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Centre for Foundation Studies, UTAR

Chapter Scopes
Chemical Equilibria
Equilibrium constant (Kc and Kp)
Reaction quotient (Qc)
Solubility product (Ksp)
Le Chateliers Principle
I. C. E. Table

Chapter 7

Equilibria
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Equilibrium

Chemical Equilibrium

Equilibrium is a state in which there


are no observable changes as time
goes by

Chemical equilibrium is achieved


when:

Equilibrium System are:

the concentrations of the reactants


& products remain constant

the rates of the forward & reverse


reactions are equal

Dynamic
Reversible
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Meaning of K

Equilibrium Constant, K

Equilibrium Will

aA + bB

cC + dD

FHSC1114 Physical Chemistry

K >> 1

Lie to the right

Favor products

K << 1

Lie to the left

Favor reactants

Centre for Foundation Studies, UTAR

Homogeneous
Equilibrium

Product- or ReactantFavored

applies to reactions in which all


reacting species are in the same
phase.
N2O4 (g)

2NO2 (g)

Kc =

Kp =

In most cases
Kc Kp
aA(g) + bB(g)

Calculation

cC(g) + dD(g)

Kp = Kc(RT)n
n = Total moles of gaseous products
Total moles of gaseous reactants

The equilibrium concentrations for the


reaction between carbon monoxide and
molecular chlorine to form COCl2(g) at
74 C are [CO] = 0.012 M, [Cl2] = 0.054
M, and [COCl2] = 0.14 M. Calculate the
equilibrium constants Kc and Kp.

= (c + d) (a + b)

CO(g) + Cl2(g)

COCl2(g)

General practice not to include units for the


equilibrium constant (dimensionless)
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CO(g) + Cl2(g)

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Heterogeneous
Equilibrium

COCl2(g)

applies to reactions in which reactants


& products are in different phases.

Kp = Kc(RT)n

CaCO3(s)
n =
R = 0.082057

Kc =

T = 273.2 + 74 = 347.2 K
Kp =
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FHSC1114 Physical Chemistry

Kc =

[CaO][CO2]
[CaCO3]

CaO(s) + CO2(g)

[CaCO3] = constant
[CaO] = constant
Kp =

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Centre for Foundation Studies, UTAR

CaCO3(s)

CaO(s) + CO2(g)

Calculation
Consider the following equilibrium at 295 K:
NH4HS (s)
NH3 (g) + H2S (g)
The partial pressure of each gas is 0.265
atm. Calculate Kp and Kc for the reaction?
Kp = PNH3 PH2S = 0.265 x 0.265 = 0.0702
Kp = Kc(RT)n

Kp = PCO 2

The [solids] & [pure liquids] are not


included in the expression for the
equilibrium constant.

Kc = Kp(RT)-n

n =
13

Writing & Manipulating


K Expressions

T = 295 K

Kc =

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ii) Changing direction of the reactions:

i) Adding equations for reactions:

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Reaction Quotient (Qc)

iii) Changing coefficient:


S(s) + 3/2O2(g)

SO3(g)

2S(s) + 3O2(g)

2SO3(g)

[SO3 ]

Knew

[O2 ]3/2
Knew

[SO3 ]2
[O2 ]3

Qc is calculated by substituting the initial


concentrations of the reactants & products
into the equilibrium constant (Kc) expression.

Qc > Kc The system proceeds from __________

[SO3 ]2
[O2 ]3

Q c = Kc

= (Kold )2

Q c < Kc
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FHSC1114 Physical Chemistry

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to reach equilibrium
(reactants product)
The system is ___________
(no net change)
The system proceeds from __________
to reach equilibrium
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(reactants products)

Centre for Foundation Studies, UTAR

Example: Reaction Quotient (Qc)


The brown gas nitrogen dioxide, NO2, will exist in
equilibrium with the colorless gas N2O4.

[NO2] = 0.015M
[N2O4] = 0.025M
Qc =

2NO2(g)

N2O4(g)

K = 170, T = 298 K

Suppose that, at a specific time, [NO2] is 0.015


M, and [N2O4] is 0.025 M. Is Q larger than,
smaller than or equal to K? If the system is not at
equilibrium, in which direction will the reaction
proceed to achieve equilibrium?
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1. Express the equilibrium concentrations of all


species in terms of the initial concentrations &
a single unknown x, which represents the
change in concentration.
2. Write the equilibrium constant expression in
terms of the equilibrium concentrations.
Knowing the value of the equilibrium constant,
solve for x.
3. Having solved for x, calculate the equilibrium
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concentrations of all species.

x =

-b

(x)(x)
[A]0 - x

b2 - 4ac
2a
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FHSC1114 Physical Chemistry

A(g)

B(g)

[A]0
-x
[A]0 - x

0
+x
x

Kc =
Kc =

[B][C]
[A]
[B][C]
[A]

(x)(x)
[A]0 - x

C(g)
0
+x
x

Kc and [A]0 are


known values

(x)(x)
[A]0

Making approximation: [A]0 x [A]0, if 100 x Kc < [A]


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1. The reaction:
N2(g) + O2(g)
2NO(g)
contributes to air pollution whenever a fuel is
burned in air at high temperature, as in a
gasoline engine. At 1500 K, Kc = 1.0 x 10-5.
Suppose a sample of air has [N2] = 0.80 mol/L
and [O2] = 0.20 mol/L before any reaction
occurs. Calculate the equilibrium concentrations
of reactants and products after the mixture has
been heated to 1500 K.

