Dynamic equilibrium

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Phase transitions:
Saturated solutions:
Chemical reactions:
Equilibrium is reached when
the rates of the forward and
the reverse processes are equal.
Examples: nitrogen dioxide
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2

at equilibrium:
K
eq
depends on temperature
Example: Co
2+
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at equilibrium:
Adding reactants shifts the equilibrium to the right.
Adding products shifts the equilibrium to the left.
Example: ammonia synthesis
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at equilibrium:
the same equilibrium state is reached starting
with reactants or with products
The law of mass action
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for gas-phase reactions
concentrations (M) or partial pressures (atm) at equilibrium
K
c
and K
p
are unit-less, written in terms of the activities of the substances involved.
The activity of a component in a mixture is the ratio of its concentration to a standard
state (1 M for solutions, 1 atm for gases) so that the activity is unit-less but equal to the
concentration or partial pressure of the component.
Equilibrium constant expressions
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Since the law of mass action specifies that the products are in the numerator and
the reactants are in the denominator of an equilibrium expression, it is critical to make
sure that the equilibrium expression matches the reaction, as written from the left to
right.

K'
c
= 1/K
c,

Equilibrium constant expressions
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Heterogeneous equilibria
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Pure phases have activity of 1.0 and do not appear in the equilibrium expression.
Equilibrium calculations
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Consider a reaction in which 1.00 mole of SO
2
(g) and 1.00 mole of O
2
(g) are
added to a 1.00 L container at 1000 K and allowed to react until equilibrium
is achieved. At equilibrium, the container has 0.919 moles of SO
3
(g).
What are the values of K
c
and K
p
?

Equilibrium calculations: ICE table
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Equilibrium calculations II
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11

Consider the following equilibrium:




What is the K
c
expression for this equilibrium?

A one L container holds 224 g of Fe(s) and 5.00 mole of H
2
O().
It is heated to 1000 K and the reaction reaches equilibrium at which point
56 g of Fe(s) is left unreacted.

What is the value of K
c
?

Equilibrium calculations II
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pure
phase
pure
phase
Meaning of K
eq
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K
eq
[products]/[reactants]

K
eq
1 (0.01 < K < 100) comparable amounts of reactants and products
K
eq
> 10
2
products are favored , the equilibrium lies to the right.
K
eq
< 10
2
reactants are favored, the equilibrium lies to the left.

Reaction quotient
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concentrations (or partial
pressures) are values at any moment
Q < K
e
The concentrations (or partial pressures) of the
products are too small and that of reactants are too large;
the reaction will form more products to reach equilibrium
(shifts to the right).

Q = K
eq
The system is at equilibrium; no changes in the
concentration (or partial pressures) will take place.


Q > K
eq
The concentration (or partial pressures) of
products are too large and that of reactants too small;
the reaction will form more reactants to reach equilibrium
(shifts to the left).
Reaction quotient: example
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Consider the decomposition reaction of iodine bromide, which produces
molecular bromine and iodine, with the equilibrium constant K
c
= 2.5 x 10
3
.
The initial concentration of each participating compound is 0.05 M.
What are the final concentrations of the reactant and products?

Reaction quotient: ICE table
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Reaction quotient: ICE table
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square root
Le Chateliers principle
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If a system at equilibrium is disturbed, it will shift to
minimize the effect of the disturbance.
Halving the volume, initially doubles the concentration of NO
2
(g) , the system
responds to the increased pressure by shifting the equilibrium to the left (N
2
O
4
),
thus lowering the number of moles and the pressure. The brown color of NO
2
fades.
Adding reactants or products
PM 19

add HCl
add H
2
O
Addition of Cl

(as HCl), the reactant, shifts the equilibrium to the right,

consuming some added Cl

.

Addition of H
2
O, the product, shifts the equilibrium to the left, consuming
Some added H
2
O.
Temperature effect on equilibrium
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Temperature affects the value of K
eq


One may treat the heat of the reaction
as a reactant (endothermic reaction) or
as a product (exothermic reaction).

