Chemical Equilibria: This Is The Reactin in Which The If The Firward and The Backward Reactins Are The

CHEMICAL EQUILIBRIA
This is the reactin in which the rate if the firward

and the backward reactins are the same.
INTRODUCTION TO CHEMICAL EQUILIBRIUM
This is the reacton that proceeds towards the products and
towards the reactants. It is denoted by double arrows “↔” or
( ).
In essence all the chemical reactons are reversable; but the
ones that are shown by “→” means that the reacton is
priduct-faviured.
Example:
2Na(s) + Cl2(g) → 2NaCl(s)
Almost all the reactants are converted to the product.
The unreacted reactants are si small that they are negligible
at equilibrium.
THE CONCEPT OF CHEMICAL EQUILIBRIUM
But the reactin of nitrigen and hydrigen to form
amminia, is purely reversible fir example
N2(g) + 3H2(g) ↔ 2NH3(g)

Befire chemical equilibrium is reached, the rate at
which the reactants are cinverted ti the priduct is
mire than the rate at which the priduct is
cinverted reactants.
At equilibrium, the rate at which the reactants are
converted to the priduct is equal to the rate at which
priduct is cinverted ti reactants.
This is called dynamic equilibrium: See below

These dynamic equilibrium, can be afected by
external factors such as
* Additin ir remival if a reactant ir a priduct.
(Cincentratin change).
* Temperature change
* Changing the vilumes (in the case if gases).
Example of physical observaton of the reversible
reacton of cibalt (II) chliride with a dilute
hydrichliric acid. At some stage you would have:
[Ci(H2O)6]2+(aq) + 4Cl-(aq)↔ [CiCl4]2-(aq) + 6H2O
The colour of this soluton is purplish.
When this soluton is placed into the water bath (ice
and a bit of water), the colour changes to red (reddish
irange).
When putng it in biiling water, the colour changes to
blue.
When adding water to this soluton, to increase
[Ci(H2O)6]2+ concentraton, the colour changes to red
(reddish irange) again.
When a bit of hydrichliric acid is added to the
soluton, to increase the Cl- ions it changes to the
iriginal purplish ciliur.
The change in these colours is shown below.
Another example that shows that almist all the
chemical reactons are reversible, is the reacton of
the solutons of calcium chliride (CaCl2) and sidium
hydrigen carbinate (NaHCO3).
CaCl2(aq)+NaHCO3(aq)→Ca2+(q) +2Cl-(aq) +Na+aq) + HCO3-(aq)
Net iinic:
Ca2+(aq) + 2HCO3-(aq) → CaCO3 (s) + CO2(g)+ H2O (l)
Adding ice or bubbling CO2 to dissolve CaCO3(s); we get:
CaCO3(s)+ CO2(g) + H2O(l) →Ca2+(aq) +2HCO3(aq)-
At equilibrium, we get,
Ca2+(aq) + 2HCO3-(aq)↔CaCO3(s) + CO2(g)+H2O(l)
THE EQUILIBRIUM CONSTANT AND REACTION QUOTIENT
The equilibrium cinstant is the quitent obtained

when the priduct of the cincentratins of the
priducts raised ti the piwer if their stiichiimetric
ciefcient is divided by the priduct of the
cincentratins of the reactants raised ti the piwer
if their stiichiimetric ciefcient on the
stiichiimetric chemical reactin equatin that is at
equilibrium.
This is indicated by K.
Example:
aA + bB cC +dD -----K = ?
Where K is an equilibrium cinstant and it is
calculated as:
c d
}
[C ] [ D ] Equilibrium cinstant
K  a b
[ A] [ B ] expressiin
For any reacton in gaseius form, if their
concentratons are given in partal pressures, then
K is writen as Kp.
The above formula becomes:
aA(g) + bB(g) cC(g) +dD(g) -----Kp = ?
c d
( pC ) ( p D )
Kp  a b
( p A ) ( pB )
Where P is a partal pressure of each reagent in a
stiichiimetric equatin.
The formaton of amminia from nitrigen gas and

hydrigen gas is one of the examples of the above
reacton:
N2(g) + 3H2(g) 2NH3(g) -----Kp = ?
2
( p NH 3 )
Kp  1 3
( pN 2 ) ( pH 2 )
For any reacton in aqueius form and if the

cincentratin is in mil/L, K is writen as Kc.
The above formula becomes:
aA(aq) + bB(aq) cC(aq) + dD(aq) -----Kc = ?
c d
[C ] [ D]
Kc  a b
[ A] [ B ]
For an example:
[Cu(NH3)4]2+(aq) Cu2+(aq) + 4 NH3(aq) --- Kc =?
2 4
[Cu ][ NH 3 ]
Kc  2
[[Cu ( NH 3 ) 4 ] ]
For an acidic silutin, and if the cincentratin is in
mil/L, Kc becomes Ka and it is called iinizatin
cinstant.
For example:
HA(aq) + H2O(ℓ) H3O+(aq) + A-(aq) -----Ka =?
[ H 3O ][ A ]
 
Ka 
[ HA]
Example of the acidic silutin is:
HCl(aq) + H2O(ℓ) H3O+(aq)+ Cl-(aq)-Ka =?
[ H 3O ][Cl ]
 
Ka 
[ HCl ]
For basic silutin, Kc becomes Kb and it is also called
iinizatin cinstant.
For example:
B + H2O (l) BH+ + OH- -----Kb =?
[ BH ][OH ]
 
Kb 
[ B]
Example of the basic silutin is :
NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) --- Kb =?

[ NH 4 ][OH  ]
Kb 
[ NH 3 ]
If the reactin is neutral then Kc = Kw :
H2O(l) + H2O(l) H3O+(aq) + OH-(aq) --- Kw =?
K w [ H 3O  ][OH  ]
•Kw is called auti-iinizatin cinstant ir iin-priduct

cinstant for water.
For the dissilutin if a precipitate that is formed
during precipitatin reactin, K is writen as Ksp.
Ksp is called the silubility equilibrium cinstant.
For the reacton:
AgCl(s) Ag+(aq) + Cl-(aq)---Ksp = ?
Then Ksp becimes:
Ksp = [Ag+][Cl-]
The Reactin quitent (Q) is the quitent obtained

when dividing the priduct of the cincentratins of
the priducts raised ti their stiichiimetric factirs by
the priduct of the cincentratins of the reactants
raised ti their stiichiimetric factirs of the
stiichiimetric chemical reactin equatin that is
NOT necessarily at equilibrium.
Q is calculated the way K was calculated, but Q is
used fir any reactin (the ones that are nit at
equilibrium and the ones that are at equilibrium).
Example
For any reacton that is at equilibrium then:
aA(aq) + bB(aq) cC(aq) + dD(aq) -----Kc = ?
c d
[C ] [ D]
Kc  a b
[ A] [ B ]
For any reacton that is NOT necessarily at

equilibrium:
aA(aq) + bB(aq) cC(aq) + dD(aq) -----Q = ?
c d
[C ] [ D ]
Q a b
[ A] [ B ]
Therefire at equilibrium Q = K.
All these are summarized beliw:
THE EQUILIBRIUM CONSTANT AND
REACTION QUOTIENT AT EQUILIBRIUM
Kp
K
Kc
Kw
Ksp
K } =Q
THE QUILIBRIUM CONSTANT AND
REACTION QUOTIENT
When writng equilibrium cinstant expressiin, (to
calculate the value of K and the value of Q, the
following must be born in mind:
*All cincentratins are equilibrium values (always fir
K and simetmes fir Q).
*Priduct cincentratins appear in the numeratir and
reactant cincentratins appear in the deniminatir.
*Each concentraton is raised ti the piwer of its
stiichiimetric ciefcient in the stiichiimetric
(balanced) chemical reacton.
THE EQUILIBRIUM CONSTANT, K AND
REACTION QUOTIENT , Q
*The value of the cinstant K depends on the
partcular reactin and on the temperature.
*The values of K are dimensiinless.
*The reagents (reactants and priducts) in a silid
firm must be imited. The concentraton of each of
them is equal to ine.
*The reagents (reactants and priducts) in a liquid
firm must be imited. The concentraton of each of
them is equal to ine.
THE EQUILIBRIUM CONSTANT, K AND REACTION QUOTIENT , Q
The value of K can tell if the reacton is reactant

favir, priduct favir or if the reacton is in dynamic
equilibrium (symmetrical).
If the value of K is greater than one (K >1), then the
reacton is priduct faviured.
That is, the rate of the firward reacton is faster than
the rate of the backward reacton.
*If the value of K is less than one (K < 1), then the
reacton is reactant faviured.
That is, the rate of the backward reacton is faster
than the rate of the firward reacton.
*If the value of K is equal ti 1 (K = 1), then the

reacton is at dynamic equilibrium (symmetrical).
That is, the rate of the firward reacton is equal to
the rate of backward reacton.
Example: Is this reacton, product or reactant favoured?
NO(g) + O3(g) NO2(g) + O2(g)
[ NO2 ][O2 ]--Kc = 6.34 x 1034 at 25iC

Kc 
[ NO ][O3 ]
K >1, the reacton is therefore priduct faviured.
[NO2][O2] >> [NO][O3], the reacton has run ti
cimpletin.
Almist all the reactants are converted to product at
equilibrium.
The reactants cannot be physically seen at equilibrium.
THE EQUILIBRIUM CONSTANT, K AND REACTION QUOTIENT, Q
2. Is this reacton, priduct or reactant faviured?

