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c 


 
c 
 
  

N2(g) + 3H2(g) 2NH3(g)


‡ Rates of the forward and reverse
reactions are equal
‡ There is no net change in the overall
composition of the reaction mixture
‡ Dynamic equilibrium
‡ µReactants¶ substances on the left
‡ µProducts¶ substances on the right
c 
 
(
c 
 
(
 

 
 
N2O4(g) 2NO2(g)
c 
 
(
c 
 
(
 

 
 

‡ For a given OVERALL system


composition equilibrium concentrations
are independent of direction of approach
c  
   (
 
   (
  
   
aA + bB cC + dD
‡ The following holds when equilibrium
is established:
 å   å


     
(    
 å   å
 ›

     
   

‡ Equilibrium constant expression


‡ ( ± equilibrium constant
‡ ( dependent on temperature, always
specify temperature when ( reported
c  
   (
 
   (
  
   
aA + bB cC + dD
‡ The following holds when equilibrium
is established:
å å 
( 
å  å ›

‡ Equilibrium constant expression


‡ ( ± equilibrium constant
‡ ( dependent on temperature, always
specify temperature when ( reported
c  
   (
 
   (
  
   
aA + bB cC + dD
å å
V 
å  å ›

‡ V ± reaction quotient
‡ Expression for systems not necessarily
at equilibrium
‡ ( can have only one positive value at
a specific temperature
‡ V can have any positive value
c  
   (
 
   (
  
   
‡ V = ( at equilibrium
‡ V > ( system reacts to use up
products and generate more reactants
‡ V < ( system reacts to use up
reactants and generate more products

   
   
(    
 
   
   
   
c  
   (
 
   (
  
   
‡ The relationship between ( and (
O
 

( (   
 
ǻ
= (number of moles of
  products) ±
(number of moles of
  reactants)
± Important to use correct units in this
equation
‡ Equilibrium concentrations in mol m-3
‡ Equilibrium pressures in Pa
l 
 O l  

c  
   (
 
   (
  
   
‡ Manipulating equilibrium constant
expressions
± When the direction of an equation is
reversed, the new equilibrium constant is
the reciprocal of the original

å l
l + lu l å l ålu
'
†
ål ålu
l l + lu
ål
' 1
( 
(
c  
   (
 
   (
  
   
‡ Manipulating equilibrium constant
expressions
± When the coefficients in an equation are
multiplied by a factor, the equilibrium
constant is raised to a power equal to
that factor.
ål
PCl3 + Cl2 PCl5 †
ål ålu
2
( "
åPCl5
2PCl3 + 2Cl2 2PCl5
åPCl3 2 åCl2 2

'' 2
†
c  
   (
 
   (
  
   
‡ Manipulating equilibrium constant
expressions
± When chemical equilibria are added,
their equilibrium constants are multiplied.
åN2O 2
2N2 + O2 2N2O ( 1
åN2 2 åO2
åNO2 4
2N2O + 3O2 4NO2 ( 2 
åN2O 2 åO2 3

†
å u Ñ
2N2 + 4O2 4NO2
å u
u
åu Ñ

åN2O 2 åNO 2 4 åNO2 4


†  2 † 3
åN2 2 åO 2 åN2O 2 åO2 3
åN2 2 åO2 4
c  
   (
 
   (
  
   
‡ The magnitude of the equilibrium
constant
± Product concentrations are in the
numerator of (
± The size of ( gives a measure of how
far the reaction proceeds towards
completion when equilibrium is reached
c 
 
(
c 
 
(
 

 
 
‡ The magnitude of the equilibrium
constant
reactant product
c  
   (
 
   (
  
   
‡ Equilibrium constant expressions for
heterogeneous systems
± Homogeneous reaction, all reactants and
products are in the same phase
± Heterogeneous reaction, more than one
phase exists in reaction mixture
2NaHCO3(s) Na2CO3(s) + H2O(g) + CO2(g)
( = [H2O(g)][CO2(g)]
± Do not include the concentrations of pure
solids or pure liquids
c 
 
(
c 
 
(
 

 
 
‡ Equilibrium constant
expressions for
heterogeneous systems
± For any pure liquid or solid at
constant temperature, the
ratio of amount of substance
to volume of substance is
constant
c 
 
 
  
