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What is Equilibrium? This is not Equilibrium?

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The Concept of Equilibrium The Concept of Equilibrium


• As a system approaches
equilibrium, both the
forward and reverse
reactions are occurring.
• At equilibrium, the forward
and reverse reactions are
proceeding at the same
rate.
Chemical equilibrium occurs when a reaction and
its reverse reaction proceed at the same rate.
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A System at Equilibrium A System at Equilibrium


Rates become equal Concentrations become constant

Once equilibrium is
achieved, the
amount of each
reactant and product
remains constant.

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Depicting Equilibrium Expression for Equilibrium Constant


Consider the following equilibrium system:
In a system at equilibrium, both the wA + xB ⇄ yC + zD
forward and reverse reactions are
[C] y [D] z

running simultaneously. We write the Kc = [A] w [B] x

chemical equation with a double arrow:


• The numerical value of Kc is calculated using the
concentrations of reactants and products that exist at
equilibrium.
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SAMPLE EXERCISE 15.1 Writing Equilibrium-Constant Expressions


Expressions for Equilibrium Constants
Write the equilibrium expression for Kc for the following reactions:

• Examples:
N2(g) + 3H2(g) ⇄ 2NH3(g); Kc = [NH 3 ] 2
[N 2 ][H 2 ] 3

PCl5(g) ⇄ PCl3(g) + Cl2(g); Kc = [PCl 3 ][Cl


[PCl 5 ]
2 ]

CH4(g) + H2(g) ⇄ CO(g) + 3H2(g);


[CO][H 2 ] 3
Kc = [CH 4 ][H 2 O] 9 10

SAMPLE EXERCISE 15.1 Writing Equilibrium-Constant Expressions Equilibrium Can Be Reached from Either
Write the equilibrium expression for Kc for the following reactions:
Direction

PRACTICE EXERCISE
Write the equilibrium-constant expression, Kc for
Kc, the final ratio of [NO2]2 to [N2O4], reaches a
constant no matter what the initial concentrations of
NO2 and N2O4 are (with const T).

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Equilibrium Can Be Reached from Equilibrium Can Be Reached from Either


Either Direction Direction
This graph shows data
from the last two trials
from the table.

It does not matter whether we start with N2 and H2 or whether


we start with NH3. We will have the same proportions of all
three substances at equilibrium.
13 What is the equilibrium expression? 14

What Does the Value of K Mean? What Does the Value of K Mean?
• If K >> 1, the reaction • If K >> 1, the reaction
is product-favored; is product-favored;
product predominates product predominates
at equilibrium. at equilibrium.
• If K << 1, the reaction is
reactant-favored;
reactant predominates
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at equilibrium. 16

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Calculating Equilibrium Constant


Calculating Equilibrium Constant for reaction: H2(g) + I2(g) ⇄ 2HI(g)
• ————————————————————————————
• Example-1:
• H2(g) + I2(g) ⇄ 2 HI(g)
1.000 mole of H2 gas and 1.000 mole of I2 vapor are introduced • ————————————————————————————
into a 5.00-liter sealed flask. The mixture is heated to a certain • Initial [ ], M: 0.200 0.200 0.000
temperature and the following reaction occurs until equilibrium is • Change in [ ], M: -0.158 -0.158 + 0.316
established. • Equilibrium [ ], M 0.042 0.042 0.316
H2(g) + I2(g) ⇄ 2HI(g)
• ————————————————————————————

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At equilibrium, the mixture is found to contain 1.580 mole of HI. Kc =
[HI] 2
=
(0.316)
= 57
(a) What are the concentrations of H2, I2 and HI at equilibrium? (b) [H 2 ][I 2 ] ( 0.042 ) 2
Calculate the equilibrium constant Kc. 17 18

Calculating Equilibrium Constant Calculating Equilibrium Constant


The reaction: H2(g) + I2(g) ⇄ 2HI(g), proceeds from right to
• Example-2:
left.
0.500 mole of HI is introduced into a 1.00 liter sealed flask and ————————————————————————————
heated to a certain temperature. Under this condition HI H2(g) + I2(g) ⇄ 2HI(g)
decomposes to produce H2 and I2 until an equilibrium is ————————————————————————————
established. An analysis of the equilibrium mixture shows that Initial [ ], M: 0.000 0.000 0.500
0.105 mole of HI has decomposed. Calculate the equilibrium Change in [ ], M: +0.0525 +0.0525 -0.105
concentrations of H2, I2 and HI, and the equilibrium constant Kc for Equil’m [ ], M 0.0525 0.0525 0.395
the following reaction: ————————————————————————————
2
(0.395)
H2(g) + I2(g) ⇄ 2HI(g), 19 Kc = (0.0525) 2
= 56.6 20

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Calculating equilibrium concentrations using Using the ICE table to calculate


initial concentrations and value of Kc equilibrium concentrations
Equation: H2(g) + I2(g) ⇄ 2 HI(g),
• Consider the reaction: 

Initial [ ], M 0.1000 0.1000 0.0000


• H2(g) + I2(g) ⇄ 2 HI(g), Change [ ], M -x -x +2x
• where Kc = 55.6 at 425oC. Equilibrium [ ], M (0.1000 - x) (0.1000 - x) 2x
 
• If [H2]0 = [I2]0 = 0.1000 M, and [HI]0 = 0.0 M, what
are their concentrations at equilibrium? [HI] 2 (2 x ) 2
K c    55.6
[H 2 ][ I 2 ] (0.100 - x ) 2
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Calculation of equilibrium concentrations Why is Equilibrium Constant Important?

