1 Chemical Equilibrium Notes Ech 1201

MZUNI CHEMISTRY DEPT ECH 1201
Wednesday, December 7, 202 TEACHING NOTES 1

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Contents
Reversible and irreversible changes
Dynamic and non-dynamic equilibrium
Law of Mass Action
Relationship between Kp and Kc
The equilibrium constant and its uses
Le Chatelier’s principle, factors affecting equilibrium
position and equilibrium constant

Solubility product, common ion effect, precipitation
prediction MZUNI CHEMISTRY DEPT ECH 1201

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Reversible and Irreversible Reactions
One of the well known reactions occurs when hydrated
copper sulfate crystals are heated.
Hydrated copper sulfate Anydrous copper sulfate + water
CuSO4.5H2O CuSO4 5H2O
The starting crystals are blue in colour while the products

are water vapour and white crystals.
If the water vapour is condensed and then added to the
white crystals, the colour changes from white to blue.
Thus, the products are changed back into the starting
material.
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In other words, the reaction is reversible.
 Reversible reactions are rxns which take place in both
directions.
 Usually, reversible reactions do not go to completion.
In eqns for reversible rxns, reactants and products are

joined by a ‘two-way’ arrow.
CuSO4.5H2O CuSO4 5H2O
In most chemical rxns, the products cannot easily be
changed back into reactants. Such rxns are said to be
irreversible.
 Irreversible reactions are rxns which take place in
one direction only. Usually, these rxns go to
completion.
 E.g.
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Equilibrium
Equilibrium is a state of a system in which there are
no observable changes in a system (e.g, concn) as
time goes by.
When a chemical rxn has reached the =bium state,
the concentration of reactants & products remain
constant over time & there are no observable changes
in the system.
However at molecular level, there is much activity.
Reactant molecules continuously form products & @
the same rate as the products form reactants in the
reverse direction, i.e., A B.
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Equilibrium
Equilibrium is a term used to denote balance, a state in
which there are no observable changes in a system as time
goes by.
If you sit balanced against another person on a see-saw,
you are in a state of static equilibrium.
 No movement is required to maintain balance.

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• Consider another system - AMEDEO walking up the steps
of a downward moving escalator:
 If Amedeo walks upwards at the same speed as the

escalator steps move downwards, where will he be
after sometime?
 Your beloved Amedeo will remain at the same
position!! Ki! Ki! Ki! Ki!
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Although there is movement in the system (both him & the
escalator), there is no observable change in the position of
Amedeo.
 The system is in a state of balance or equilibrium.
 This state of balance is referred to as “Dynamic
equilibrium”.
o Dynamic equilibrium is a balance between two objects
actively moving in opposite directions.
TYPES OF DYNAMIC EQUILIBRIA
o There are two types of Dynamic equilibria: Physical &
Chemical Dynamic Equilibria
o Chemical dynamic equilibrium involves different
substances as reactants & products
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Types of Dynamic Equilibria
Physical Dynamic equilibrium however involves 2
phases of the same substance.
Examples of Physical dynamic equilibria include
vapourisation of H2O or sublimation of I2 in a closed
container at a given temperature as per the
following equations:
H2O(ℓ) H2O(g) and I2(s) I2(g).
In the case of H2O, there will come a time when
rate of vapourisation = rate of condensation.
At this time, the vapour pressure of H2O(g) in the
closed container will be constant (will be saturated)
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Types of Dynamic Equilibria
How will the physical dynamic equilibrium be manifested in the
closed container containing I2(s) in equilibrium with I2(g)?
The study of physical equilibrium provides useful information
in equilibria studies of vapour pressures as will be appreciated
later.
CHEMICAL EQUILIBRIUM
This is the reversible rxn involving production of new products
that are different from the reactants.
This type of =bium is of particular interest to production
chemists & it leads to production of the required products.
Example is the reversible rxn involving
N2O4(g) 2NO2(g)
Colourless Browm
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Analogy of a Chemical equilibrium
A chemical equilibrium can be likened to transferring a fixed
number of pple (20) to and from 2 points, A & B
A B
20 0
If there are 2 cars carrying 5 passengers per trip, travelling in
opposite directions & same loading and off loading times:
A B
20 0
15 5
10 10
It is only when there are 10 passengers at each point when each
of the two cars will be ferrying 5 pple from each point at any
time t where there will also be 5 pple remaining at each point.
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Reversible reactions
At the start of a reversible rxn, the rate of the
forward rxn is higher than that of the reverse rxn
because the concentration of reactants is higher
than that of products.
This may be shown by
These are reactions that go/proceed in both
forward & reverse direction with time.
Note that the forward & reverse rates may be
different, but after some time, an =bium is
reached.
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Chemical equilibrium
Reversible reactions
Will the position of =bium be on the reactants’ side,
at the middle or on the products’ side?
A B A B A B
What will matter is the position of the =bium.
The position of =bium will be discussed later.
At the start of the a reversible process/rxn, the rxn
proceeds towards the formation of products.
As soon as some product molecules are formed from
reactant molecules, the reverse process commences &
reactant molecules are formed from product molecules.
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Chemical Equilibrium
As the rxn progresses, the concentration of reactants

gradually decreases.
 This decreases the rate of the forward rxn.
On the other hand, as the rxn progresses,
concentration of the products increases.
 This increases the rate of the reverse reaction.