‡ Free energy diagrams
± Phase changes
c 
 
 
  
‡ Free energy diagrams
± Chemical reactions

3
4

4
1
2
c  
    

‡ The relationship between §>l and (
O> † O>  È  lnV
± is the gas constant, 8.3141 J K±1 mol±1
± is the temperature in kelvin
± lnV is the natural logarithm of the
reaction quotient
‡ >      V is calculated using
partial pressures expressed in Pa
‡       V is calculated from
molar concentrations
c  
    

‡ The relationship between §>l and (
>  >  È  lnV
The reaction 2NO2(g) N2O4(g) has ǻ>l = ±5.40
kJ mol-1 at 298 K. In a reaction mixture, the partial
pressures of NO2 and N2O4 are 0.25 × 105 Pa and
0.60 x 105 Pa, respectively. In which direction must
this reaction proceed to reach equilibrium?
=   = 
2 4
 u
  Ñ


V= 
=   = 
2 O †O È l  u
 =  
 2
   =  
 =   =  
u

    
c  
    

O  † .Ñ kJ l  † .Ñ  J l  † u (

† . Ñ J ( l  =   1 10 5 Pa
  † .    
u Ñ
  u
† .u   
 5 
 0.60 10 
 

5
3 -1 ã1 -1
>  ã5.40 10 J mol È 8.314 J K mol 298K
ln  1 10
2 
  0.25 105  
 5  
  1 10  
 Èu.  u J l ã

ǻ> is positive, forward reaction is nonspontaneous


so the reverse reaction occurs
c  
    

‡ The relationship between §>l and (

O †O È l V

± If the system is at equilibrium


i §> = 0
‡ V=(

0†O È l (

O † l
c  
    

‡ The relationship between §>l and (

O> †  (
2SO2(g) + O2(g) 2SO3(g)
ǻ> = -1.40 x 102 kJ mol-1 for this reaction at 25 °C.
What is the value of (= at this temperature?

O      .
l  †

   uÑ
ln ( = 

ã ã1.40 105 J molã1

8.314 J K -1 molã1 298K

ln ( =  È56.5
c  
    

‡ The relationship between §>l and (
± Thermodynamic data collected at 25 °C
may be used to calculate the values of
equilibrium constants at temperatures
other than 25 °C
± Values of §Rl and § l do not change
much with temperature
c   
  
  
‡ Le Châtelier¶s principle
± If an outside influence upsets an
equilibrium, the system undergoes a
change in a direction that counteracts
the disturbing influence and, if possible,
returns the system to equilibrium
± Better to compare equilibrium constant, (,
and reaction quotient, V, when examining
the effect of perturbation to a chemical
process at equilibrium
c   
  
  
‡ Adding or removing a product or
reactant
± When not a pure solid or liquid removal
or addition of a reactant or product
instantaneously alters the concentration
of that species in the reaction mixture
± The value of V changes so that V  (,
the system is no longer at equilibrium
c   
  
  
‡ Adding or removing a product or
reactant
± V = ( equilibrium
± V < ( shift towards products
± V > ( shift towards reactants
[Cu(H2O)4]2+(aq) + 4Cl-(aq) [CuCl4]2-(aq) + 4H2O(l)


lÑu 
V†  
Ñ

u
uÈ  l 
 Ñ   
c   
  
  
‡ Changing the pressure in gaseous
reactions
± Two ways of changing the total pressure
‡ Changing the volume of the system
‡ Adding an inert gas
± Consider the equilibrium
N2(g) + 3H2(g) 2NH3(g)
2
 =NH 
 3

 = 
V=   
3
 =N  =H 
 2
 2

 =   =  
  
c   
  
  
‡ Changing the pressure in gaseous
reactions
± Changing the volume of the system
 

u u
  
 
  
V †   V  u 

   
 u
 u





ÿ
  
u u

    
NH

2 2
V †
åNH3 V  3

ÿ2
N H

3 3
åN2 åH2
2 2
c   
  
  
‡ Changing the pressure in gaseous
reactions
± Adding an inert gas
‡ Increases total pressure of system
‡ Does not alter the position of equilibrium
‡ Add helium to N2/H2/NH3 equilibrium mixture
‡ Does not react with products or reactants
u
‡ V= is not changed   
 