3/2O2(g) O3(g)
[O3 ]
Kc  3/ 2
---Kc = 2.5x 10-29 at 25iC
[O2 ]
K < 1, the reacton is therefore reactant faviured.
[O2] >> [O3], the reacton did nit run ti cimpletin.
Almist all the products are converted to reactants at
equilibrium.
The priduct cannit be physically seen at equilibrium.
THE EQUILIBRIUM CONSTANT AND THE REACTION QUOTIENT , Q
Therefore:
If K>1 the reacton is priduct favired.
If K=1 the equilibrium is at dynamic equilibrium (symmetrical).
If K<1 the reacton is reactant favired.
The relatonship between K and Q can also tell if the

reacton is at equilibrium or nit.
If K > Q the reacton is priduct favired.
If K = Q the equilibrium is symmetrical.
If K < Q the reacton is reactant favired.
THE EQUILIBRIUM CONSTANT AND
REACTION QUOTIENT
The relatonship between K and Q can also tell if the reacton is at equilibrium or
nit.
If K > Q the reacton is priduct favired.
If K = Q the equilibrium is symmetrical.
If K < Q the reacton is reactant favired.
OR
If Q < K the reacton is priduct favired.
If Q = K the equilibrium is symmetrical.
If Q > K the reacton is reactant favired.
In this case K is given and Q have to be calculated.
DETERMINING AN EQUILIBRIUM
CONSTANT
The value of K can be determined in diferent ways:
*If the equilibrium cincentratins of the reactants
and the priduct are known, then the value of K can
be determined.
*If the inital cincentratins of the reactants and the

equilibrium cincentratin of the priduct are known,
then the value of K can be determined.
This will be dine in Theme 2.
CONSTANT
*If the inital cincentratins of the reactants and the
value if K are known, then the equilibrium
cincentratins of the reagents can be calculated.
*If the number if miles and the vilume of the

reactants; and the equilibrium cincentratin of the
priduct are known, then the value of K can be
determined. etc.
TEST ON CALCULATIONS INVOLVING
EQUILIBRIUM CONSTANT
Calculate the value of K for the following chemical

reacton.
2SO2(g) + O2(g) 2SO3(g)
If the equilibrium cincentratin of the reactants and
the priducts are as follows:
[SO2] = 3.61 x 10-3M
[ O2 ] = 6.11 x 10-4M
[SO3] = 1.01 x 10-2M
CALCULATIONS INVOLVING EQUILIBRIUM
CONSTANT
2
[ SO3 ]
Kc  2
[ SO2 ] [O2 ]
2
(1.010]
Kc  3 2 4
(3.61x10 ) (6.11x10 )
4
K c 1.28 x10
CONCENTRATIONS OF THE REAGENTS
If the inital cincentratins of the reactants and the
value if K are known, then the equilibrium
cincentratins of the reagents can be calculated
using three diferent methids.
*The imissiin ir appriximatin method.
*The perfect square method.
*The quadratc equatin.
*The successive appriximatin methid.?????
CALCULATIONS WHERE THE SOLUTION INVOLVES AN
APPROXIMATION EXPRESSION
This is the method that is used if the value of K << [ A]0
in any equaton:
A ↔ B+ C
That is if 100 x K < [A]0, then the above method can be
applied.
TEST ON THE CALCULATIONS WHERE THE SOLUTION
INVOLVES AN APPROXIMATE EXPRESSION
Calculate the equilibrium cincentratin of I2 and the
concentraton of I if I2 molecules dissociates into I
atoms for which the inital concentraton of I2 is
0.45M and the value of K is 5.6 x 10-12 at 500iC.
Soluton
*Write down a stoichiometric equaton.
*Set up an ICE table
*Make approximaton and solve for x.
I2(g) ↔ 2I(g)
At equilibrium:
I2(g) ↔ 2I(g)
Inital (M) 0.45 0
Change (M) -x +2x

Equilibrium (M) 0.45 -x 2x
2
[I ]
Kc 
[I2 ]
2
 12 (2 x)
5.6 x10 
(0.45  x )
x is very small compared to 0.45 (0.45-x ≈ 0.45)
because 100 x K < [A]0
100 x 5.6 x 10-12 < 0.45 (4.5 x 10-1 )
2
 12 4x
5.6 x10 
 12
0 .45
2 5.6 x10 x 0.45
x 
4
 12
5.6 x10 x 0.45
x
4
= 7.9 x 10-7
Therefore at equilibrium:
[I2] = 0.45 – x
= 0.45 – 7.9 x 10-7
= 0.44999921
= 0.45M
[I] = 2x
= 2 (7.9 x 10-7)
= 15.8 x 10-7
= 1.6 x 10-6 M
TEST ON CALCULATING EQUILIBRIUM CONCENTRATIONS
USING AN APPROXIMATE EXPRESSION
1. Consider the reacton:
N2(g) + O2(g) ↔ 2 NO(g)
Calculate the equilibrium cincentratin of each
reagent if the inital concentratons of N2 and O2 are
0.080M and 0.020M respectvely and the value of Kc
is 1.0 x 10-5 at 1500K.
2. Calculate the cincentratin if H3O+ in the 0.020 M
soluton of C6H5CO2H that is dissolved in water to
give C6H5CO2- and H3O+, given that
KC = 6.3 x 10-5 M for the C6H5CO2H.
TEST ON CALCULATING EQUILIBRIUM CONCENTRATIONS USING AN
APPROXIMATE EXPRESSION
3. The equilibrium constant, Kc = 55.64 for
H2(g) + I2(g) ↔ 2HI(g)
has been determined at 425iC. If 0.130mil each of H2
and I2 is placed in a 25.0L fask at 425iC; what are the
concentratons of H2, I2 and HI when equilibrium has
been achieved?
4. Calculate the cincentratin if the priducts and
the reactant when the reacton reach equilibrium for
the decompositon of PCl5 to PCl3 and Cl2 if the Kc is
1.20 at a given temperature and the inital
concentraton of PCl5 is 0.0920M.
1.Consider the reacton:
N2(g) + O2(g) ↔ 2 NO(g)
Calculate the equilibrium cincentratin of each
reagent if the inital concentratons of N2 and O2 are
0.080M and 0.020M respectvely and the value of Kc
is 1.0 x 10-5 at 1500K.
Silutin
*Use the ICE table to calculate the equilibrium
concentraton.
*100 x 1.0 x 10-5 = 1.0 x 10-3 <<< 0.080 K <<< [N2]i
and
*100 x 1.0 x 10-5 = 1.0 x 10-3 <<< 0.020 K<< [O2] i
Therefore, the appriximatin expressiin can be used
At equilibrium:
N2(g) + O2(g) ↔ 2NO(g)

Inital (M) 0.080 0.020 0
Change (M) -x -x +2x
Equilibrium (M) 0.080-x 0.020-x 2x

N2(g) + O2(g) ↔ 2 NO(g)
[ NO ]2
K 
[ N 2 ][O2 ]
2
5 (2 x)
1.0 x10 
(0.080  x)(0.020  x)
Since 100 x K <<< [N2]i and 100 x K<< [O2] i;

then the appriximatin methid can be used
APPROXIMATE EXPRESSION
2
5 4x
1.0 x10 
(0.080)(0.020)
5
2 (1.0 x10 )(0.080)(0.020)
x 
4
x = 10.-50 x10  5 )(0.080)(0.020)

6.3(x1
x
4
[N2] = 0.080 – x = 0.080 – 6.3 x 10-5
= 0.079937
≈ 0.080 M
[O2] = 0.020 –x = 0.020 – 6.3 x 10-5

