Lecture Presentation

Unit 7
Day 1

Chemical
Equilibrium

James F. Kirby
Quinnipiac University
Hamden, CT
Edited by M. Day
2015 Pearson Education, Inc.
Warm Up:
The Concept of Equilibrium

As a system approaches equilibrium, both

____________ are ___________.
At equilibrium, the ____________________are
proceeding ___________________.
At equilibrium, the amount ________________
Equilibrium
______________________________.
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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.
At equilibrium, the amount of each reactant and
product is constant. Equilibrium

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 Agenda
15.1 Concept of Equilibrium
15.2 The Equilibrium Constant
15.3 and 15.4 Understanding & Working
with Equilibrium Constants

Equilibrium

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The Concept of Equilibrium

Chemical equilibrium occurs when a reaction

and its reverse reaction proceed at the same
rate. In the figure above, equilibrium is finally
reached in the third picture. Equilibrium

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Writing the Equation for an
Equilibrium Reaction
Since, in a system at equilibrium, both
the forward and reverse reactions are
being carried out, we write its equation
with a double arrow:

N2O4(g) 2 NO2(g)

Equilibrium

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 Comparing Rates
For the forward reaction
N2O4(g) 2 NO2(g)
The rate law is
Rate = kf [N2O4]

For the reverse reaction

2 NO2(g) N2O4(g)
The rate law is
Rate = kr [NO2]2
Equilibrium

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The Meaning of Equilibrium
Therefore, at equilibrium
Ratef = Rater
kf[N2O4] = kr[NO2]2

Rewriting this, it becomes the expression

for the equilibrium constant, Keq.

Equilibrium

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 Another Equilibrium
The Haber Process
Consider the Haber Process, which is
the industrial preparation of ammonia:
N2(g) + 3 H2(g) 2 NH3(g)
The equilibrium constant depends on
stoichiometry:

Equilibrium

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The Equilibrium Constant
Consider the generalized reaction
aA + bB dD + eE
The equilibrium expression for this reaction
would be

Also, since pressure is proportional to

concentration for gases in a closed system, the
equilibrium expression can also be written

Equilibrium

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 HA H+ + A
[HA] = 1.65 102 M and
[H ] = [A ] = 5.44 10 M at
+ 4

equilibrium. Kc = _______.
a. 1.79 102
b. 1.79 103
c. 1.79 104
d. 1.79 105
Equilibrium

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More with Gases and Equilibrium
We can compare the equilibrium constant
based on concentration to the one based
on pressure.
For gases, PV = nRT (the Ideal Gas Law).
Rearranging, P = (n/V)RT; (n/V) is [ ].
The result is

Where

Equilibrium

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 KP = KC when

a. the reaction is at equilibrium.

b. the reaction is exothermic.
c. all of the gases present are at
the same pressure.
d. the number of moles of gas
on both sides of the balanced
equation is the same.
Equilibrium

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 KP = KC when
d. the number of moles of gas on
both sides of the balanced
equation is the same.
WHY? Pressure is proportional to
concentration for gases in a closed
system. And,
If the number of moles remains the
same, RT is raised to the power of zero,
making KP = KC Equilibrium

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 Equilibrium Can Be Reached
from Either Direction
As you can see, the ratio of [NO2]2 to [N2O4] remains
constant at this temperature no matter what the
initial concentrations of NO2 and N2O4 are.

Equilibrium

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Magnitude of K
If K>>1, the reaction
favors products;
products predominate
at equilibrium.
If K<<1, the reaction
favors reactants;
reactants predominate
at equilibrium.

