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Chemical

Equilibrium
Non-Reversible Reaction
• Most reaction goes to completion. The reaction
will continue until one or more reactants are
completely used up in the reaction. When this
happens, the reaction stops. All reactants are
converted to products

• Example:
MgCO3 +H2SO4 → MgSO4 + CO2 + H2O
Reversible Reaction
• There are also reactions which do not go to
completion. As soon as some product molecules
are formed, they react with one another to form
reactant molecules. Such reactions are called
reversible reactions.
A + B  C + D
• Reversible reactions will reach a state called
EQUILIBRIUM where the concentration of both
reactants and products remain constant with
time, but reaction is not static!
Equilibrium definition:
• The DYNAMIC state of a chemical reaction is
where the rate of forward reaction is equal to the
rate of reverse reaction.
Rate forward = Rate reverse

• Rate refer to the ‘’speed’’ of the formation of


products and reactants
• Dynamic means ‘’changing’’, where reaction does
not stop once equilibrium is reached;
– Reactants keep changing into products
– And products keep changing back into reactants
Equilibrium and Rates
Initially, the [reactants] is
the high, so the forward
reaction (kf) is fast while
the [products] is zero so
reverse reaction (kr) is
slow.

As the reaction proceed to equilibrium, the rate of


forward reaction decreases while the rate of reverse
reaction increases until they become equal
Equilibrium is attained.
Equilibrium and
Concentrations
Initially, [reactants] is high
while [products] is zero;
as reaction proceed,
reactants are use up while
more products are
formed until reaction
reaches equilibrium.

At equilibrium, the concentration of each reactant


and product remains constant (stop changing).
An Equilibrium System

At chemical equilibrium, N2O4  NO2


While [N2O4] and [NO2] become constant
• Also can refer to the following website for more information
regarding dynamic equilibrium and some equilibrium system
examples:
– Dynamic equilibrium Note 1
– Dynamic equilibrium Note 2
– Q & A on equilibrium
– Investigate equilibrium:
Practical
Result and discussion
– Equilibrium of solution (video)
– Reversible reaction
Questions
Answers
The Equilibrium Constant
aA +bB  cC+dD
• When equilibrium is reached, equilibirum
constant, Kc is the ratio between [products] over
the [reactants] in terms of molar concentration
and at constant temperature.
conc. of products
[C] c [D] d
K=
[A] a [B] b
conc. of reactants
equilibrium constant
Writing K Expression
• For homogenous system:
2SO2(g) + O2(g)  2 SO3(g)
Kc = [SO3(g) ]2
[SO2(g) ]2 [O2(g) ]

• For heterogeneous system:


Zn (s) + 2HCl (aq)  ZnCl2(aq) + H2(g)
Kc = [ZnCl2(aq) ] [H2(g) ]
[HCl(aq) ]2
The Value of Kc

• If Kc >> 1, the reaction


is product-favored;
product predominates
at equilibrium.

• If Kc << 1, the reaction


is reactant-favored;
reactant predominates
at equilibrium.
Manipulating and
calculating Kc value
The equilibrium constant, Kc of a reaction in the reverse reaction is the
reciprocal of the equilibrium constant of the forward reaction, at constant
temperature.

N2O4(g)  2NO2(g) Kc = = 0.212

2NO2(g)  N2O4(g) Kc = = [NO2]2


[N2O4]
[N2O4] 1
[NO2]2 0.212
Kc Calculations
A closed system initially containing
1.000 x 10−3 M H2 and 2.000 x 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 x 10−3 M. Calculate Kc
at 448°C for the reaction taking place, which is

H2 (g) + I2 (g)  2HI (g)


What Do We Know?

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

Initially 1.000 x 10-3 2.000 x 10-3 0

Change

At equilibrium 1.87 x 10-3


[HI] Increases by 1.87 x 10-3 M

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

Initially 1.000 x 10-3 2.000 x 10-3 0

Change +1.87 x 10-3

At equilibrium 1.87 x 10-3


Stoichiometry tells us [H2] and [I2]
decrease by half as much
[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At equilibrium 1.87 x 10-3


We can now calculate the equilibrium
concentrations of all three compounds…
[H2], M [I2], M [HI], M