  
V †  
    
 u
 u

  
    
c   
  
  
‡ Changing the temperature of a
reaction mixture
± Value of the equilibrium constant, (, can
only be changed by altering the
temperature
± The van¶t Hoff equation states:
d ln ( OR 
†
d  u
± The slope of the plot of ln( versus  has
the same sign as ǻRl
c 
 


‡ Changing the temperature of a reaction
mixture

ǻRl is positive ǻRl is negative


Endothermic Exothermic
V<( V>(
Products are favoured Reactants are favoured
c   
  
  
‡ Changing the temperature of a
reaction mixture
O     
ln ( ln ( †  
u 
  u 

± Can use the van¶t Hoff equation to


calculate the ( at a specified
temperature if the value of ( at
another temperature is known
c   
  
  
‡ Addition of a catalyst
± Catalysts affect the rates of chemical
reactions without being used up
± Addition of a catalyst may help bring a
system to chemical equilibrium more
rapidly
± Addition of a catalyst does not affect the
position of equilibrium
c ! 
  



‡ Calculating (c from equilibrium


concentrations
± Measure the concentrations of reactants
and products after equilibrium reached
± Substitute these equilibrium values into
the equilibrium constant expression to
calculate (
c ! 
  



At a certain temperature, a mixture of H2 and


I2 was prepared by placing 0.020 mol of H2
and 0.020 mol I2 into a 2.00 litre flask. After a
period of time, the equilibrium:
H2(g) + I2(g) 2HI(g)
was established. The purple colour of the
I2 vapour was used to monitor the reaction,
and it was determined that, at equilibrium, the
I2 concentration had dropped to 0.020 mol L±1.
What is the value of Kc for this reaction at this
temperature?
c ! 
  



åHI 2
( 
åH2 åI2
equilibrium initial change in
= +
concentration concentration concentration

H2(g) + I2(g) 2HI(g)


Initial concentration (mol L-1) 0.100 0.100 0.000
Change in concentration (mol L-1) -0.080 -0.080 +2(0.080)
Equilibrium concentration (mol L-1) 0.020 0.020 0.160

. 
u
 †
.u
.u

 † Ñ
c ! 
  



‡ The concentration table ² a summary


1. Only equilibrium concentrations can be
substituted into the equilibrium constant
expression
2. Initial concentrations should be in mol L±1.
The initial concentrations are those present
in the reaction mixture when it is prepared
3. Changes in concentrations 
  occur in
the same ratio as the coefficients in the
balanced equation
c ! 
  



‡ The concentration table ² a summary


4. In constructing the µChange in
concentration¶ row reactant concentrations
should all change in the same direction
and have the same sign.
Row product concentrations should all
change in the opposite direction and have
the opposite sign.
c ! 
  



‡ Calculating equilibrium concentrations


from initial concentrations
± Involves the use of initial concentrations
and ( to calculate equilibrium
concentrations

± Require a little applied algebra


± Concentration tables can be very helpful
c ! 
  



The water-gas shift reaction:


CO(g) + H2O(g) CO2(g) + H2(g)
has ( = 4.06 at 500 °C.
If 0.100 mol of CO and 0.100 mol of H2O(g)
are placed in a 1.00-litre reaction vessel at
this temperature, what are the concentrations
of the reactants and products when the
system reaches equilibrium?
c ! 
  



( 
åCO2 åH2  4.06
åCO åH2O
CO(g) + H2O(g) CO2(g) + H2(g)
Initial concentration (mol L-1) 0.100 0.100 0.0 0.0
Change in concentration (mol L-1) -x -x +x +x
Equilibrium concentration (mol L-1) 0.100-x 0.100-x x x

°
°
° † u. . °

(   4.06
0.100 ã °
0.100 ã °
° † .u u.°
°2
 4 .06
0.100 ã °
2
° È u.° † .u
° .° † .u
† Ñ. † u. ° †  . 
. °

c ! 
  



åCO  0.100 ã °  0.100 ã 0.0668  0.033M


åu  † . ° † . .  † .
åCu † ° † . 
åu † ° † . 

V 
åCO2 åH2
åCO åH2O
0.0668
2
V  2
 4.1
0.033

Rounding ( to 2 significant figures gives 4.1, so the


calculated concentrations are correct.