2x
 55.6  7.46 • Knowing Kc and the initial concentrations, we can
( 0.100 - x
determine the concentrations of components at
2 x  0.746 - 7.46 x ;  9.46 x  0.746
equilibrium.
x  0.0789 ;
[H 2 ]  [I 2 ]  0.0211 M; [HI]  0.158 M

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Relationships between chemical equations and


Expression and Value of the expressions of equilibrium constants
Equilibrium Constant for a Reaction
• The expression of equilibrium constant depends on how the
equilibrium equation is written. For example, for the
• The expression for K depends on the equation; following equilibrium: 2
• The value of K applies to that equation; it does not [HI]
• H2(g) + I2(g) ⇄ 2 HI(g); K c  [H ][I ]
depend on how the reaction occurs; 2 2
• For the reverse reaction:
• Concentrations used to calculate the value of K are [H 2 ][I 2 ]
those measured at equilibrium. • 2HI(g) ⇄ H2(g) + I2(g); K c '   1/ K c
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[HI] 2 26

Applications of Equilibrium Constant


Homogeneous & Heterogeneous Equilibria
For any system or reaction:
Homogeneous equilibria: 1. Knowing the equilibrium constant, we can predict
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g);
whether or not a reaction mixture is at equilibrium, and
we can predict the direction of net reaction.
CO(g) + H2O(g) ⇄ CO2(g) + H2(g);
• Qc = Kc  equilibrium (no net reaction)
Heterogeneous equilibria: • Qc < Kc  a net forward reaction;
CaCO3(s) ⇄ CaO(s) + CO2(g); • Qc > Kc  a net reverse reaction
HF(aq) + H2O(l) ⇄ H3O+(aq) + F-(aq); 2. The value of K tells us whether a reaction favors the
PbCl2(s) ⇄ Pb2+(aq) + 2 Cl-(aq); products or the reactants.
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Equilibrium constant is used to predict the direction of What does the reaction quotient tell us?
net reaction
• For a reaction of known Kc value, the direction of net reaction If Qc = Kc,  the reaction is at equilibrium;
can be predicted by calculating the reaction quotient, Qc.
If Qc < Kc,  the reaction is not at equilibrium and
• Qc is called the reaction quotient, where for a reaction such
as:
there’s a net forward reaction;
[C] c [ D] d
• aA + bB ⇄ cC + dD; Q c  If Qc > Kc,  the reaction is not at equilibrium and
[A] a [ B] b
• Qc has the same expression as Kc , but there’s a net reaction in the opposite direction.
• Qc is calculated using concentrations that are not necessarily
at equilibrium.
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Reaction Quotient Reaction Quotient

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Le Châtelier’s Principle Le Châtelier’s Principle


• The Le Châtelier's principle states that: Factors that influence equilibrium:
when factors that influence an equilibrium are altered, the Concentration, temperature, and partial pressure
equilibrium will shift to a new position that tends to (for gaseous)
minimize those changes.

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The Effect of Changes in Concentration Effects of Pressure Change on Equilibrium


• Consider the reaction: N2(g) + 3H2(g) ⇄ 2 NH3(g);
• If the volume of a gas mixture is compressed, the
K 
[NH] 2
overall gas pressure will increase. In which direction
c
[N 2 ][H 2 ]3 the equilibrium will shift in either direction depends
• If [N2] and/or [H2] is increased, Qc < Kc on the reaction stoichiometry.
•  a net forward reaction will occur to reach new equilibrium
position. • However, there will be no effect to equilibrium if the
• If [NH3] is increased, Qc > Kc, and a net reverse reaction total gas pressure is increased by adding an inert gas
will occur to come to new equilibrium position. that is not part of the equilibrium system.
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Reactions that shift right when pressure increases Reaction that shifts left when pressure increases,
and shift left when pressure decreases but shifts right when pressure decreases
Consider the reaction: Consider the reaction: PCl5(g) ⇄ PCl3(g) + Cl2(g);
2SO2(g) + O2(g) ⇄ 2SO3(g),
1. The total moles of gas decreases as reaction proceeds in the 1. Forward reaction results in more gas molecules.
forward direction. 2. Pressure increases as reaction proceeds towards equilibrium.
2. If pressure is increased by decreasing the volume 3. If mixture is compressed, pressure increases, and reverse
(compression), a forward reaction occurs to reduce the reaction occurs to reduce pressure;
stress. 4. If volume expands and pressure drops, forward reaction
3. Reactions that result in fewer moles of gas favor high occurs to compensate.
pressure conditions. 5. This type of reactions favors low pressure condition
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Reactions not affected by pressure changes The Effect Temperature on Equilibrium