Initially 1.000 x 10-3 2.000 x 10-3 0

Change -9.35 x 10-4 -9.35 x 10-4 +1.87 x 10-3

At equilibrium 6.5 x 10-5 1.065 x 10-3 1.87 x 10-3


…and, therefore, the equilibrium constant

[HI]2
Kc =
[H2] [I2]
(1.87 x 10-3 )2
=
(6.5 x 10-5 )(1.065 x 10-3 )
= 51
• Can refer to the following website for more
information regarding writing equilibrium constant,
Kc expression and some exercises on Kc
calculations.
– Note 1 (Writing equilibrium constant)
– Note 2 (Equilibrium calculation)
– Note 3 (Equilibrium constant and calculations)
– Equilibrium Law
– Study note Q & A
– Equilibrium calculation 1
Le Châtelier’s Principle

“If a system at equilibrium is


disturbed by a change in
temperature, pressure, or the
concentration of one of the
Henri Le Chatelier
components, the system will
1850-1936
shift its equilibrium position
- Studied mining
so as to counteract the effect of engineering
the changes / disturbance.”
- specialized in glass
and ceramics.
Effect of Concentration on the
Position of Equilibrium
• According to Le Chatelier’s Principle, when the
[reactants] in an equilibrium system is
increased, the equilibrium will shift to the right
hand side so that part of the added reactant is
converted into products, in order to counteract
the changes / disturbance.

[Products] increased, equilibrium shift to the left


Consider
N2(g) + 3H2(g)  2NH3(g)

Equilibrium position shifted


• If H2 is added at ta, [H2]
increases
• According to LCP,
equilibrium position will
shift to the right to
counteract the changes (ta
to tb)
• At tb attained new
ta tb equilibrium
• N2 will be consumed and
At equilibrium New equilibrium will form more NH3.
Effect of Pressure on the
Position of
Equilibrium
• According to Le Chatelier’s Principle, an increase in
the pressure to the system, will cause the equilibrium
to shift to the side with lesser number of moles of
gas, in order to counteract the disturbance.
–Pressure only affect gaseous systems, because the
volume occupied by a gas can be altered by
pressure.
–Total no. of moles of R ≠ total no. of moles of P
Consider: N2(g) + 3H2(g)  2NH3(g)

4 moles of gas ≠ 2 moles of gas

• When the pressure of the above equilibrium is


increased, the volume occupied by the gas will
decrease. The molecules are crowded closer to
one another. The addition pressure can be
relieved if the molecules are able to react so as
to reduce the total number of molecules present.
Hence the equilibrium will shift to the right
hand side, according to LCP.
• At ta, pressure of system
increased (concentration
of all the gaseous in
2y system increases

Equilibrium position shifted


according to mole ratio)
• According to LCP,
3y equilibrium position will
shift to the right (the side
where there’s lesser no.
of moles of gaseous),
y counteract the changes
(ta to tb)
ta tb • At tb attained new
equilibrium
At equilibrium New equilibrium• N2 & H2 will be consumed
to form more NH3.
Effect of Temperature on
the Position of
Equilibrium
• According to Le Chatelier’s Principle, an increase
in the temperature of the system, will cause the
equilibrium favor the side which is endothermic
reaction, in order to counteract the disturbance.
–For reaction that goes to completion [→],
if ΔH = -ve means the reaction is exothermic.
–For reversible reaction []; if ΔH = -ve means
that the forward reaction is exothermic, while
the reverse reaction is endothermic.
N2(g) + 3H2(g)  2NH3(g)
ΔH = -ve

Equilibrium position shifted


• If Temp is decrease at ta
3y • According to LCP,
2y
equilibrium position will
shift to the right to
counteract the changes
(ta to tb)
y • At tb attained new
equilibrium
ta tb • N2 will be consumed and
will form more N2 & NH3.
At equilibrium New equilibrium
• Catalysts increase the rate of both the forward
and reverse reactions.
Equilibrium is achieved faster, but the equilibrium
composition remains unaltered (equilibrium
position will not change).

Only a change in temperature of equilibrium


system will change the Kc value, changes in
concentration and pressure will not change the
Kc value.
More on Le Chatelier’s Principle:
• Study note Q & A
• Note
• Le Chatelier Lab:
– Practical
– Result and Discussion
View the videos below regarding the effect of
concentration, temperature and pressure on the
equilibrium position based on Le Chatelier’s
Principle through simple experiment in the
laboratory:
– Video 1 (temperature)
– Video 2 (pressure)
– Video 3
– Video 4
– Video 5
• Online videos on Chemical equilibrium:
equilibrium
– Equilibrium 1
– Equilibrium 2
– Equilibrium 3
– Equilibrium 4
– Equilibrium 5
– Equilibrium 6
– Equilibrium 7
• Extra notes for Chemical equilibrium:
equilibrium
– Study note Q & A
– Note 1
– Note 2
– Note 3

• Application of chemical equilibrium to industry process:


• Haber Process
• Contact Process
• Manufacture of Ethanol