= 0.019937 M
≈ 0.020 M
[NO] = 2(x) = 2(6.3 x 10-5)
= 1.26 x 10-5 M
≈ 1.3 x 10-4 M
2. Calculate the cincentratin if H3O+ in the 0.020M
soluton of C6H5CO2H that is dissolved in water to give
C6H5CO2- and H3O+, given that
KC = 6.3 x 10-5 M for the C6H5CO2H.
Soluton:
Write down a stiichiimetric equatin.
* use an ICE table to calculate the [H3O+].
C6H5CO2H(aq)+H2O(ℓ)↔C6H5CO2-(aq) + H3O+
Inital (M) 0.020 0 0
Change (M) -x +x +x
Equilibrium (M) 0.020-x x x

[ H 3O ][C6 H 5CO2 ]

Kc 
[C6 H 5CO2 H ]
5 ( x )( x )
6.3 x10 
0.020  x
100 x 6.3 x 10-5 = 6.3 x 10-3 6.3 x 10-3 <<< 2.0 x 10-2
100 x K <<< [N2]i
Therefore, the appriximatin methid can be used
5 ( x)( x)
6.3 x10 
0.020
2 5
x 0.020 x6.3x10
6
x  1.2620 x10
= 0.0011
Therefire [H3O+] = 1.1 x 10-3 M
INVOLVES PERFECT SQUARES METHOD
3. The equilibrium constant, Kc = 55.64 for
H2(g) + I2(g) ↔ 2HI(g)
has been determined at 425iC. If 0.130mil each of H2 and I2 is placed in a
25.0L fask at 425iC; what are the concentratons of H2, I2 and HI when
equilibrium has been achieved?
Soluton:
*Calculate the inital concentraton of each reactant.
*Make the change in concentraton to be equal to x on the ICE table.
n
CH 2 
v
0.130 mol

25.0 L
= 5.20x10-3M
n
CI2 
v
0.130mol

25.0 L
= 5.20x10-3M
At equilibrium:
H2(g) + I2(g) ↔ 2HI(g

Inital (M) 5.20x 10-3 5.20x 10-3 0
Change (M) -x -x +2x
Equilibrium (M) 5.20x 10-3-x 5.20x 10-3-x 2x

100 x 55.64 x 100 = 5.564 x 103 >> 5.20x 10-3; K>>[H2]i
and
100 x 55.64 x 100 = 5.564 x 103 >> 5.20x 10-3; K>>[I2]i
Therefore, the appriximatin methid cannit be used
2
[ HI ]
Kc 
[ H 2 ][ I 2 ]
2
(2 x)
55.64  3 3
(5.20 x10  x)(5.20 x10  x)
2
(2 x)
55.64  3 2
(5.20 x10  x)
2
(2 x)
55.64  3 2
(5.20 x10  x)
(2 x)
7.459  3
(5.20 x10  x)
7.459(5.20 x10-3-x) = 2x
0.0388-7.459x = 2x
9.459x = 0.0388
x = 4.10x10-3
[H2] = 5.20x 10-3-x
= 5.20x 10-3-x
= 5.20x 10-3- 4.10x10-3
= 1.1x 10-3M
[I2] = 5.20x 10-3-x
= 5.20x 10-3-x
= 5.20x 10-3- 4.10x10-3
= 1.1x 10-3M
[HI] = 2x = 2(4.10x10-3)
= 8.20 x 10-3M
INVOLVES A QUADRATIC EQUATION
4.Calculate the cincentratin if the priducts and
the reactant when the reacton reach equilibrium
for the decompositon of PCl5 to PCl3 and Cl2 if the
Kc is 1.20 at a given temperature and the inital
concentraton of PCl5 is 0.0920M.
Silutin:
* Set up the ICE table to get
*Use quadratc equatin to get the value of x.
* Use x to get the equilibrium cincentratin of the
product.
At equilibrium:
PCl5(g) ↔ PCl3(g) + Cl2(g)

Inital (M) 0.0920 0 0
Change (M) -x +x +x
Equilibrium (M) 0.0920 -x x x
[ PCl3 ][Cl 2 ]
Kc 
[ PCl5 ]
( x )( x )
1.20 
0.0920  x
1.20(0.0920- x) = x2
x2 + 1.20x - 0.110 = 0
ax2 + bx + c = 0
a = 1 ; b=1.20; c = -0.110
a = 1 ; b=1.20; c = - 0.110
2
 b  b  4ac
x
2a
2
 1.20  (1.20)  4(1)( 0.110)
x
2(1)
x = 0.0859 ir x = -1.29
x = 0.0859 because x = -1.29 is invalid
Therefore from :
PCl5(g) ↔ PCl3(g) + Cl2(g)
[PCl5] = 0.0920 M – 0.0859 M

= 0.0061 M
[PCl3] = 0.0859 M
[Cl2] = 0.0859 M
BALANCED EQUATIONS AND EQUILIBRIUM CONSTANTS
Chemical equatons can be balanced using diferent
sets of stoichiometric coefcients. Examples:
*When the chemical reacton equaton is multplied
by 2, then square the value if K1. That is K2 = K12.
*When the chemical reacton equaton is reversed,

then invert the value if K1. That is K2 = 1/K1..
*When the chemical reacton equatons are added

tigether, then the values if K1 and K2 are multplied.
That is Knet = K1 x K2.
MULTIPLYING THE CHEMICAL REACTION
EQUATION BY A CERTAIN FACTOR
When the chemical reacton equaton is multplied by
2, then square the value of K1. That is K2 = K12.
Example
C(s) + 1/2O2(g) ↔ CO(g) ---K1 = 4.6 x 1023
The equilibrium constant expression for this equaton is
[CO ]
K1  1/ 2
[C ][O2 ]
= 4.6 x 1023 at 25iC

When the above equaton is multplied by

a certain factor (e.g 2), the equilibrium
constant (K1), must also be squared if the
factor is 2 then square that K (e.g. 2) to get
a new equilibrium constant (K2).
MULTIPLYING THE CHEMICAL REACTION EQUATION BY A
CERTAIN FACTOR
Example:
C(s) + 1/2O2(g) ↔ CO(g) ---K1 = 4.6 x 1023----- (1)
When multplying equaton (1) by 2 to get equaton (2),
then square K1.
2(C(s) + 1/2O2(g) ↔ CO(g))---K2 = K12 ---- (2)
2C(s) + O2(g) ↔ 2CO(g)) ----- K2 = (4.6 x 1023 ) 2

= (4.6 x 1023 )2
= 21.16 x 1046
= 2.1 x 1047
The equilibrium constant expression for this equaton
is
2
[CO ]
K2  2
[C ] [O2 ]
= 2.1 x 1047 at 25iC
When the above equaton is multplied by a certain

factor (e.g 2), the equilibrium constant must be
squared.
REVERSING THE CHEMICAL REACTION
When the chemical reacton equaton is reversed,
then invert the value if K1. That is K2 = 1/K1..
Example using Carbinius Acid :
HCO2H(aq) + H2O(l) ↔ HCO2-(aq) + H3O+(l)--- K1=1.8 x 10-4
The equilibrium constant expression for this equaton


is [ HCO2 ][ H 3O ] 
K1 
[ HCO2 H ]
= 1.8 x 10-4 at 25iC

REVERSING THE CHEMICAL REACTION
HCO2H(aq) + H2O(l) ↔ HCO2-(aq) + H3O+(l)--- K1=1.8 x 10-4
When reversing the above reacton, then invert the
value of K1. That is K2 = 1/K1.
HCO2-(aq)+H3O+(l)↔ HCO2H(aq)+H2O(l)--K2 =1/K1
=1/1.8 x 10-4
= 5.6 x 103 at 25iC
The equilibrium constant expression for this equaton is
[ HCO2 H ]
K2  
[ HCO2 ][ H 3O ]

= 5.6 x 103 at 25iC

ADDING TWO CHEMICAL REACTION
EQUATIONS
When the chemical reacton equatins are added
together, then the value of their K’s (e.g. K1 and K2) are
multplied. That is Knet = K1 x K2.
Example:
AgCl(s) ↔ Ag+(aq) + Cl-(aq)--- K1 = [Ag+][Cl-] = 1.8 x 10-10
Ag+(aq) + 2NH3(aq) ↔ Ag(NH3)2]+(aq) --------K2 = 1.1 x 107


[ Ag ( NH 3 ) 2 ]
K2 
[ Ag  ][2 NH 3 ]2
= 1.1 x 107
EQUATIONS
The Knet
AgCl(s) ↔ Ag+(aq) + Cl-(aq)--- K1 =1.8 x 10-10
Ag+(aq) + 2NH3(aq) ↔ Ag(NH3)2+(aq) ---K2 = 1.1 x 107
Net equatin is:

AgCl(s) + 2NH3(aq ↔ Ag(NH3)2+ + Cl-(aq)
Knet = K1 x K2
= 1.8 x 10-10 x 1.1 x 107
= 2.0 x 10-3
+
ADDING TWO CHEMICAL REACTION EQUATIONS
The above can be shown in the following way:
Knet = K1 x K2

[ Ag ][Cl ] [ Ag ( NH 3 ) 2 ][Cl  ]
 
 x 2
1 [ Ag ][ NH 3 ]


[Cl ] [ Ag ( NH 3 ) 2 ][Cl ]
 
 x
1 [ NH 3 ]2
= 1.8 x 10-10 x 1.1 x 107

= 2.0 x 10-3
TEST ON BALANCED EQUATION AND AN
EQUILIBRIUM CONSTANTS
K1 ; K2; K3 ,K4 etc. can be calculated from the same
equatin with diferent numerical ciefcients.
consider the chemical reacton equaton:
N2(g) + 3H2(g) ↔ 2NH3(g) --- K1 = 3.5 x 108 --(1)
Use K1 to calculate (a) K2 and (b) K3 from the following
chemical reacton equatons:
(a)1/2N2(g) + 3/2H2(g) ↔ NH3(g) --- K2 = ? --(2)

(b) NH3(g) ↔ 1/2N2(g) + 3/2 H2(g) ---- K3 = ? --(3)
N2(g) + 3H2(g) ↔ 2NH3(g) --- K1 = 3.5 x 108 --(1)
(a) 1/2N2(g) + 3/2H2(g) ↔ NH3(g) --- K2 = ? --(2)
Equaton (1) is multplied by half in order to get equatin (2).
Therefore: K2 = (K1)1/2
= (3.5 x 108)1/2
8
3.x510x410
 = 1.9
N2(g) + 3H2(g) ↔ 2NH3(g) --- K1 = 3.5 x 108 --(1)
(a) 1/2N2(g) + 3/2H2(g) ↔ NH3(g) --- K2 = 1.9 x 104 --(2)
(b) NH3(g) ↔ 1/2N2(g) + 3/2 H2(g) ---- K3 = ? --(3)
Equaton (2) is reversed in order to get equatin (3).

Therefore: K3 = 1/K2
=1/ (1.9 x 104)
= 5.263157895 x 10-5
= 5.3 x 10-5
Calculate Kc for equilibrium constant 3,
given equilibrium constant 1 and 2:
SnO2(s) + 2H2 ↔ Sn(s) + 2H2O(g) -----K1 = 7.45---(1)

H2(s) + CO2 ↔ H2O(g) + CO(g)----------K2 = 0.88---(2)
SnO2(s) + 2CO(g) ↔ Sn(s) + 2CO2(g) ----K3 = ?? ---(3)
TEST ON BALANCED EQUATION AND AN EQUILIBRIUM CONSTANTS
Reverse 2 and take the reciprical if the square of its K and

add it ti equatin 1.
1.SnO2(s) + 2H2(g ↔ Sn(s) + 2H2O(g) -------K1 = 7.45
2.2H2O(g) + 2CO(g) ↔ 2H2(g) + 2CO2(g)-----K2 = (1/Kc)2
= (1/0.88)2
= 1/0.7744
=1.291322314
3. SnO2(s) + 2CO(g) ↔ Sn(s) + 2CO2(g) -----K3 = K1 x K2
= 7.45 x 1.291322314
= 9.62
DISTURBING A CHEMICAL EQUIBRIUM
There are many ways of disturbing chemical
equilibrium, but only three of them will be studied in
this secton:
* Additin ir remival if a reactant ir a priduct.
(Cincentratin change).
* Temperature change
* Changing the vilumes (in the case if gases).
The change in any if the factirs that determine the
equilibrium cinditins if a system will cause the
system ti change in such a manner as ti reduce ir
ciunteract the efect if the change.
EFFECT OF THE ADDITION OR REMOVAL OF A
REACTANT OR PRODUCT
When adding or remiving some priducts or
reactants from the system that is at equilibrium, the
system will ni linger be at equilibrium.
When the system returns ti a new equilibrium, the
cincentratins of the reactants and the priducts will
be diferent, but the value if K will remain cinstant.
That is, the value of K fir the ild and the new
equilibriums will be the same.
REACTANT OR PRODUCT
Consider the isomerizaton of nirmal butane to
isibutane (Kc = 2.5).
Assume the equilibrium has been established in a 1.00L
fask with [butane] = 0.00500mil/L and [isibutane] =
0.0125 mil/L.
Butane ↔ Isibutene --- Kc = 2.50
Then 0.0150mil of butane is added to the fask.
What are the cincentratins of butane and isibutane
when equilibrium is re-established.
Soluton
* Set up the ICE table and solve for x.
CALCULATIONS WHERE THE SOLUTION
INVOLVES A QUADRATIC EXPRESSION
At equilibrium:
Butane ↔ Isibutane
Inital (M) 0.00500 0.0125
C.I. A.B. (M) (0.00500 + 0.0150)/1L 0.0125
C.C .R. E. (M) -x +x
Equilibrium (M) 0.0200 -x 0.0125 + x
C.I. A.B. = Cincentratin immediately in adding butane

C.C.R.E. = Change in cincentratin ti re-establish equilibrium.
EFFECT OF THE ADDITION OR REMOVAL OF A REACTANT OR PRODUCT
[ Isobu tan e]
Kc 
[ Bu tan e]
0.0125  x
2.5 
0.0200  x
2.5(0.02 -x ) = 0.0125 + x
0.05 - 2.5x = 0.0125 + x
0.05 - 0.0125 = x + 2.5x
3.5x = 0.0375
x = 0.0107M
REACTANT OR PRODUCT
[butane] = 0.0200 -x
= 0.0200 -0.0107
= 0.093 M
[Isibutane] = 0.0125 + x
= 0.0125 + 0.0107
= 0.0232 M
Therefire when the cincentratin/s if the reactant/s
is/are increased, then the cincentratin/s if the
priduct/s will alsi increase; but the value if K stays
cinstant.
EFFECT OF VOLUME CHANGE ON GAS-PHASE EQUILIBRIA
When the vilume of a gas is degreased, the pressure

of that gas increases and the cincentratin increases
When the vilume of a gas is increased, the pressure
of that gas decreases and the cincentratin
decreases.
TEST ON THE EFFECT OF VOLUME CHANGE ON GAS-PHASE
EQUILIBRIA
Consider the reacton:
2NO2(g) ↔ N2O4(g)
If [N2O4] = 0.0280M and [NO2] = 0.0128M. When the
volume is halved, then the concentratons are doubled
[N2O4] = 0.0560M and [N2O] = 0.0256M
Is this reacton reactant ir priduct faviured?

TEST ON EFFECT OF VOLUME CHANGE ON GAS-
PHASE EQUILIBRIA
Before the vilume is halved, the value of K was:
[ N 2O4 ]
Kc  2
[ N 2O ]
0.028

= 170(0.0128) 2
Q = Kc Because the reactin is at
equilibrium = 170
TEST ON EFFECT OF VOLUME CHANGE ON GAS-PHASE
EQUILIBRIA
Afer the vilume is halved, (the equilibrium is disturbed), the
cincentratins are increased and the new value if Q will be:
[ N 2O4 ]
Q 2
[ N 2O ]
= 85.4 0 .0560
 2
(0.0256
Kc > Q ir Q < Kc That) is 170 > 85.4 ir
85.4 < 170 . The reacton is priduct faviured.
EFFECT OF VOLUME CHANGE ON GAS-PHASE
EQUILIBRIA
According to Le Chatedlier‘s principle, the system
have to ciunteract the “stress” in order to atain the
new equilibrium mixture where Q = Kc again.
The lesser the vilume, the faster the cillisiin and
the faster the reactin if the reactants,
the mire the priduct is priduced than the reactant.
The system is therefore priduct faviured.
When the deniminatir decreases twice while the
numeratir decreases ines, then the quitent will
increase because the [NO2] increased twice as much
as [N2O4].
Therefore Q will increased untl Q = Kc.
2NO2(g) ↔ N2O4(g)
Decrease vilume if the cintainer, NO2 is cinverted
ti N2O4 untl equilibrium is atained.
EQUILIBRIA
2NO2(g) ↔ N2O4(g)
For this equaton, if the concentratons are given in
partal pressures, then:
PN 2O4
Q 2
K p 170
( PNO2 )
In summary for gases:
Reactin Cause if Disruptin Ti Ciunteract Change Directin if Shif
Mire miles if
Decrease volume (and
gaseius priducts than Decrease pressure To reactants
increase pressure)
reactants
Mire miles if
Increase volume (and
gaseius priducts than Increase pressure To products
decrease pressure)
reactants
Mire miles if
gaseius reactants Decrease pressure To products
increase pressure)
than priducts
Mire miles if
gaseius reactants Increase pressure To reactants
decrease pressure)
than priducts
Equal miles if
gaseius reactants and No efect No Shif
increase pressure)
priducts
Equal miles if
gaseius reactants and No efect No Shif
increase pressure)
priducts
EQUILIBRIA
To summarize the above:
* When decreasing the vilume of the cintainer
(increasing the pressure), the equilibrium will shif
toward the side that has less number if miles if the
gas.
*When increasing the vilume of the cintainer