Equilibrium

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 If the value of the equilibrium
constant is large, then at
equilibrium mostly _______
will be present.
a. reactants
b. products
c. catalysts
d. water
Equilibrium

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The Direction of the Chemical
Equation and K
The equilibrium constant of a reaction in
the reverse reaction is the reciprocal of
the equilibrium constant of the forward
reaction:
[NO2]2
N2O4(g) 2 NO2(g) Kc = = 0.212 at 100 C
[N2O4]

2 NO2(g) N2O4(g) Kc = ?

Equilibrium

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The Direction of the Chemical
Equation and K
The equilibrium constant of a reaction in
the reverse reaction is the reciprocal of
the equilibrium constant of the forward
reaction:
[NO2]2
N2O4(g) 2 NO2(g) Kc = = 0.212 at 100 C
[N2O4]
[N2O4]
2 NO2(g) N2O4(g) Kc = = 4.72 at 100 C
[NO2] 2

Equilibrium

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 Stoichiometry and
Equilibrium Constants
[NO2]2
N2O4(g) 2 NO2(g) Kc = = 0.212 at 100 C
[N2O4]
[NO2]4
2 N2O4(g) 4 NO2(g) Kc = = (0.212) 2
at 100 C
[N2O4] 2

To find the new equilibrium constant of a

reaction when the equation has been
multiplied by a number, simply raise the
original equilibrium constant to that power.
Here, the stoichiometry is doubled; the
constant is the squared!
Equilibrium

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Consecutive Equilibria
When two consecutive equilibria occur, the
equations can be added to give a single
equilibrium.
The equilibrium constant of the new reaction is
the product of the two constants:
K3 = K1 K2
Example
2 NOBr 2 NO + Br2 K1 = 0.014
Br2 + Cl2 2 BrCl K2 = 7.2
2 NOBr + Cl2 2 NO + 2 BrCl
K3 = K1 K2 = 0.014 7.2 = 0.10 Equilibrium

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Consecutive Equilibria
When two consecutive equilibria occur, the
equations can be added to give a single
equilibrium.
The equilibrium constant of the new reaction is
the product of the two constants:
K3 = K1 K2
Example
2 NOBr 2 NO + Br2 K1 = 0.014
Br2 + Cl2 2 BrCl K2 = 7.2
2 NOBr + Cl2 2 NO + 2 BrCl
K3 = K1 K2 = 0.014 7.2 = 0.10 Equilibrium

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Homogeneous vs. Heterogeneous
Homogeneous equilibria occur when all
reactants and products are in the same
phase.
Heterogeneous equilibria occur when
something in the equilibrium is in a
different phase.
The value used for the concentration of a
pure substance is always 1.
Therefore, whenever a pure solid or pure
liquid appears in an equilibrium reaction,
its concentration is not included in the Equilibrium

equilibrium expression.
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 The Decomposition of CaCO3
A Heterogeneous Equilibrium
The equation for the reaction is
CaCO3(s) CaO(s) + CO2(g)
This results in
Kc = ?
and
Kp = ?

Equilibrium

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 The Decomposition of CaCO3
A Heterogeneous Equilibrium
The equation for the reaction is
CaCO3(s) CaO(s) + CO2(g)
This results in
Kc = [CO2]
and
Kp = PCO2

Equilibrium

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 Deducing Equilibrium
Concentrations
1) Tabulate all known initial and equilibrium
concentrations.
2) For anything for which initial and equilibrium
concentrations are known, calculate the change.
3) Use the balanced equation to find change for all
other reactants and products.
4) Use initial concentrations and changes to find
equilibrium concentration of all species.
5) Calculate the equilibrium constant using the
equilibrium concentrations. Equilibrium

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An Example
A closed system initially containing
1.000 103 M H2 and 2.000103 M
I2 at 448 C is allowed to reach
equilibrium. Analysis of the equilibrium
mixture shows that the concentration of
HI is 1.87 103 M. Calculate Kc at
448 C for the reaction taking place,
which is
H2(g) + I2(g) 2 HI(g)
Equilibrium

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What Do We Know?

[H2], M [I2], M [HI], M

Initially 1.000 103 2.000 103 0

Change

At equilibrium 1.87 103

Equilibrium

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[HI] Increases by 1.87 103 M

[H2], M [I2], M [HI], M

Initially 1.000 103 2.000 103 0

Change +1.87 103

At equilibrium 1.87 103

Equilibrium

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Stoichiometry tells us [H2] and [I2] decrease
by half as much.