The formation of NO
2
is endothermic (it requires
bond breaking) , the increase in temperature
favors product.
300 K 77 K
Temperature effect on equilibrium
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Temperature affects the value of K
eq



The formation of chloride is endothermic.

The increase in temperature favors product.
Perturbations of ammonia equilibrium
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The reaction is run in a 1.0 L container at 500
o
C. We start with:

[N
2
] = 1.00 M [H
2
] = 3.0 M [NH
3
] = 0.0 M

Under these conditions ,we find at equilibrium:

[N
2
] = 0.70 M [H
2
] = 2.10 M [NH
3
] = 0.60 M

The amount of ammonia is less than desired.

Can we take advantage of any of the perturbations to increase the production of ammonia?
K
c
= 5.6 x 10
2
Ammonia synthesis : adding reactants
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Initial: [N
2
] = 1.00 M [H
2
] = 3.0 M [NH
3
] = 0.0 M
At equilibrium : [N
2
] = 0.70 M [H
2
] = 2.10 M [NH
3
] = 0.60 M

Add 3 moles of H
2
and 1 mole of N
2

Chatelier's prediction: more product formed

Confirm: Q = (0.60)
2
/[(1.70)(5.10)
3
] = 1.6 x 10
3
Q < K
c
the product must increase

New equilibrium: [N
2
] = 1.16 M [H
2
] = 3.50 M [NH
3
] = 1.67 M

Thus doubling of both reactants gives only 2.7 increase in the product.



Ammonia synthesis : decrease volume
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Initial: [N
2
] = 1.00 M [H
2
] = 3.0 M [NH
3
] = 0.0 M
At equilibrium : [N
2
] = 0.70 M [H
2
] = 2.10 M [NH
3
] = 0.60 M

Decrease the volume from 1 L to 0.5 L (double the pressure)


Chatelier's prediction: increased pressure => more product formed (fewer moles)

Confirm: Q = (1.20)
2
/[(1.40)(4.20)
3
] = 1.4 x 10
2
Q < K
c
the product must increase

New equilibrium: [N
2
] = 1.05 M [H
2
] = 3.15 M [NH
3
] = 1.90 M

(but the number of moles of NH
3
at equilibrium is 0.95, i.e. 58% increase)


Ammonia synthesis : adding inert gas
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Initial: [N
2
] = 1.00 M [H
2
] = 3.0 M [NH
3
] = 0.0 M
At equilibrium : [N
2
] = 0.70 M [H
2
] = 2.10 M [NH
3
] = 0.60 M

Increase total pressure by adding 5 mol of an inert gas (He)


Chatelier's prediction: partial pressures not affected => no difference
concentrations not affected => no difference


No change in equilibrium



Ammonia synthesis : changing temperatures
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Initial: [N
2
] = 1.00 M [H
2
] = 3.0 M [NH
3
] = 0.0 M
At equilibrium : [N
2
] = 0.70 M [H
2
] = 2.10 M [NH
3
] = 0.60 M

Change the temperature from 500 K to 400 K


Chatelier's prediction: the reaction is exothermic => more product formed

Confirm: at 500 K K
c
= 5.6 x 10
2
at 400 K K
c
= 0.50 (independent data)

New equilibrium: [N
2
] = 0.51 M [H
2
] = 1.54 M [NH
3
] = 0.97 M

But the equilibrium will be achieved at slower rate!



Ammonia production
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Favored by:

adding reactants (limited
by a maximum total pressure)

increasing partial pressures (limited by
the resilience of the reaction
vessel to rapture)

lowering the temperature (limited
by the reaction rate; at lower
temperature the reaction is too
slow to rapidly reach the equilibrium)




% ammonia at equilibrium, starting with
1:3 mixture of N
2
and H
2
Ammonia production
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Use a catalyst: it does not change equilibrium position, only the rate at which
equilibrium is achieved.
Use a flow reactor, continually adding H
2
and N
2
, removing the product, and recycling
the unused reactants.
Use liquefaction of NH
3
to separate it from other gases which liquefy only at much lower
temperature.