(decreasing the pressure), the equilibrium will shif
toward the side that has mire number if miles if
the gas.
EQUILIBRIA
•When decreasing ir increasing the vilume of the
cintainer (increasing ir decreasing the pressure)
that has the same number if miles if gas, the
equilibrium will NOT shif tiward any if the side.
EFFECT OF TEMPERATURE ON THE
EQUILIBRIUM COMPOSITI0NS
The change in temperature if system, changes the
value if K.
This will therefore not be studied in detail in this
secton.
Only the efect of the endithermicity and the
exithermicity of the system on the value of K will be
studied.
EFFECT OF TEMPERATURE ON THE EQUILIBRIUM COMPOSITI0NS
If the reacton is endithermic, the heat added is

taken as the reactant.
This will be alleviated by producing more priducts.
Example:
N2(g) + O2(g) ↔ 2NO(g) -- ∆rHi = +189.6kJ/mil
Adding energy to this system will speed up the
reacton, use up N2 and O2, decrease [N2] and [O2]
and increase [NO],.
N2(g) + O2(g) ↔ 2NO(g) -- ∆rHi = +189.6kJ/mil

The value if K will therefire increase.
Therefore for endithermic reactin, the equilibrium
will shif tiward the right and the reactin will be
priduct faviured.
2
[ NO ]
Kc 
[ N 2 ][O2 ]
Fir endithermic reactin, the higher the
temperature, the higher the value if K.
Equilibrium cinstant, Kc Temperature, K
4.5 x 10-31 298

6.7 x 10-10 900
1.7 x 10-3 2300

If the reacton is exithermic, the heat priduced is
taken as the priduct.
This will be alleviated by producing mire reactant.
The system will be reactant faviured.
Example:
2NO2(g) ↔ N2O4(g) --∆rH = -57.1kJ/mil
Producing energy from this system will decrease
[N2O4] and increase the firmatin NO2.
The value if K will therefire decreases.
[ N 2O4 ]
Kc  2
[ NO2 ]
Fir exithermic reactin. the higher the
temperature, the liwer the value if K.
Equilibrium cinstant, Kc Temperature, K
1300 273
170 298
THE RELATIOSHIP BETWEEN KC AND KP
The relatonship between Kc and Kp:
CaCO3(s) ↔ CaO(s) + CO2(g)
Kc = [CO2].
KP = PCO2
PV = nRT
PCO2V= nCO2RT
nCO2
PCO2  RT
v
PCO2= [CO2]RT
KP = KcRT
Consider the reacton:
N2(g) + 3H2(g) ↔ 2NH3(g)
( PNH 3 ) 2
Kp  1 3
( PN 2 ) ( PH 2 )
2
([ NH 3 ]RT )
Kp  1 3
([ N 2 ]RT ) ([ H 2 ]RT )
2
[ NH 3 ] 1
Kp  1 3
( 2
)
[ N 2 ] [ H 2 ] ( RT )
2
[ NH 3 ] 1
Kp  1 3
( 2
)
[ N 2 ] [ H 2 ] ( RT )
1
Kp K c ( 2
)
( RT )
Kp = Kc(RT)-2
Kc = Kp(RT)2
N2(g) + 3H2(g) ↔ 2NH3(g)

In general
Kp = Kc(RT)∆n
Where ∆n is the diference between the number of

moles of the product subtract the number of moles
of the reactants.
If ∆n is negatve, then the above equaton becomes:

Kc = Kp(RT)∆n
TEST ON CALCULATING EQUILIBRIUM CONCENTRATIONS USING AN EQUILIBRIUM CONSTANT
Correct3. Consider the following reacton at 600iC.

2NH3(g) ↔ N2(g) + 3H2(g) -- Kp = 6.9 x 104
When the reactin reaches equilibrium at 600, the
reacton vessel contains 26.5 kPa of N2 and 49.2kPa
if H2. The pressure of NH3 was nit measured.
The vessel is then ciiled to 400iC and the
equilibrium is re-established. The pressure if
hydrigen is now 30.6kPa.
(a) Calculate the equilibrium constant, Kp for this
reacton at 400iC.
(b)Is the forward reacton exithermic or endithermic? Why?
(c) Calculate the value if Kc at 400iC.
USING AN EQUILIBRIUM CONSTANT
2NH3(g) ↔ N2(g) + 3H2(g)
Inital (P) ?? 26.5 49.20 --T=69000iC
Change (P) +?? -?? -x
Equilibrium (P) ?? ?? 30.6 --T= 400iC
Soluton: Calculate the inital and the equilibrium PNH3 :
2NH3(g) ↔ N2(g) + 3H2(g) -- Kc = 6.9 x 104
3
( PN 2 )( PH 2 )
Kp  2
( PNH 3 )
3
2
( PN 2 )( PH 2 )
( PNH 3 ) 
Kp
3
2 ( 26.5)( 49.2)
( PNH 3 )  4
6.9 x10
2
( PNH 3 ) 45.74
2
( PNH 3 )  45.74
PNH 3 6.76kPa
PNH 3 6.8kPa
The pressure if H2 drips when the vessel is ciiled ti
400iC. This means that the reactin shifed ti the lef. It
is reactant favir.
PH2 = 49.2 + x = 30.6 therefire; x = - 18.6
PN2 = -18.2/3 = - 6.2
PNH3 = 18.2 x 2/3 = 12.4
2NH3(g) ↔ N2(g) + 3H2(g)
Inital (P) 6.76 26.5 49.20
Change (P) +12.4 -6.2 -18.6
Equilibrium (P) 19.2 20.3 30.6

3
( PN 2 )( PH 2 )
Kp  2
( PNH 3 )
3
( 20.3)(30.6)
Kp  2
(19.2)
3
K p 1.58 x10
Therefore, at 400K the value of K will be Kp= 1.58 x 103 .

The forward reacton was endithermic because the
liwer the temperature the liwer the value if K and
the reacton shifed ti the lef when ciiled.
??That is it shifed to the exithermic in order to

counter act the change.
The reacton is therefore reactant faviured.
The concentraton of H2 decreased.
n
K p K c ( RT )
2
K p K c ( RT )
Kc
Kp   2
( RT )
2
K c K p ( RT )
2
K c K p ( RT )
If R =8.315 Pam3/K mil
3 2
then K 1.58 x10 {(8.315(673.15)}
c
1.58 x103
Kc 
{(8.315(673.15)}2
= 5.04 x 10-5
Consider the following equilibrium:

2NO(g) ↔ N2(g) + O2 (g) -------Kc = 0.490 at 500.K
(a)At a certain stage the concentratons are as
follows:
[NO(g)] = 0.300M; [N2(g)] = 0.300M; [O2(g)] = 0.300M
(a) Calculate the cincentratin if NO at equilibrium
at 500.K .
(b) Is this reactin priduct ir reactant faviured?

(c) Calculate the value if Kp at 500K.