[H2], M [I2], M [HI], M

Initially 1.000 103 2.000 103 0

Change 9.35 104 9.35 104 +1.87 103

At equilibrium 1.87 103

Equilibrium

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We can now calculate the equilibrium
concentrations of all three compounds.

[H2], M [I2], M [HI], M

Initially 1.000 103 2.000 103 0

Change 9.35 104 9.35 104 +1.87 103

At equilibrium 6.5 105 1.065 103 1.87 103

Equilibrium

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And, therefore, the equilibrium
constant

[HI]2
Kc =
[H2] [I2]
(1.87 103)2
=
(6.5 105)(1.065 103)
= 51
Equilibrium

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 Warm Up
Why is the equilibrium constant
constant?

Equilibrium

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Is a Mixture in Equilibrium? Which
Way Does the Reaction Go?
To answer these questions, we calculate
the reaction quotient, Q.
Q looks like the equilibrium constant, K,
but the values used to calculate it are the
current conditions, not necessarily those
for equilibrium.
To calculate Q, one substitutes the initial
concentrations of reactants and products
into the equilibrium expression.
Equilibrium

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 Comparing Q and K
Nature wants Q = K.
If Q < K, nature will
make the reaction
proceed to products.
If Q = K, the reaction
is in equilibrium.
If Q > K, nature will
make the reaction
proceed to reactants.
Equilibrium

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 Calculating Equilibrium
Concentrations
If you know the equilibrium constant, you
can find equilibrium concentrations from
initial concentrations and changes (based
on stoichiometry).
You will set up a table similar to the ones
used to find the equilibrium concentration,
but the change in concentration row will
simple be a factor of x based on the
stoichiometry.
Equilibrium

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 An Example
A 1.000 L flask is filled with 1.000 mol of H 2(g)
and 2.000 mol of I2(g) at 448 C. Given a Kc of
50.5 at 448 C, what are the equilibrium
concentrations of H2, I2, and HI?
H2(g) + I2(g) 2 HI(g)
initial concentration 1.000 2.000 0
(M)
change in x x +2x
concentration (M)
equilibrium 1.000 x 2.000 x 2x
concentration (M)

Equilibrium

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 Example (continued)
Set up the equilibrium constant expression,
filling in equilibrium concentrations from
the table.

Solving for x is done using the quadratic

formula, resulting in x = 2.323 or 0.935.

Equilibrium

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 Example (completed)
Since x must be subtracted from 1.000 M,
2.323 makes no physical sense. (It results
in a negative concentration!) The value
must be 0.935.
So
[H2]eq = 1.000 0.935 = 0.065 M
[I2]eq = 2.000 0.935 = 1.065 M
[HI]eq = 2(0.935) = 1.87 M
Equilibrium

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LeChteliers Principle
If a system at equilibrium is disturbed by a change
in temperature, pressure, or the concentration of
one of the components, the system will shift its
equilibrium position so as to counteract the effect
of the disturbance.

Equilibrium

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 Warm Up

What three conditions did we

manipulate in the lab that shifted the
equilibrium of the five systems tested?

Equilibrium

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How Conditions Change Equilibrium
We will use LeChteliers Principle
qualitatively to predict shifts in equilibrium
based on changes in conditions.

Equilibrium

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How Conditions Change Equilibrium
We will use LeChteliers Principle
qualitatively to predict shifts in equilibrium
based on changes in conditions.