Need to use the quadratic formula to


solve the x

[A]

Equation
Initial (M)
Change (M)
Equilibrium (M)

Exercise

If 100 x Kc > [A]0, so [A]0 x [A]0, the


approximation is not acceptable!

[B][C]

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Calculating Equilibrium Concentrations


(Making approximation)

Calculating Equilibrium
Concentrations

Kc =

Qc ___ K, the reaction is not at


equilibrium.
The system proceeds to equilibrium
by converting more NO2 to N2O4
(from _________), increasing [N2O4]
and decreasing [NO2] until Q = K.

Answer:
[N2] 0.80 M ; [O2] 0.20 M ;
[NO] 1.3 x 10-3 M

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Centre for Foundation Studies, UTAR

Nitrogen Dioxide Equilibrium


N2O4(g)

Kc = 0.0059 =

2 NO2(g)

If initial concentration of N2O4 is 0.50 M,


what are the equilibrium concentrations?
Kc =

[NO2 ]2
= 0.0059 at 298 K
[N2O4 ]

Concentration
Initial (M)
Change (M)
Equilibrium (M)

x =

0.0059

-b

[N2O4]
0.50
-x
0.50 - x

[NO2]
0
+ 2x
2x

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b2 - 4ac
2a

2( 4)

x = -0.00074 1/8(0.047)1/2 = -0.00074 0.027

Rearrange: 0.0059 (0.50 - x) = 4x2


0.00295 - 0.0059x = 4x2
4x2 + 0.0059x - 0.00295 = 0
This is an QUADRATIC EQUATION
ax2 + bx + c = 0
a=4
b = 0.0059
c = -0.00295 26

Defined as the product of the


concentration of the ions in a saturated
solution of the salt, raised to the power of
the stoichiometric coefficient of the
respective ions.
AgCl(s) Ag+(aq) + Cl-(aq)
Ksp = [Ag+ ][Cl-]
* higher the Ksp value, the higher is the
solubility

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Give the expression of Ksp for


the sparingly soluble salts
(i) NiS(s) Ni2+(aq) + S2-(aq)
Ksp =
(ii) Pb(OH)2(s) Pb2+(aq) + 2OH- (aq)
Ksp =

(iii) Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43-(aq)


Ksp =
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FHSC1114 Physical Chemistry

As 100 x Kc > [N2O4]0, the approximation


0.50 x 0.50 is not acceptable!

Solubility Products, Ksp

0.00592 4( 4) ( 0.00295)

x = 0.026 or - 0.028
But a negative value is not reasonable.
Conclusion: x = 0.026 M
[N2O4] = 0.50 - x = 0.474 M
[NO2] = 2x = 0.052 M

[NO2 ]2
(2x)2
=
[N2O 4 ]
(0.50 - x)

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Questions
The Ksp for AgCl is 1.8 x 10-10. If Ag+ and
Cl- are both in solution and in equilibrium
with AgCl. What is [Ag+] if [Cl-] = 0.020 M
Answer: [Ag+] = __________ M

If Ag+ and Cl- were both present at 0.0001


M, would a precipitate occur?
Answer: Yes, a precipitate would occur
because these concentrations together
are higher than what the Ksp allows.
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Centre for Foundation Studies, UTAR

Le Chateliers
Principle

Le Chateliers
Principle

When a system at
equilibrium is disturbed,
the equilibrium position
will shift in the direction
which tends to minimize
or counteract, the effect
of the disturbance.

Ways to change the conditions


of the reaction:
1. Concentration
2. Pressure & volume
3. Temperature
4. Adding catalyst

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Changes in
Concentration

Changes in
Concentration

aA + bB

Haber Process
N2 (g) + 3H2 (g)
Equilibrium
shifts left to
offset stress

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2NH3

(g)

Add
NH3

Change
[product/s]
[product/s]
[reactant/s]
[reactant/s]

cC + dD
Shifts the Equilibrium
left
right
right
left

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Changes in
Temperature

Changes in Volume
& Pressure
aA (g) + bB (g)

Change

cC (g)

Exothermic Reaction

T
Shifts the Equilibrium

shifts to the
K Equilibrium
left

pressure
pressure

Side with fewest moles of gas


Side with most moles of gas

shifts to the
K Equilibrium
right

volume
volume

Change

Side with most moles of gas


Side with fewest moles of gas

Change

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FHSC1114 Physical Chemistry

T
T

Endothermic Reaction
Equilibrium shifts to the

K right
shifts to the
K Equilibrium
left
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Centre for Foundation Studies, UTAR

Le Chateliers Principle
(adding a catalyst)
aA + bB

Le Chateliers Principle
(adding a catalyst)

cC + dD

Adding a Catalyst
does not change K
does not shift the position of an
equilibrium system
system will reach equilibrium sooner
Lowers Ea for both forward and
reverse reactions
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Le Chateliers
Principle

catalyzed
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Summary

Change

Shift
Equilibrium

Concentration

yes

Change
Equilibrium
Constant
no

Pressure

yes

no

Volume

yes

no

Temperature

yes

yes

Catalyst

no

no

FHSC1114 Physical Chemistry

uncatalyzed

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Understand & calculate equilibrium


constants in term of Kc & Kp
Understand & calculate reaction
quotient, Q
Kp = Kc(RT)n
Express solubility constant, Ksp
Calculate equilibrium concentration
using ICE table
Le Chateliers Principle
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