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Equilibrium

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10 views42 pages

Equilibrium

Uploaded by

perezshecaniah
Copyright
© © All Rights Reserved
We take content rights seriously. If you suspect this is your content, claim it here.
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What happens

in a reversible
reaction?
Reversible reactions may
be represented as
follows:

aA + bB ↔ cC + dD
What is
chemical
equilibrium?
What can you say about the number of cars inside San
Francisco if the rate at which cars enter the city is also the
same as the rate at which the cars leave the city?
Changes in the rate of the forward
and backward reactions in a
reversible reaction. Figure 2
Changes in the amount of
reactants and products in a
reversible reaction.
Figure 3
The state of
chemical
equilibrium is a
highly dynamic
state.
The Law of Mass
Action Expression/

Equilibrium Constant
Expression
For the general equilibrium
reaction:

The law of mass action


expression is written as:
Example
:

the law of mass action expression


is written as:
Seatwork
Equilibrium constants for
homogeneous gaseous
equilibria may also be
expressed in terms of
partial pressures.
For equilibrium reactions
where the reactants and
products are in different
phases (heterogeneous
equilibria), pure solids and
pure liquids are excluded in
writing equilibrium constant
expressions.
consider the reaction:

The equilibrium constant expression for


the reaction is:
Why do we omit pure
solids and pure liquids
in the equilibrium
constant expression?
When the mass of a certain pure
solid substance is doubled, its
volume is also doubled.

Therefore, when the mass and


volume is related to get the
concentration, a constant value
is obtained.
Here are other examples:
The Equilibrium Constant, K

The equilibrium constant, K, is


the numerical value that is
obtained when equilibrium
concentrations are substituted
to the equilibrium constant
expression.
Consider the reaction for the production of
phosgene (COCl2), a toxic gas used in the
manufacture of certain polymers and
insecticides, at 100°C:
Q: If a certain
fraction equates to a
very large value, then
which has a larger
value between the
numerator and the
denominator?
A: The numerator
should have the
larger value.
The relationship of K value and the
composition of the equilibrium
mixture.
The Reaction Quotient, Q

Q: What if the
concentrations of reactant
and products given are not
equilibrium
concentrations?
A: If the concentrations
given are not
equilibrium
concentrations, we can
calculate for the
reaction quotient.
The reaction quotient can be
expressed as:
In what direction
will the reaction
proceed in order
to attain the
equilibrium?
The Kc for the reaction N2 (g) + 3H2(g) →
2NH3(g) at 472 0C is 0.105. Suppose a mixture
of 2.00 mol of H2, 1.00 mol of N2 and 2.00 mol
of NH3 is placed on a sealed 1.00 L -container.

Q : How would you know if the reaction is


already at equilibrium?
To attain equilibrium, the quotient
must decrease to 0.150.
This will only happen if the
concentration of NH3 will decrease
and the concentrations of N2 and H2
will increase.
Thus, the reaction must proceed
inthe backward direction until
equilibrium is attained.
Write the equilibrium constant
expression, Kc, for the following
reactions.
For the following reactions at
equilibrium, identify which between the
reactants and products is dominant
At 450 °C, the Kp for the reaction N2(g) + 3
H2(g) 2NH3(g) is 4.5 × 10–5. For each mixture
listed, indicate whether the mixture is at
equilibrium at 450 °C. If it is not at equilibrium,
indicate the direction (toward product or
toward reactants) in which the mixture must
shift to achieve equilibrium.
1. 98 atm NH3, 45 atm N2, 55 atm H2
2. 2. 57 atm NH3, 143 atm N2, 79.6 atm H2
3. 3. 13 atm NH3, 172 atm N2, 82 atm H2
A. Calculating K when all equilibrium
concentrations/partial pressures are known
Determining equilibrium constants when
equilibrium concentrations or partial pressures
are known involves straightforward substitution
to the equilibrium constant expression.
Example A.1: A mixture of hydrogen and nitrogen in
a reaction vessel is allowed to attain equilibrium at
472 °C. The equilibrium mixture of gases was
analyzed and found to contain 7.38 atm H2, 2.46 atm
N2 and 0.166 atm NH3. From these data, calculate
the equilibrium constant Kp for the reaction:
Example A.2: An aqueous solution of acetic acid is
found to have the following concentrations at 25 °C:
[CH3COOH] = 1.65 × 10–2 M; [H3O+] = 5.44 × 10–4 M;
and [CH3COO–] = 5.44 × 10–4 M. Calculate the
equilibrium constant Kc for the ionization of acetic
acid at 25 °C. The reaction is:
B. Calculating K from initial and equilibrium
concentrations/partial pressures In most cases,
what is known to the experimenter is the
equilibrium constant at a certain temperature and
the initial concentrations or partial pressures of the
species present. This means that equilibrium
quantities must be determined before calculating
for K. This can be done by treating the change as a
variable where the stoichiometric coefficients
from the balanced equation can be used to denote
the relationship between the changes in the
concentration/partial pressure of the reactants and
products.
Example B1: A closed system initially containing
1.000 × 10–3 M H2 and 2.000 × 10–3 M I2 at 448 °C is
allowed to reach equilibrium. Analysis of the
equilibrium mixture shows that the concentration of
HI is 1.87 × 10–3 M. Calculate Kc at 448 °C for the
reaction taking place which is
Example B2: Sulfur trioxide decomposes at high
temperature in a sealed container according to the
reaction

Initially, the vessel is charged at 1000 K with SO3(g)


at a partial pressure of 0.500 atm. At equilibrium the
SO3 partial pressure is 0.200 atm. Calculate the
value of Kp at 1000 K.
C. Calculating equilibrium concentrations/partial
pressures from initial concentrations/partial
pressures and K values

Example C1 For the equilibrium

the equilibrium constant Kp is 7.0 at 400 K. If a


cylinder is charged with BrCl(g) at an initial pressure
of 1.00 atm and the system is allowed to come to
equilibrium, what is the equilibrium partial pressure
of BrCl?
Example C2: For the reaction

Kc = 280 at 150 °C. Suppose that 0.500 mol IBr in a


2.00-L flask is allowed to reach equilibrium at 150
°C. What are the equilibrium concentrations of IBr,
I2 and Br2?

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