Equilibrium

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Lab Report: Procedure, Data, Discussion of Theory
A. HIn (aq) H+ (aq) + ln-(aq)

H+(aq) + OH-(aq) H2O(l)

Procedure Observations Explanation
Initial color of water and Solution is green The green color shows
bromothymol blue that the pH of distilled
water is between 6 and
7.6, and the indicator is
a mix of Hln and I-
Add 0.1 M HCl Solution turned yellow
pH < 6.0
Add 0.1 M NaOH Solution turned green
and finally ended on
blue, pH > 7.6
Additional drops of HCl Solution changes from
and NaOH yellow (with HCl) to Equilibrium
blue (with NaOH)
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Lab Report: Procedure, Data, Discussion of Theory
B. Cu2+(aq) + 4NH3 (aq) [Cu(NH3)4]2+(aq)

H+(aq) + NH3(aq) NH4+(aq)

Procedure Observations Explanation
Initial color of copper Solution is blue
solution
Add concentrated NH3 Solution turned light
drops blue and solid formed;
with more NH3, solid
dissolved and turned
deep blue
Add 1.0 M HCl Deep blue faded to
lighter blue and solid
formed again
Additional drops of NH3 Solid dissolved again
and solution turned Equilibrium
deep blue
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Lab Report: Procedure, Data, Discussion of Theory
C. [Co(H2O)6]2+(aq) + 4HCl (aq) + Heat [CoCl4]2-(aq) + 6H2O(l)
Ag+(aq) + Cl-(aq) AgCl(s)
Procedure Observations Explanation
Add 6.0 M HCl drops Solution turned blue
(tube A)
Add 0.1 M AgNO3 drops White solid precipitate
(tube B) and solution turned pink
Add distilled water drops Solution turned pink
(tube C)
Add 5-6 grains CaCl2 to Crystals dissolved and
tube C solution turned blue
Test tube C placed in ice Solution turned pink
water bath for 2-3
minutes
Test tube C placed in hot Solution turned blue
bath for 2-3 mins Equilibrium

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Lab Report: Procedure, Data, Discussion of Theory
D. 2CO2 (g) + H2O (l) CO2 (aq) + H+(aq) + HCO3-(aq)

Procedure Observations Explanation

Initial color of solution
Pull back on syringe to
decrease pressure
Push syringe to increase
pressure
Green color = pH 4.4
Solution turned teal, pH =
4.8
Solution turned green,
pH = 4.4

Equilibrium

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E. Mg(OH)2 (s) Mg2+(aq) + 2OH-(aq)

H+(aq) + OH-(aq) H2O (l)

Procedure Observations Explanation
Initial color of milk of Purple solution with white White solid is undissolved
magnesia and solid suspended in liquid Mg(OH)2. Purple color is from
universal indicator the universal indicator and
shows that some of the OH-
ions are present b/c purple =
pH > 10
Add 1 drop of 3 M HCl Solution immediately turned
with constant stirring pink with more stirring pink
color turned orange, green,
then blue
Additional drops of 3 M Solution immediately turned
HCl pink; slower change to the
blue-green end color
Additional drops of HCl Solution immediately turned
and NaOH pink; color remained pink and
Equilibrium
solution not cloudy
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 Change in Reactant or Product
Concentration
If the system is in equilibrium
adding a reaction component will result in some
of it being used up.
removing a reaction
component will
result in some if it
being produced.

Equilibrium

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 Change in Volume or Pressure
When gases are involved in an equilibrium,
a change in pressure or volume will affect
equilibrium:
Higher volume or lower pressure favors the
side of the equation with more moles (and
vice-versa).

Equilibrium

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 Change in Temperature
Is the reaction endothermic or
exothermic as written? That matters!
Endothermic: Heats acts like a reactant;
adding heat drives a reaction toward
products.
Exothermic: Heat acts like a product;
adding heat drives a reaction toward
reactants.

Equilibrium

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 An Endothermic Equilibrium

Equilibrium

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 An Exothermic Equilibrium
The Haber Process for producing
ammonia from the elements is exothermic.
One would think that cooling down the
reactants would result in more product.
However, the activation energy for this
reaction is high!
This is the one instance where a system in
equilibrium can be affected by a catalyst!

Equilibrium

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Catalysts
Catalysts increase the rate of both the forward
and reverse reactions.
Equilibrium is achieved faster, but the equilibrium
composition remains unaltered.
Activation energy is lowered, allowing equilibrium
to be established at lower temperatures.

Equilibrium

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 END DAY 2 LECTURE

Equilibrium

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