2NO(g) ↔ N2(g) + O2 (g) -------Kc = 0.490 at 500.K
(a)At a certain stage the concentratons are as follows:
[NO(g)] = 0.300M; [N2(g)] = 0.300M; [O2(g)] = 0.300M
Calculate the cincentratin if NO at equilibrium at
500.K .
Nite: x is nit negligibly small
Hind : Liik iut fir simplifcatin if the algebra.
At equilibrium:
2NO(g) ↔ N2(g) + O2(g

Inital (M) 0.300 0.300 0.300
Change (M) -2x +x +x
Equilibrium (M) 0.300 - 2x 0.300+x 0.300+x

2
(0.300  x)
0.490  2
(0.300  2 x)
(0.300  x)
0.7 
(0.300  2 x)
0.7(0.300 - 2x) = 0.300 + x
0.21 - 1.4x = 0.300 + x
1.4x+ x = 0.21 - 0.300
2.4x = - 0.09
x = -0.0375
[NO] = 0.300 - 2(-0.0375)

= 0.375M
(b) Neither priduct nir reactant faviured because

the number if miles are the same on both sides of
the yield sign,
(c)
n
K p K c ( RT )
= 0.490 (RT)0
= 0.490 x 1
= 0.490
StipTEST ON CALCULATING EQUILIBRIUM CONCENTRATIONS USING AN EQUILIBRIUM
CONSTANT
3. Consider the following reacton at 600iC.
2NH3(g) ↔ N2(g) + 3H2(g) -- Kp = 6.9 x 104
When the reactin reaches equilibrium at 600, the
reacton vessel contains 26.5 kPa of N2 and 49.2kPa if
H2. The pressure of NH3 was nit measured.
The vessel is then ciiled to 400iC and the equilibrium
is re-established. The pressure if hydrigen is now
30.6kPa.
(a) Calculate the equilibrium constant, Kp for this
reacton at 400iC.
(b)Is the forward reacton exithermic or endithermic? Why?
2NH3(g) ↔ N2(g) + 3H2(g)
Inital (P) ??? 26.5 49.20
Change (P) ??? ?? ??
Equilibrium (P) ?? ?? 30.6

Soluton: Calculate the inital and the equilibrium PNH3 :
2NH3(g) ↔ N2(g) + 3H2(g) -- Kc = 6.9 x 104
3
( PN 2 )( PH 2 )
Kp  2
( PNH 3 )
3
2
( PN 2 )( PH 2 )
( PNH 3 ) 
Kp
3
2 ( 26.5)( 49.2)
( PNH 3 )  4
6.9 x10
2
( PNH 3 ) 45.74
2
( PNH 3 )  45.74
PNH 3 6.76kPa
PNH 3 6.8kPa
is reactant favir.
PH2 = 49.2 + x = 30.6 therefire; x = - 18.6
PN2 = -18.2/3 = - 6.2
PNH3 = 18.2 x 2/3 = 12.4
2NH3(g) ↔ N2(g) + 3H2(g)
Inital (P) 6.76 26.5 49.20
Change (P) +12.4 -6.2 -18.6
3
( PN 2 )( PH 2 )
Kp  2
( PNH 3 )
3
( 20.3)(30.6)
Kp  2
(19.2)
3
K p 1.58 x10
Therefore, at 400K the value of K will be Kp= 1.58 x 103 .

??That is it shifed to the exithermic in order to
counter act the change.
n
K p K c ( RT )
2
K p K c ( RT )
Kc
Kp   2
( RT )
2
K c K p ( RT )
2
K c K p ( RT )
3 2
then K 1.58 x10 {(8.315(673.15)}
c
1.58 x103
Kc 
{(8.315(673.15)}2
= 5.04 x 10-5
n
K p K c ( RT )
2
K p K c ( RT )
Kc
Kp  2
(RT )
2
K c K p (RT )
2
K c K p (RT )
then
3 2
K c 1.58 x10 {(8.315(673.15)}
= 1.58x 103(31329120.81)
= 4.95 x 1010

2NO(g) ↔ N2(g) + O2 (g) -------Kc = 0.490 at 500.K
(a)At a certain stage the concentratons are as
follows:
[NO(g)] = 0.300M; [N2(g)] = 0.300M; [O2(g)] = 0.300M
(a) Calculate the cincentratin if NO at equilibrium
at 500.K .


2NO(g) ↔ N2(g) + O2 (g) -------Kc = 0.490 at 500.K
(a)At a certain stage the concentratons are as follows:
[NO(g)] = 0.300M; [N2(g)] = 0.300M; [O2(g)] = 0.300M
Calculate the cincentratin if NO at equilibrium at
500.K .
Nite: x is nit negligibly small
At equilibrium:
2NO(g) ↔ N2(g) + O2(g

Inital (M) 0.300 0.300 0.300
Change (M) -2x +x +x
Equilibrium (M) 0.300 - 2x 0.300+x 0.300+x

2
(0.300  x)
0.490  2
(0.300  2 x)
(0.300  x)
0.7 
(0.300  2 x)
0.7(0.300 - 2x) = 0.300 + x
0.21 - 1.4x = 0.300 + x
1.4x+ x = 0.21 - 0.300
2.4x = - 0.09
x = -0.0375
[NO] = 0.300 - 2(-0.0375)

= 0.375M
(b) Neither priduct nir reactant faviured because

the number if miles are the same in bith side
(c)
n
K p K c ( RT )
STOP TEST ON CALCULATING EQUILIBRIUM
CONCENTRATIONS USING AN EQUILIBRIUM CONSTANT
At equilibrium:
2NO(g) ↔ N2(g) + O2(g

Inital (M) 0.300 0.300 0.300
Change (M) +2x -x -x
Equilibrium (M) 0.300 + 2x 0.300-x 0.300-x

A the end yiu will get:
Hind x = -0.0375
[NO] = 0.300 - 2(-0.0375)
= 0.375M
??TEST ON CALCULATING EQUILIBRIUM CONCENTRATIONS
N2(g) + O2(g) ↔ 2 NO(g)
[ N 2 ][O2 ]
Kc 
[ 2 NO ]2
(0.300  x)(0.300  x)
0.490  2
(0.300  2 x)
2
(0.300  x)
0.490  2
(0.300  2 x)
N2(g) + O2(g) ↔ 2 NO(g)
[ N 2 ][O2 ]
Kc 
[ 2 NO ]2
(0.300  x)(0.300  x)
0.490  2
(0.300  2 x)
2
(0.300  x)
0.490  2
(0.300  2 x)
2
(0.300  x)
0.490  2
(0.300  2 x)
(0.300  x)
0.7 
(0.300  2 x)
0.7(0.300 - 2x) = 0.300 + x
0.21 - 1.4x = 0.300 + x
1.4x+ x = 0.21 - 0.300
2.4x = - 0.09
x = -0.0375
[NO] = 0.300+ 2(0.0375)

= 0.375M
Stip TEST ON BALANCED EQUATION AND AN EQUILIBRIUM
CONSTANTS
At a certain stage the concentratons are as follows:
[NO(g)] = 0.300M
[N2(g)] = 0.300M
[O2(g)] = 0.300M
The cincentratin if NO(g) at equilibrium at 500.K
will be :
Nite x is nit negligibly small
A 0.0375M B 0.375M E 0.225M
C 0.300M D 0.107M F Nine if the abive
[NO(g)] = 0.300M
[N2(g)] = 0.300M
[O2(g)] = 0.300M
will be :
A 0.0375M B 0.375M E 0.225M
Stip TEST ON CALCULATING EQUILIBRIUM
CONCENTRATIONS USING AN EQUILIBRIUM CONSTANT
n
K p K c ( RT )
Kp
Kc  n
( RT )
3
1.58 x10
Kc  2
{(0.0821)(673.15)}
= 0.5173054722
= 0.517
STOP TEST ON THE CALCULATIONS WHERE THE SOLUTION
INVOLVES PERFECT SQUARES EXPRESSION
The equilibrium constant Kc (= 55.64) for
H2(g) + I2(g) ↔ 2HI(g)
Has been determined at 425iC. If 0.130mil each of H2 and I2 is placed in a
Soluton:
*Make the change in concentraton to be equal to x and ICE table.
D n
CH 2 
v
0.130 mol

25.0 L
= 5.20x10-3M
n
CI2 
v
0.130mol

25.0 L
= 5.20x10-3M
At equilibrium:
H2(g) + I2(g) ↔ 2HI(g

Inital (M) 5.20x 10-3 5.20x 10-3 0
Change (M) 5.20x 10-3-x 5.20x 10-3-x +2x
Equilibrium (M 5.20x 10-3-x 5.20x 10-3-x 2x

