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Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
1
Thermodynamic Equilibrium Constant 
In addition to
K 
c 
and
K 
 p
,we often run into the “
thermodynamic equilibrium constant 
”,
K 
.Recall that
¨G 
o
can be found directly from the tables provided thatthe temperature is 298 K and all substances are in their standardstates (e.g. concentrations are 1.0 M and gas pressures are 1.0atm).
¨G 
o
may be obtained
at any temperature
providing thesubstances are in their standard states using the equation
¨G 
o
=¨H 
o
- T¨S 
o
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
2
However,
for a process A + B
Î
Cwhere A, B and C are not in their standard states,
¨G =¨G 
o
+ RTln[C]/([A][B])
 At equilibrium,
¨G=0 and [C]/([A][B] = K ¨G 
o
= -RT lnK K 
is:
x
unitless constant found by using ratios of effective partial  pressures to a “reference pressure” of 1.0 atm or by using ratios of effective concentrations to a “referenceconcentration” of 1.0 mol/L 
x
these ratios are often called “
relative activities (a)”.
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
3
Relative Activity 
“
 Activity” 
of substance measures effectiveness of substance ininfluencing the position of equilibrium.
 3 NO(g)
Ù
N 
2 
O(g) + NO 
2 
(g)
e.g. the
higher [NO] 
, the more equilibrium pushed to right.
“Relative activity (a)” 
of substance:
x
is its activity relative to activity if present in standard state.
x
standard state activities of solutions (1.0 M) and gases(pressure/100kpa) or (pressure/1.0 atm)
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
4
Let’s get better understanding of 
activities
x
activies
required because equilibrium influenced by“effective”concentrationsand notstoichiometric concentrations
x
suppose a solution of strong electrolyte such as 1.0 mol/LMgCl
2
is made
x
from stoichiometry, assumption is that [Mg
2+
] = 1.0 mol/L and[Cl
-
] = 2.0 mol/L
x
however, in solution, ions not independent of one another 
x
instead, each ion surrounded by cluster of ions of oppositecharge
 
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
5
 
x
instead of 1.0 mol/L MgCl
2
reacting as if [Mg
2+
] = 1.0 mol/Land [Cl
-
] = 2.0 mol/L (
stoichiometric concentrations
),attractionsby ionic atmosphere might reduce ionic mobility resulting in
“effective” concentrations
of 0.9 mol/L and 1.8 mol/L.
x
These
effective concentrations – concentrations that appear tobe present as far as reaction concerned –are
called
activities
x
If solutions sufficiently dilute,
stoichiometric concentrations
and
effective concentrations
are the same
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
6
Note:
in this course, systems will be considered ideal so that activities may be considered equal to concentrations and  partial pressures. That is,effective or activeconcentrationsand stoichiometric concentrationswill be treated as equal 
x
e.g. If partial pressure of oxygen in air is 20.9 kPa, relativeactivity of oxygen in air is
a(O 
2 
 ) = 20.9 kPa/100 kPa = 0.209
Oxygen in this case has less influence on equilibrium thanoxygen at 100 kPa because relative activity less than 1.
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
7
x
e.g. For a
3.2 mol/L
solution of sulfuric acid, relative activity of sulfuric acid in solution is
a(H 
2 
SO 
4
 ) = 3.2 M/ 1.0 M = 3.2 
Sulfuric acid with this concentration influences equilibriummore than sulfuric acid with a concentration of 1.0 M.
Note: pure liquids – H 
2 
O(l) - and pure solids - NaCl(s), areassigned relative activities equal to 1
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
8
For reaction
3 NO(g)
Ù
N 
2 
O(g) + NO 
2 
(g)K 
 p
= (P 
N2O(g)
 )(P 
NO2(g)
 )/(P 
NO(g)
 )
3
 
which has units atm
-1
or thermodynamic equilibrium constant
K = a(NO 
2 
 ) a(N 
2 
O)/a(NO)
3
 = (P 
N2O(g)
 / P 
ref 
 )(P 
NO2(g)
 / P 
ref 
 )/(P 
NO(g)
 / P 
ref 
 )
3
which has no units
 
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
9
Thermodynamic equilibrium constant(
K 
) has benefits over 
K 
c 
and
K 
 p
.
x
It can be calculated from
¨G 
o
(that is, from ¨H 
o
and ¨S 
o
 )
soextent of any equilibrium reaction can be calculated
using thermodynamic data alone
.
x
Since great deal of thermodynamic data known, additionalexperimentation is not required
x
K 
is always dimensionless.
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
10
Consider the dissociation of the weak acid
HB(aq)
HB(aq) + H 
2 
O(l)
Ù
H 
3
O 
+
(aq) + B
- 
(aq)
K 
c 
= [H 
3
O
+
(aq)][B
-
(aq)]/[HB(aq)][ H 
2 
O(l)] = [H 
3
O
+
(aq)][B
-
(aq)]/[HB(aq)] K = a(H 
3
O
+
 )a(B
-
 )/a(HB)a(H 
2 
O)= ([H 
3
O
+
 ]/1.0 M)([ B
-
 ]/1.0M)/([HB]/1.0M)([ H 
2 
O]/1.0M)= ([H 
3
O
+
 ]/1.0 M)([ B
-
 ]/1.0M)/([HB]/1.0M) because“a(H 
2 
O
liquid 
 )”=1= K is same numerical value as K 
c 
but without units so squarebrackets kept = [H 
3
O
+
 ][ B
-
 ]/[HB] 
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
11
Heterogeneous Equilibrium 
When all reactants and products in equilibrium system are gases,system is example of 
homogeneous equilibrium
because onephase is present.
If the equilibrium contains more than one phase
, equilibrium issaid to be
heterogeneous
.In heterogeneous systems involving a gas
x
final equilibrium position does not depend on amounts of  pure solids or liquids present since concentrations of  pure solids and liquids are intrinsic properties and 
have
relative activities of 1
.
x
activities of solids and liquids are not included inequilibrium expression
for the reaction.
Chemistry 132 – 
Equilibrium Lecture 3-02– 
UsingEquilibrium Constant Expressions
12
Consider reaction
CaCO 
3
(s)
Ù
CaO(s) + CO 
2 
(g)
CO
2
CaCO
3
CaO
x
the amount of carbon dioxide doesn’t depend on amountsof solid present.
x
K doesn’t depend on amounts of solid present 
.For the above system:
K 
P 
= P 
CO2 
 K 
c 
= [CO 
2 
(g)] K = a(CO 
2 
 ) = P 
CO2 
 /P 
ref 
 
where P
ref 
= 1.0 atm
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