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Topic 4.

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EQUILIBRIA
Dynamic equilibria
Equilibrium constants
Can!in! te position o" equilibrium
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REVERSIBLE REACTIONS
Consider a reversible reaction A + B C + D
As the reaction proceeds, the rate of the forward reaction decreases and the rate of the
reverse reaction increases. Eventually, the reaction will reach a stage where both forward
and backward reactions are proceeding at the same rate
At this stage, a dynamic equilibrium has been reached. !he reaction has not stopped" it
is simply moving in both direction at the ame rate. !his is in contrast to a static
e#uilibrium, in which there is no movement in either direction. Chemical e#uilibria are in
general dynamic rather than static.
All reactions are reversible in theory" although in practice many are not considered to be
so
$n some reactions, the reverse reaction is not allowed to take place. %any reactions take
place in an open system, where the products, often gases, are allowed to escape as they
are formed. !he reverse reaction is therefore not possible and e#uilibrium is never
reached. !he evaporation of water is an e&ample of this
Eg '()*l+ '()*g+
!his reaction would not be e&pected to proceed significantly under normal conditions,
since water is more stable than steam at normal temperatures. 'owever puddles will
disappear completely if left for long enough. !his is because the water vapour is removed
by wind currents as soon as it is produced, and so the reverse reaction is not allowed to
take place.
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$n other reactions, even where the system is closed, the reverse reaction is insignificant
Eg '
+
*a#+ + )'
,
*a#+ '()*l+
As the reverse reaction is not significant, the reaction is represented by single arrow.
-eactions are therefore only represented by e#uilibrium signs if
- the system is closed
- the reverse reaction is significant
Eg '(*g+ + $(*g+ ('$*g+, closed system, reverse reaction significant" reaction
represented by e#uilibrium sign.
E!"ILIBRI"# CONSTANTS
$% E&'reion (or equilibrium contant )*c+
Consider the reversible reaction A + .B C + (D
!he rate e&pression for the forward reaction can be written
-ate / kf0A10B1
.
, where kf is the rate constant for the forward reaction.
!he rate e&pression for the reverse reaction can be written
-ate / kr0C10D1
(
, where kr is the rate constant for the reverse reaction.
At e#uilibrium, the rates of the forward and reverse reactions are e#ual
kf0A10B1
.
/ kr0C10D1
(
!his can be rearranged to give kf2 kr / 0C10D1
(
0A10B1
.
3ince the rate constants are constant at a given temperature, it follows that the term
kf2 kr is also constant at a given temperature. $t is therefore normally regarded as a single
constant 4c and is known as the equilibrium contant of the reaction.
4c / 0C10D1
(

0A10B1
.
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,% "nit (or equilibrium contant )*c+
!he units of the e#uilibrium constant vary, depending on the number of species involved.
!he units can be deduced by multiplying out the units of concentration and cancelling as
appropriate. !he units of the above e#uilibrium constant are mol
,5
dm
.
.
Eg '(*g+ + $(*g+ ('$*g+
4c / 0'$1
(
$t has no units.
0'(10$(1
Eg 6Cl7*g+ 6Cl.*g+ + Cl(*g+
4c / 06Cl.10Cl(1 $t has units of moldm
,.
.
06Cl71
E&tenion - equilibrium contant
!he value and units of e#uilibrium constant depends on the way the reaction is
written.
Eg consider the e#uilibrium (3)(*g+ + )(*g+ (3).*g+
4
5
c / 03).1
(
units mol
,5
dm
.
.
03)(1
(
0)(1
$f written in the following way, however 3)(*g+ + 52()(*g+ 3).*g+
4
(
c / 03).1 units mol
,52(
dm
.2(
.
03)(10)(1
52(
4
5
c and 4
(
c do not have the same units or the same numerical value" in fact
4
5
c / *4
(
c+
(
.
!he e#uilibrium constants of the forward and reverse reactions are not the same, but
are related by a simple relationship
Eg for the reaction (3)(*g+ + )(*g+ (3).*g+
4c*f+ / 03).1
(
4c*r+ / 03)(1
(
0)(1
03)(1
(
0)(1 03).1
(
!he two e#uilibrium constants can be related by the relationship 4c*f+/ 524c*r+
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.% Calculation o( equilibrium contant )*c+
$f the concentrations of all the reacting species are known, the e#uilibrium constant can
be calculated by putting the values into the e&pression for the e#uilibrium constant and
computing the value.
)ften, however, the concentration of only one of the species at e#uilibrium is given, and
the others must be deduced. !his is done by considering the way in which the species
react
Eg Consider the e#uilibrium '(*g+ + $(*g+ ('$*g+
$f the initial amounts of hydrogen and iodine are a and b, and & moles of hydrogen react
with & moles of iodine to give (& moles of hydrogen iodide, then the amounts of
hydrogen and iodine in the mi&ture at e#uilibrium are *a,&+ and *b,&+ respectively.
'(*g+ + $(*g+ ('$*g+
$nitially a b 8
At e#uilibrium *a,&+ *b,&+ (&
$f a, b and the amount of one of the species present at e#uilibrium is known, then the
value of & can be deduced and the amounts of all the other species at e#uilibrium can also
be deduced.
Eg $f 5.7 mol of hydrogen and 5.( mole of iodine are mi&ed together and allowed to reach
e#uilibrium, the amount of hydogen iodide present at e#uilibrium is found to be 5.9 mol.
(& / 5.9, so & / 8.:, *a,&+ / 8.; and *b,&+ / 8.<
!herefore at e#uilibrium there are 8.; moles of hydrogen, 8.< moles of iodine and 5.9
moles of hydrogen iodide.