Consider the following reactions: • Consider the following exothermic reaction:
1. CO(g) + H2O(g) ⇄ CO2(g) + H2(g); N2(g) + 3H2(g) ⇄ 2NH3(g); DHo = -92 kJ,
2. H2(g) + Cl2(g) ⇄ 2HCl(g); • The forward reaction produces heat => heat is a product.
• When heat is added to increase temperature, reverse reaction will take place
1. Reactions have same number of gas molecules in reactants to absorb the heat;
and products. • If heat is removed to reduce temperature, a net forward reaction will occur
2. Reducing or increasing the volume will cause equal effect to produce heat.
on both sides – no net reaction will occur. • Exothermic reactions favor low temperature conditions.
3. Equilibrium is not affected by change in pressure.
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The Effect Temperature on Equilibrium Le Châtelier’s Principle


Consider the following endothermic reaction:
CH4(g) + H2O(g) ⇄ CO(g) + 3H2(g), DHo = 205 kJ
1. Endothermic reaction absorbs heat  heat is a reactant;
2. If heat is added to increasing the temperature, it will cause a net forward
reaction.
3. If heat is removed to reduce the temperature, it will cause a net reverse
reaction.
4. Endothermic reactions favor high temperature condition.

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Le Châtelier’s Principle Le Châtelier’s Principle

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Le Châtelier’s Principle Water Dissociation Constant


• autoionization of water

[ H 3O  ][OH  ]
Keq 
[ H 2O ]

Keq  Kw  [ H 3O  ][OH  ]  1x1014


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Water Dissociation Constant Water Dissociation Constant

Keq  Kw  [ H 3O  ][OH  ]  1x1014 1. [OH-] = 1.2 x 10-6


Kw = [H+][OH-] = 1 x 10-14
[H3O+] = [OH-] = 1 x 10-7 substitute the value of [OH-]
1 x 10-14 = [H+] 1.2 x 10-6
• Added solutes could affect the H+ and OH- concentrations rearrange the equation to solve for [H+]
of water [H+] = 1 x 10-14 / 1.2 x 10-6 = 8.3 x 10-9
– concentration will change 2. [H+] = 2.45 x 10-5
– could be accounted for using the Kw expression 3. [OH-] = 2.48 x 10-11
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Water Dissociation Constant Water Dissociation Constant


• pH scale • pH then is use to determine whether the solution is acidic, basic or
neutral
–pH is defined as the negative logarithm of
the concentration of H+ From the previous example [H+] = 8.3 x 10-9, the pH of the solution
–pH range from 1 to 14 could be calculated.
–measure of acidity of solutions
pH = - log [H+] = -log 8.3 x 10-9 = 8.1
–acidic, basic or neutral
Consequently pH could be used to calculate the [H+] of solution
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Water Dissociation Constant Water Dissociation Constant


• For example
pH = 5.8
[H+] = antilog – pH
[H+] = antilog – 5.8
[H+] = 1.5 x 10-6

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[H+] will be use to calculate [OH-] of the solution. 52

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Water Dissociation Constant Acid Dissociation Constant


• a related value to pH is pOH defined as: • Concepts of acids and bases
– Arrhenius, Bronstead-Lowry, Lewis Concepts
pOH = -log [OH-]
• the Kw expression could now be expressed in its logarithmic • strong or weak acids and bases
form – Strong acids/bases undergo complete dissociation
Kw = [H+][OH-]
- Weak acids/bases undergo incomplete dissociation
1 x 10-14 = [H+][OH-]
- log 1 x 10-14 = (-log [H+]) + (-log [OH-])
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Acid Dissociation Constant Acid Dissociation Constant

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Acid Dissociation Constant Acid Dissociation Constant

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Acid Dissociation Constant Acid Dissociation Constant

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The Henderson-Hasselbalch Equation Buffered Solutions Resist Changes in pH


• Defines the pH of a solution in terms of: • Buffer capacity is the ability of a solution to resist changes in
pH
(1) The pKa of the weak acid
• Most effective buffering occurs where:
(2) Concentrations of the weak acid (HA) and conjugate
base (A-) solution pH = buffer pKa
• At this point: [weak acid] = [conjugate base]
• Effective buffering range is usually at pH values equal to the
pKa ± 1 pH unit
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Buffered Solutions Resist Changes in pH Buffered Solutions Resist Changes in pH


Find the pH of the solution prepared by dissolving 12.43 gms of tris (B-),
FM = 121.136 gms/mol and 4.67 gms of tris hydrochloride (BH+), FM =
157.597 gms/mol in 1.0 L of water. pKa of BH+ = 8.075
Solution:
moles B- = 12.43 gms/121.136 gms/mol
= 0.10 mol
+
moles BH = 4.67 gms/157.597 gms/mol
= 0.03 mol
pH = pKa + log [B-]/[BH+]
pH = 8.075 + log 0.10/0.03 = 8.60
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Base Dissociation Constant


Base Dissociation Constant

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Base Dissociation Constant Base Dissociation Constant

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Solubility Equilibrium

PbCl2(s) ⇄ Pb2+(aq) + 2Cl-(aq);


Ksp = [Pb2+][Cl-]2

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