Sect 7.

3 Equilibrium [Text pg 110 113]

Reversible reactions
Until now we have assumed that once a chemical reaction has started it will continue until
all of the available reactants have been used up. Many reactions do behave in this way but
others do not.
If a mixture of H
2
(g) and I
2
(g) is placed in a sealed container of fixed volume some HI(g)
molecules are formed by the reaction!
H
2
(g) " I
2
(g) 2HI(g)
Initially the reaction is very fast as the concentration of the two reactants is high but as
the reaction proceeds their concentration and the rate of reaction decreases. #onversely
the chance of two HI molecules colliding and decomposing is very small initially because
their concentration is so small but as the HI concentration increases so does the rate of
the reverse reaction!
H
2
(g) " I
2
(g) 2HI(g)
$ventually the rates of the forward and reverse reactions become e%ual and no other net
change occurs to the concentrations of any of the species present. It is called !namic
equilibrium because although no visible change is observed the reaction is still proceeing
but at t"e same rate in bot" irections.
$%uilibrium is possible because the reaction is reversible and the container is sealed so
that no elements of the system can enter or leave & eg no particles and no heat. 'he
s!stem is close.
'he characteristics of a system in e%uilibrium are!
'he system is closed.
(oth forward and reverse reactions are occurring simultaneously and their rates are
e%ual.
(oth reactants and products are present together but )*' necessarily in e%ual amounts
'here is no observable change in colour pressure temperature and the ratio of
reactants to products.
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Exercises# Equilibrium reactions
+. ,hich of the following processes are examples of dynamic e%uilibrium.
a. -i%uid and gaseous mercury in a sealed thermometer at a given temperature. ./)
b. ,ater running into a la0e at the same rate at which it is leaving. ./)
c. 1 saturated solution of 2b#l
2
in a bea0er at a constant temperature. ./)
d. 1 sealed bottle of soft3drin0. ./)
e. 1 pencil contained in a sealed 4ar. ./)
S!stems at equilibrium
1 system stays at e%uilibrium unless is it sub4ected to a change from outside.
$e %"atelier&s 'rinciple states that (a s!stem at equilibrium sub)ecte to ne* conitions
*ill a)ust itsel+ to reuce t"e e++ect o+ t"e ne* conitions in orer to restore
equilibrium&. In other words the reaction will read4ust itself so that it opposes and
minimi5es the effect of the new conditions. 'his applies to any system in e%uilibrium
,ppl!ing $e %"atalier&s 'rinciple to s!stems in equilibrium
1. %"ange in concentration
If the concentration of a chemical on one side of the e%uation is lowered for some
reason the reaction shifts in the direction that replaces that which is lost.
If the concentration of one side is increased then that side will react %uic0ly to get
rid of the excess and restore e%uilibrium conditions.
-. %"ange in temperature
1 change in temperature will affect the e%uilibrium. 1 reversible reaction is
exothermic in one direction and endothermic in the other.
If the temperature is raised ie the heat of the system is increased the e%uilibrium
shifts so more endothermic reactions occur and so the temperature decreases
again. 'he excess heat is absorbed.
If the temperature is lowered the e%uilibrium shifts so the more exothermic
reactions occur and more energy is released to increase the temperature.
3. %"ange in pressure
If the reaction involves gaseous particles with different numbers of molecules on
each sides and a pressure change occurs the e%uilibrium shifts so that e%uilibrium
pressure is restored.
If the pressure is increased on a gaseous e%uilibrium it must somehow create less
pressure to reduce the effect and does this by ma0ing a smaller number of gas
particles by shifting toward the side with less gas particles.
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If the pressure is decreased then the e%uilibrium needs to ma0e more gas particles
in order to bring the pressure bac0 up again and shifts toward the side with more
gas particles.
.. ,ing a catal!st
'he addition of a catalyst oes not c"ange the concentrations of reactants or products.
It does speed up the reaction rate in bot" forward and reverse directions and allows the
system to reach e%uilibrium more rapidly but neither reaction is favoured and thus no
more/less of either reactants/products is used/formed. )* #H1)6$ I) $7UI-I(8IUM.
T"e /aber 'rocess 0 ,n example o+ an equilibrium s!stem
'he Haber process is the process by which ammonia is made from nitrogen and hydrogen.
It is an important industrial process for changing nitrogen into a form that is useful for
plants to absorb as a source of nitrogen.
'he reaction follows the e%uation below!
)
2
" 9H
2
2)H
9
H : 3;2 0< mol
3+
'he reaction is exothermic in the forward direction and endothermic in the reverse
direction. 1ccording to -e #hatelier=s principle an increase in temperature should move
the e%uilibrium to the left to produce less ammonia because this will use up the added
heat. -owering the temperature will produce a greater yield of ammonia but it will also
decrease the rate of the overall reaction.
1ccording to -e #hatelier=s principle an increase in pressure should move the e%uilibrium to
the right to produce more ammonia. However disadvantages to increasing pressure are!
(i) increased cost because of the thic0ness of the walls of the plant needed to contain the
reaction.
(ii) increased pressure means increased temperature and its disadvantages.
High pressure is expensive to maintain and at low temperature the e%uilibrium is slow to
reach e%uilibrium so a compromise has to be reached. 'he conditions at which the Haber
process usually operates are as follows!
2ressure of 2>> atm.
'emperature from 9?> to @A> #.
6round Iron catalyst. (to increase the rate at the lower temperature)
'he e%uilibrium mixture is cooled to li%uefy the ammonia and remove it.
Becreasing the concentration of a product causes the e%uilibrium to shift to ma0e more.
Unused nitrogen and hydrogen is continuously recycled bac0 into the system.
Increasing the concentration of the reactants causes the e%uilibrium to shift to ma0e
more products.
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