!hese amounts can be converted into concentrations, and then inserted into the
e&pression for e#uilibrium constant.
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C/AN0IN0 T/E 1OSITION O2 E!"ILIBRI"#
$f the conditions are changed after e#uilibrium has been established, the system may no
longer be at e#uilbrium and may move in one direction or another to re,establish
e#uilibrium. !he direction in which the system will move to re,establish e#uilibrium can
be predicted by =e Chatelier>s principle
?$f a constraint is imposed on a system at e#uilibrium, then the system will respond in
such a way as to counteract the effect of that constraint.?
3uch constraints can be the addition or removal of one of the reactants or products, a
change in pressure, a change in temperature or the addition of a catalyst.
Each must be treated separately
5. Concentration
=e Chatelier>s principle predicts that if a reactant>s concentration in a system is increased,
the system will move to the right in order to decrease the concentration of that reactant. $f
the reactant>s concentration is decreased, the system will move to the left in order to
replace that reactant. 3imilarly, if a product>s concentration is increased then the system
will move to the left and if a product>s concentration is decreased then the system will
move to the right.
Changing the concentration o( reactant and 'roduct has no effect on the rate
constants of the forward or reverse reactions. !herefore it ha no e((ect on the
equilibrium contant.
@iven that 4c is unchanged, the effect of changing the concentration of one of the species
can be shown with reference to 4c
Consider the reaction aA + bB cC + dD
4c / 0C1
c
0D1
d
0A1
b
0B1
b
$f the concentration of A or B is increased, then 0C1 and 0D1 must increase to maintain 4c.
3imilarly if the concentration of C or D is increased, then 0A1 and 0B1 must increase to
maintain 4c.
(. 6ressure
!he pressure in a system depends on the number of gas molecules in the system. =e
Chatelier>s principle therefore predicts that if the pressure of the system is increased, the
system will move towards the side which has fewer gas moles. $f the pressure of the
system is decreased, the system will move towards the side which has more gas moles. $f
the number of gas moles on both sides in the same, then pressure has no effect on the
e#uilibrium position.
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Eg 6Cl7*g+ 6Cl.*g+ + Cl(*g+
$f the pressure is increased, the system will move to the left. $f the pressure is decreased,
the system will move to the right.
Eg (3)(*g+ + )(*g+ (3).*g+
$f the pressure is increased, the system will move to the right. $f the pressure is decreased,
the system will move to the left.
Eg ('(3*g+ + 3)(*g+ .3*s+ + ('()*l+
$f the pressure is increased, the system will move to the right. $f the pressure is decreased,
the system will move to the left.
Eg '(*g+ + $(*g+ ('$*g+
Changing the pressure will have no effect on the position of this e#uilibrium.
3ince changes in pressure affect the reactant concentrations and not the rate constants, it
follows that the equilibrium contant i not a((ected by change in 'reure.
.. !emperature
$f the forward reaction is e&othermic, then the temperature of the system will rise if the
forward reaction takes place. !he reverse reaction will therefore be endothermic, and the
temperature of the system will fall if the reverse reaction takes place.
=e Chatelier>s principle therefore predicts that an increase in temperature will favour the
endothermic reaction, and that a decrease in temperature will favour the e&othermic
reaction. $f the forward reaction is e&othermic, then an increase in temperature will cause
the system to shift to the left, and a decrease in temperature will cause the system to shift
to the right. $f the forward reaction is endothermic, than an increase in temperature will
cause the system to shift to the right, and a decrease in temperature will cause the system
to shift to the left. $f ' / 8, then a change in temperature will have no effect on the
position of e#uilibrium.
Eg (3)(*g+ + )(*g+ (3).*g+, ' / ,ve
!he forward reaction is e&othermic so is favoured by decreasing the temperature. !he
reverse reaction is endothermic so is favoured by increasing the temperature.
Eg CaC).*s+ Ca)*s+ + C)(*g+, ' / +ve
!he forward reaction is endothermic so is favoured by increasing the temperature. !he
reverse reaction is e&othermic so is favoured by decreasing the temperature.
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A change in temperature changes the rate constants for both forward and reverse reactions
and is therefore likely to change the value of the e#uilibrium constant. I( the reaction i
e&othermic3 then an increae in tem'erature 4ill caue the value o( *c to decreae3
and i( the reaction i endothermic3 then an increae in tem'erature 4ill caue the
value o( *c to increae.
<. Catalysts
!he addition of a catalyst will have no effect on the position of e#uilibrium. $t will
increase the rate of the forward and reverse reactions, but by the same amount. !he
position of e#uilibrium will thus be unchanged.
As the position of e#uilibrium is unchanged, it follows that adding a catalyt ha no
e((ect on the equilibrium contant.
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7. 3ummary
E((ect o( changing condition on a ytem at equilibrium
Change !ype of change Effect on e#uilibrium position Effect on e#uilibrium
constant
Concentration Add reactant or
remove product
%oves to right Ao effect
Add product or
remove reactant
%oves to left Ao effect
6ressure
*or volume+
$ncrease pressure or
decrease volume
%oves towards side with fewer gas moles
*right if n / ,ve, left if n / +ve+
Ao effect
Decrease pressure or
increase volume
%oves towards side with more gas moles
*left if n / ,ve, right if n / +ve+
Ao effect
!emperature $ncrease temperature %oves in endothermic direction
*right if ' / +ve, left if ' / ,ve+
$ncreases *if ' / +ve+
Decreases *if ' / ,ve+
Decrease temperature %oves in e&othermic direction
*left if ' / +ve, right if ' / ,ve+
Decreases *if ' / +ve+
$ncreases *if ' / ,ve+
Catalyst Add or remove
catalyst
Ao effect Ao effect
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