
66% N2O4 react – 66% x 1 = 0.66 mol N2O4 react
1  x   3  3x   2 x
0.66 mol N2O4 react - 1.32 mol NO2 produced X = 0.26
Amt N2O4 left = 1 – 0.66 = 0.34 mol
[N5] = 0.74, [H2] = 2.22, [NH3] = 0.52
 Simulation on Dynamic equilibrium

Click here simulation using paper clips Click here to view simulation Click here simulation on reversible rxn

Click here on reversible rxn Click here equilibrium constant

Click here simulation equilibrium Click here simulation

 Acknowledgements
Thanks to source of pictures and video used in this presentation

Thanks to Creative Commons for excellent contribution on licenses

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Prepared by Lawrence Kok

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