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Dynamic equilibria
If a reversible reaction is carried out in a closed container
so that the reactants and products cannot escape, a state of
dynamic equilibrium can be established.
A + B C + D
This state is dynamic because both the forward and reverse
reactions are ongoing.
It is an equilibrium because:
the rates of the forward and reverse reactions are
the same
the net concentrations of the components of the reaction
mixture remain constant.
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Position of equilibrium
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The equilibrium constant
At equilibrium, the ratio of the concentrations of products to
reactants is constant. The ratio value is called the
equilibrium constant, Kc. It is always the same for a
particular reaction under fixed conditions.
For the general reaction:
aA + bB cC + dD
the equilibrium constant (Kc) is given by:
[C]c[D]d
Kc =
[B]b[A]a
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Units of Kc
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Work out the units of Kc
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Calculating Kc
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The value of Kc
The size of Kc tells us about how the equilibrium mixture is
made up.
[products]
KC =
[reactants]
If Kc > 1, the concentration of products is greater than the
concentration of reactants and we say that the equilibrium
lies to the right hand side.
If Kc < 1, then the concentration of reactants is greater
than the concentration of products and we say that the
equilibrium lies to the left hand side.
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Kc calculations
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Gas equilibria
For reactions involving gases, it is difficult to measure the
concentration of a particular gas. Instead the quantity of
each gas in an equilibrium mixture is described in terms of
the pressure that it exerts the partial pressure.
partial pressure = mole fraction total pressure
(pA) (xA) (ptot)
The mole fraction is given by:
no. moles of species A
mole fraction of A =
total no. moles of all species
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Calculating partial pressures
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Calculating partial pressures
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The equilibrium constant, Kp
The equilibrium constant for gas phase reactions is called Kp.
aA(g) + bB(g) cC(g) + dD(g)
For this general equilibrium, Kp is given by:
p(C)cp(D)d
Kp =
p(A)ap(B)b
where p(A) means the partial pressure of species A
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Units of Kp
Like Kc, the units for Kp must be worked out for each reaction.
For the gas phase equilibrium:
A(g) + 2B(g) C(g) + D(g)
The equilibrium constant, Kp, is given by:
p(C)p(D)
Kp =
p(A)2p(B)
So units are calculated as follows:
(kPa) (kPa) 1
Kp = = = kPa1
(kPa) (kPa) kPa
2
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Kp expressions and units
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Calculating Kp
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Calculating Kp
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Le Chateliers Principle
Le Chateliers principle states that:
If a factor affecting the
position of an equilibrium is
altered, the position of the
equilibrium shifts to oppose
the effect of the change.
Le Chateliers principle is used to
determine what effect a change will
have on a mixture at equilibrium.
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Effect of temperature on Kc
Changing the temperature changes the value
of the equilibrium constant, Kc.
The effect on Kc depends on whether the reaction
is exothermic or endothermic.
If the reaction is exothermic, increasing the
temperature shifts the equilibrium to the left
and the value of Kc decreases.
If the reaction is endothermic, increasing the
temperature shifts the equilibrium to the right
and the value of Kc increases.
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Effect of concentration on Kc
The value of the equilibrium constant is only affected
by temperature.
If the concentration of a reactant or product changes, the
equilibrium shifts to oppose the change.
If the concentration of a product is decreased, the
equilibrium shifts to convert more of the reactants into
products.
If the concentration of a reactant is decreased, the
equilibrium shifts to favour the backward reaction.
The ratio of products to reactants is restored and the value
of Kc remains the same.
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The effect of pressure
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The effect of a catalyst
A catalyst increases the
rate of reaction without without
energy
being used up itself. catalyst
with catalyst
time
A catalyst increases the rate of the forward and backward
reactions equally.
It does not affect the position of equilibrium, the yield or the
value of the equilibrium constant.
It does, however, increase the speed at which equilibrium
is achieved.
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Le Chateliers principle: true or false?
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Industrial equilibria
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Maximizing atom economy
Industrial processes are continually being made more
economical and efficient.
Unreacted reagents are
recycled. In the Haber
process, hydrogen and
nitrogen that pass out of the
reaction vessel with ammonia
are separated out and fed
back in.
Research is ongoing for alternative
reactions that require lower
temperatures and pressures and
cheaper, more effective catalysts.
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Glossary
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Whats the keyword?
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Multiple-choice quiz
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