2
[ HI ]
Kc 
[ H 2 ][ I 2 ]
2
(2 x)
55.64  3 3
(5.20 x10  x)(5.20 x10  x)
2
(2 x)
55.64  3 2
(5.20 x10  x)
2
(2 x)
55.64  3 2
(5.20 x10  x)
(2 x)
7.459  3
(5.20 x10  x)
7.459(5.20 x10-3) = 2x
0.0388-7.459x = 2x
9.459x = 0.0388
x = 4.10x10-3
[H2] = 5.20x 10-3-x
= 5.20x 10-3-x
= 5.20x 10-3- 4.10x10-3
= 1.1x 10-3M
[I2] = 5.20x 10-3-x
= 5.20x 10-3-x
= 5.20x 10-3- 4.10x10-3
= 1.1x 10-3M
[H2] = 2x = 2(4.10x10-3)
= 8.20 x 10-3
STOPDETERMINIG AN EQUILIBRIUM
CONSTANT
If the inital cincentratins of the reactants and the
equilibrium cincentratin of the priduct are known,
then the value of K can be determined.
Example:
Calculate the value of K for the following chemical
reacton.
2SO2(g) + O2(g) 2SO3(g)
If the equilibrium cincentratin of the reactants and
the priducts are as follows [SO2] = 3.61 x 10-3M
[ O2 ] = 6.11 x 10-4M
[SO3] = 1.01 x 10-2M
DETERMINIG AN EQUILIBRIUM
CONSTANT
If the equilibrium cincentratins of the reactants and
the priduct are known, then the value of K can be
determined.
Example:
Calculate the value of K for the following the following
chemical reacton.
2SO2(g) + O2(g) 2SO3(g)
If the [SO2] = 3.61 x 10-3M
[ O2 ] = 6.11 x 10-4M
[SO3] = 1.01 x 10-2M
INVOLVES AN APPROXIMATE2
EXPRESSION
 12 4x
5.6 x10 
0.45
2
 b  b  4ac
x
2a
 12
5.6 x10 x 0.45
x
4
= 7.9 x 10-7
[I] = 2x
= 2 (7.9 x 10-7)
= 15.8 x 10-7
= 1.6 x 10-7
EQUATIONS
When the chemical reacton equaton are added
together, then the value of K1 and K2 are multplied.
That is Knet = K1 x K2.
For an example:
HCO2H(aq) + H2O(l) ↔ HCO2-(aq) + H3O+(l)--- K=1.8 x 10-4

CALCULATIONS INVOLVING EQUILIBRIUM
CONSTANT
2
[ SO3 ]
Kc  2
[ SO2 ] [O2 ]
2
(1.010]
Kc  3 2
(3.61x10 ) (6.11x10  4)
4
K c 1.28 x10
CALCULATIONS WITH EQUILIBRIUM
CONSTANT TEST 2
Calculate the cincentratin H3O+ in the 0.020 M
soluton of C6H5CO2H that is dissolved in water to
give C6H5CO2- + and H3O+, given that KC
= 6.3 x 10-5 M a for the C6H5CO2H.
Soluton:
Write down a stiichiimetric equatin.
Use an ICE table to calculate the [H3O+].
Apply the formula to calculate the value pH.
CONSTANT TEST 2
C6H5CO2 H(aq)+H2O(ℓ)↔C6H5CO2-(aq) + H3O+
Inital (M) 0.020 0 0
Change (M) -x +x +x
Equilibrium (M) 0.020-x x x
CONSTANT TEST 2

[ H 3O ][C6 H 5CO2 ]

Kc 
[C6 H 5CO2 H ]
( x)( x)
5
6.3 x10 
0.020
0.020-x ̴ 0.020 because x is very small compared to
0.020.
CONSTANT TEST 2
5 ( x)( x)
6.3 x10 
0.020
2 5
x 0.020 x6.3x10
6
x  1.2620 x10
= 0.0011
Therefire[H3O+] = 1.1 x 10-3 M
CONSTANT
pH = -log [H3O+]
= -log 1.10 x 10-3
= 2.96
3. Consider the following reacton at 983oC.
H2(g) + CO2(g) ↔ H2O(g) + CO(g)-- Kc = 1.6
Suppose 0.050 mol each of H2 and CO2 are paced in a 2.0
dm3 container. What would the concentraton of CO(2)
and H2O be when equilibrium is achieved is achieved at
986oC.
Soluton:
Calculate the concentraton of each of H2 and CO2.
Let the change for H2 be x
n
cH 2 
v
0.050mol
cH 2  3
2.0dm
=0.25mol/dm 3
= 0.25M
[CO2]0 = [H2]0 = 0.25M
At equilibrium:
H2(g) + CO2(g) ↔ H2O(g) + CO2(g

Inital (M) 0.250 0.250 0 0
Change (M) -x -x 0 +x
Equilibrium (M) 0.250-x 0.250-x x x

( x )( x )
1.6 
(0.025  x )(0.025  x )
x2
1.6 
(0.025  x ) 2
1.2649(0.025-x) = x
-2.2649x=-0.03164
x = 0.01396
≈0.014
Example of the basic silutin is:
NaOH(aq) Na+(aq) + OH-(aq) -----Kb =?
[ Na ][OH ]
 
Kb 
[ NaOH ]
LE CHATELIER’S PRINCIPLE
Gi in
Questin 3 [3]
Calculate Kc fir equilibrium 3, given equilibria 1 and 2:
1.SnO2(s) + 2H2(g) ⇋ Sn(s) + 2H2O(g) Kc = 7.45
2.H2(g) + CO2(g) ⇋ H2O(g) + CO(g) Kc = 0.881
3.SnO2(s) + 2CO(g) ⇋ Sn(s) + 2CO2(g) Kc = ?
A 8.46
B 6.57
C 6.56
D 5.69
E 9.60
F Nine if the abive.
[NO(g)] = 0.300 M
[N2(g)] = 0.300 M
[O2(g)] = 0.300 M
The concentraton of NO(g) at equilibrium at 500.K will be:
Nite: x is not negligibly small.
Hint: Look out for simplifcaton of the algebra.
A 0.0375 M B 0.375 M
C 0.300 M D0.100 M
E 0.225 M
F None of the above.
The equilibrium constant Kc (= 55.64) for
H2(g) + I2(g) ↔ 2HI(g)
has been determined at 425iC. If 0.130mil each of H2 and I2 is placed in a
Soluton:
*Make the change in concentraton to be equal to x and draw the ICE table.
+
n
CH 2 
v
0.130mol

25.0 L
[H2]0 = 5.20x10-3M
n
CI 2 
v
0.130mol

25.0 L
[H2]0 = 5.20x10-3M
At equilibrium:
H2(g) + I2(g) ↔ 2HI(g

Inital (M) 5.20x 10-3 5.20x 10-3 0
Change (M) 5.20x 10-3-x 5.20x 10-3-x +2x
Equilibrium (M 5.20x 10-3-x 5.20x 10-3-x 2x

2
[ HI ]
Kc 
[ H 2 ][ I 2 ]
2
(2 x)
55.64  3 3
(5.20 x10  x)(5.20 x10  x)
2
(2 x)
55.64  3 2
(5.20 x10  x)
2
(2 x)
55.64  3 2
(5.20 x10  x)
(2 x)
7.459  3
(5.20 x10  x)
7.459(5.20 x10-3-x) = 2x
0.0388 - 7.459x = 2x
9.459x = 0.0388
x = 4.10x10-3
[H2] = 5.20x 10-3-x
= 5.20x 10-3-x
= 5.20x 10-3- 4.10x10-3
= 1.1x 10-3M
[I2] = 5.20x 10-3-x
= 5.20x 10-3-x
= 5.20x 10-3- 4.10x10-3
= 1.1x 10-3M
[HI] = 2x = 2(4.10x10-3)
= 8.20 x 10-3
The forward reacton is endithermic because the
reacton shifed ti the lef when ciiled.
That is it shifed to the exithermic in order to
produce more energy.
3 2
K c 1.58 x10 {(0.0821)(673.15)}
= 1.580(3054288201)
= 4825775.358
= 4.83 x 106
2 NO(g) ↔ N2(g) + O2(g)
[ N 2 ][O2 ]
Kc 
[ 2 NO ]2
2
(0.300  2 x)
0.490 
(0.300  x)(0.300  x)
2
(0.300  2 x)
0.490  2
(0.300  x)
2
(0.300  2 x)
0.490  2
(0.300  x)
0.300  2 x
0 .7 
(0.300  x)
0.7(0.300-x) = 0.300 + 2x
0.21 - 0.7x = 0.300 + 2x
-2x-0.7x = 0.300-0.21
-2.7x = 0.09
CALCULATIONS WHERE THE SOLUTION INVOLVES A
QUADRATIC EXPRESSION
N2(g) + O2(g) ↔ 2NO(g)
[N2] = 0.300 - 0.132M
= 0.177M
[O2] = 0.300 - 0.132M
= 0.177M
[NO2] = 2( 0.132M)
= 0.246M
??TEST ON CALCULATING EQUILIBRIUM CONCENTRATIONS
2
(0.300  x)
0.490  2
(0.300  2 x)
(0.300  x)
0.7 
(0.300  2 x )
0.7(0.300 + 2x) = 0.300 - x
0.21 +1.4x = 0.300 - x
2x+ x = 0.300 - 0.21
3x = 0.09
X = 0.03
N2(g) + O2(g) ↔ 2 NO(g)
Niiii!!!
[ 2 NO ]2
Kc 
[ N 2 ][O2 ]
2
(0.300)

(0.300)(0.300)
Kc = 1.00
Since K nit <<< [N2] and K nit << [O2]
In general
Kc = Kp(RT)∆n
Where ∆n is the diference between the number of

moles of the product subtract by the number of
moles of the reactants.
1.Calculate the equilibrium cincentratin of I2 and the
concentraton of I if I2 molecules dissociates into I atoms
for which the inital concentraton of I2 is 0.45M and the
value of K is 5.6 x 10-12 at 500iC.
2.Consider the reacton:

N2(g) + O2(g) ↔ 2 NO(g)
Calculate the equilibrium cincentratin of each reagent
if the inital concentratons of N2 and O2 are 0.080M and
0.020M respectvely and the value of Kc is 1.0 x 10-5 at
1500K.
Calculate the equilibrium cincentratin of I2 and the
concentraton of I if I2 molecules dissociates into I
atoms for which the inital concentraton of I2 is
0.45M and the value of K is 5.6 x 10-12 at 500iC.
3
( P )( P )
N2 H2
K  p 2
(P )
NH 3
3
(20.3)(30.6)
Kp  2
(19.2)
3 2
K p 1.58 x10 kPa
= 1.58x103kPa2
If R =8.315 x10 3 kPacm3/K mil

then
3 2 3 3 1 1 2
K c 1.58 x10 kPa {(8.315x10 kPacm K mol )(673.15K )}
= 1.58 x 106(31329120.81x103) kPa4m6/mil

= 49500010.57 x 103kPa4m6/mil
= 4.95 x 1016kPa4m6/mil
then
6 2 3 1 1 2
K c 1.58 x10 Pa {(8.315Pam K mol )(673.15K )}
= 1.58x 106(31329120.81) p4m6/mil

= 49500010.57p4m6/mil
= 4.95 x 1013p4m6/mil
18.6kPaH 2 1kPaN 2
? kPaN 2  x
1 3kPaH 2
= 6.2kPaN2
18.6kPaH 2 2kPaNH 3
? kPaNH 3  x
1 3kPaH 2
= 12.4kPaNH3
is reactant favir.
PCH2 = 30.6 - 49.2 = - 18.6
CN2 = -18.2/3 = - 6.2
CNH3 = 18.2x2/3 = 12.4
2NH3(g) ↔ N2(g) + 3H2(g)
Inital (P) 6.76 26.5 49.20
Change (P) +12.4 -6.2 -18.6
3
( P )( P )
N2 H2
K  p 2
(P )
NH 3
3
(20.3)(30.6)
Kp  2
(19.2)
3
K p 1.58 x10
= 1.58x106
That is it shifed to the exithermic in order to
produce more energy.
Calculate Kc for equilibrium 3, given equilibrium 1 and 2:
1.SnO2(s) + 2H2 ↔ Sn(s) + 2H2O(g) ---------Kc = 7.45
2.H2(s) + CO2 ↔ H2O(g) + CO(g)---------------Kc = 0.88
3.SnO2(s) + CO(g) ↔ Sn(s) + 2CO2(g) ---------Kc = ??
A.8.46
B.6.57
C. 6.56
D.5.69
E.9.62
F.Nine if the abive
Calculate Kc for equilibrium 3, given equilibrium 1 and 2:
1.SnO2(s) + 2H2 ↔ Sn(s) + 2H2O(g) ---------Kc = 7.45
2.H2(s) + CO2 ↔ H2O(g) + CO(g)---------------Kc = 0.88
3.SnO2(s) + CO(g) ↔ Sn(s) + 2CO2(g) ---------Kc = ??
A.8.46
B.6.57
C. 6.56
D.5.69
E.9.62
F.Nine if the abive
[NO(g)] = 0.300M
[N2(g)] = 0.300M
[O2(g)] = 0.300M
will be :
A 0.0375M B 0.375M E 0.225M
[NO(g)] = 0.300M
[N2(g)] = 0.300M
[O2(g)] = 0.300M
will be :
A 0.0375M B 0.375M E 0.225M
For the dissilutin if a precipitate that is formed
during precipitatin reactin, K is writen as Ksp.
Ksp is called the silubility equilibrium cinstant.
For the reacton:
AxBy(s) xAy(aq) + yBx(aq)---Ksp = ?
Then Ksp becimes:
Ksp = [Ay]x[Bx]y
Example of the above reacton is the dissoluton of

AgBr:
• AgBr(s) Ag+(aq, 7.35 x 10-7M) + Br-(aq, 7.35 x 10-7M)
• When AgBr has dissolved and equilibrium is
atained, the soluton is said to be saturated.
• The solubility equilibrium constant Ksp:
• ksp = [Ag+][Br-]
• =(7.35 x 10-7) (7.35 x 10-7)
• =5.4 x 10-13
• If the inital cincentratins of the reactants
and the equilibrium cincentratin of the
priduct are known, then the value of K can be
determined.

Chemical Equilibria: This Is The Reactin in Which The If The Firward and The Backward Reactins Are The

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CHEMICAL EQUILIBRIA

This is the reactin in which the rate if the firward

N2(g) + 3H2(g) ↔ 2NH3(g)

This is called dynamic equilibrium: See below

The equilibrium cinstant is the quitent obtained

The formaton of amminia from nitrigen gas and

For any reacton in aqueius form and if the

aA(aq) + bB(aq) cC(aq) + dD(aq) -----Kc = ?

[Cu(NH3)4]2+(aq) Cu2+(aq) + 4 NH3(aq) --- Kc =?

Example of the acidic silutin is:

HCl(aq) + H2O(ℓ) H3O+(aq)+ Cl-(aq)-Ka =?

B + H2O (l) BH+ + OH- -----Kb =?

NH3(aq) + H2O(l) NH4+(aq) + OH-(aq) --- Kb =?

H2O(l) + H2O(l) H3O+(aq) + OH-(aq) --- Kw =?

•Kw is called auti-iinizatin cinstant ir iin-priduct

Then Ksp becimes:

The Reactin quitent (Q) is the quitent obtained

For any reacton that is at equilibrium then:

aA(aq) + bB(aq) cC(aq) + dD(aq) -----Kc = ?

For any reacton that is NOT necessarily at

aA(aq) + bB(aq) cC(aq) + dD(aq) -----Q = ?

The value of K can tell if the reacton is reactant

*If the value of K is equal ti 1 (K = 1), then the

[ NO2 ][O2 ]--Kc = 6.34 x 1034 at 25iC

2. Is this reacton, priduct or reactant faviured?

The relatonship between K and Q can also tell if the

*If the inital cincentratins of the reactants and the

*If the number if miles and the vilume of the

Calculate the value of K for the following chemical

Change (M) -x +2x

N2(g) + O2(g) ↔ 2NO(g)

Equilibrium (M) 0.080-x 0.020-x 2x

Since 100 x K <<< [N2]i and 100 x K<< [O2] i;

x = 10.-50 x10  5 )(0.080)(0.020)

[O2] = 0.020 –x = 0.020 – 6.3 x 10-5

H2(g) + I2(g) ↔ 2HI(g

Equilibrium (M) 5.20x 10-3-x 5.20x 10-3-x 2x

PCl5(g) ↔ PCl3(g) + Cl2(g)

[PCl5] = 0.0920 M – 0.0859 M

*When the chemical reacton equaton is reversed,

*When the chemical reacton equatons are added

= 4.6 x 1023 at 25iC

When the above equaton is multplied by

2C(s) + O2(g) ↔ 2CO(g)) ----- K2 = (4.6 x 1023 ) 2

When the above equaton is multplied by a certain

The equilibrium constant expression for this equaton

= 1.8 x 10-4 at 25iC

= 5.6 x 103 at 25iC

Ag+(aq) + 2NH3(aq) ↔ Ag(NH3)2]+(aq) --------K2 = 1.1 x 107

Net equatin is:

= 1.8 x 10-10 x 1.1 x 107

(a)1/2N2(g) + 3/2H2(g) ↔ NH3(g) --- K2 = ? --(2)

Equaton (2) is reversed in order to get equatin (3).

SnO2(s) + 2H2 ↔ Sn(s) + 2H2O(g) -----K1 = 7.45---(1)

Reverse 2 and take the reciprical if the square of its K and

Equilibrium (M) 0.0200 -x 0.0125 + x

C.I. A.B. = Cincentratin immediately in adding butane

When the vilume of a gas is degreased, the pressure

[N2O4] = 0.0560M and [N2O] = 0.0256M