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When the rate of the forward rxn becomes equal to that of
the reverse rxn, the rxn mixture is said to be in a state of
dynamic chemical equilibrium. (Shown by )
E.g. N2O4(g) 2NO2(g)

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Once equilibrium is achieved, the concentration of each
reactant and product remains constant.
As such, although the forward and reverse rxns are

continuing, there is no observable net change.
Since at molecular level particles are still moving, the rxn
mixture is said to be in a state of Dynamic chemical
equilibrium.
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A System at Equilibrium
Rates become equal Concentrations become constant

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The equilibrium constant, K
Consider the following data on the rxn which was collected
over a period of time:
Table 14.1: The NO2-N2O4 system at 25 °C
Initial Equilibrium Ration of Concns
Concn (M) Concn (M) at Equilibrium
[NO2] [N2O4] [NO2] [N2O4] [NO2] [NO2]2

[N2O4] [N2O4]
0.000 0.670 0.0547 0.643 0.0851 4.65 x 10-3
0.0500 0.446 0.0457 0.448 0.102 4.66 x 10-3
0.0300 0.500 0.0475 0.491 0.0967 4.60 x 10-3
0.0400 0.600 0.0523 0.594 0.0880 4.60 x 10-3
0.200 0.000 0.0204 0.0898 0.227 4.63 x 10-3
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The Equilibrium expression &
equilibrium constant, K
Analysis of data in Table 14.1 shows that although the
ratio [NO2] gives scattered values, while the ratio
[N2O4]
2
gives
[NO 2] a nearly constant value which averages
to 4.63 x 10-3, the equilibrium constant, K
[N2O4]
[NO2]2
i.e, K = where K is a constant for the =bium
[N2O4]
N2O4(g) 2NO2(g) at 25 °C (At 100 °C, it is 2.11 x 10-1
(Silberberg, page 718).
Note that the exponent (power) 2 for [NO2] in the
expression is the same as the stoichiometric coefficient
for NO2 in the reversible rxn.
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We generalise this phenomenon with the following general
reversible rxn:
aA + bB ⇌ cC + dD, where a, b, c & d are the
stoichiometric coefficient for the reaction species A, B, C &
D.
For such a rxn at =bium & at a particular temperature,
K = [C]c [D]
, where
d
K is the equilibrium constant.
[A]a [B]b
Remember that =bium concns must be used to calculate K.
The above eqn was formulated in 1864 by 2 Norwergian
Chemists; Cato Maximilian Guidberg (1836-1902) & Peter
Waage (1833-1900).

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Equilibrium Constant, K
The equation is a Mathematical expression of their
LAW THE MASS ACTION, which is true for a
reversible reaction at equilibrium and at a
constant temperature, where a certain ratio of
reactant concns raised to their power & product
concentrations also raised to their power has a
constant value, K, called the equilibrium constant.
Note that although the concns may vary, as long as a
given reversible rxn is at equilibrium & at a
constant temperature, according to the Law of Mass
Action, the value of K remains constant.

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The Equilibrium Constant Expression
The validity of the equilibrium constant (& the Law of
Mass Action) has been established empirically
(exptally) by studying many reversible reactions.
Guildberg & Waage studied many rxns in which
reactant & product concentrations varied widely and
found that the Law of Mass Action has a major
implication.
Thus for a particular system at =bium & temperature,
the same equilibrium state (Value of K) is attained
regardless of how the reaction is run, i.e. whether you
start with the reactant or product, as long as
temperature remains constant, the same value of K is
obtained.
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The Law Of Mass Action
Concentration of a substance expressed in mole/dm3 is
called Active mass.
 Active mass is represented by square brackets.
 Active mass of substance X is written as [X].
 The Law of mass action states that:
At constant temperature, the rate of a chemical rxn
is directly proportional to the active mass of the
reactant present at that time. Thus Rate of rxn ∞
[A]a. If more than one reactant takes part in the rxn
then the rate of the rxn is proportional to the
product of the active masses of the reactants.
Thus Rate of rxn ∞ [A]a[B]b.
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The Law of Mass Action
 According to the law of mass action for the general
reversible reaction aA + bB ⇌ cC + dD :
Rate of forward rxn α [A]a[B]b
Or Rate of forward rxn = kf [A]a[B]b
 Similarly,
Rate of reverse rxn α [C]c[D]d
Or Rate of reverse rxn = kr[C]c[D]d
{kf & kr are rate constants for forward and reverse rxns,
respectively& a, b, c and d are number of moles the
stoichiometric coefficients}
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At equilibrium:
Rate of the forward rxn = Rate of the reverse rxn.
I.e., kf[A]a[B]b = kr[C]c[D]d
kf c
[C] [D] d [C]c[D]d
= & what is ??
kr [A]a[B]b
[A]a[B]b
[C]c[D]d kf
Since = Kc Kc =
[A]a[B]b kr
In this form, the Law of Mass Action relates to the

equilibrium concentrations of reactants and products.
As such the Law of Mass action is also known as the
Equilibrium Law.
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The Equilibrium Constant

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What Does the Value of K Mean?
The value of K for a reversible rxn indicates whether

reactants or products are favored at equilibrium.
If K >> 1, the reaction is product-favored; product
predominates at equilibrium.

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If K << 1, the rxn is reactant-favored; reactant
predominates at equilibrium.

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 Intermediate K means significant amounts of both
reactant and product are present at equilibrium. E.g. a rxn
with K = 3.92.
Any K ˃ 10 is considered much greater than 1 and a K of 0.1 is
considered much less than 1.
WRITING EQUILIBRIUM CONSTANT EXPRESSIONS
Firstly, let us discuss the importance of knowing
equilibrium constants for systems/rxns.
Knowledge of equilibrium constants is extremely
important in Chemistry for the following reasons
1. Equilibrium constants (as will be appreciated later) are
the key to solving a wide variety of stoichiometric
problems involving reversible equilibrium systems.
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Importance of knowing equilibrium
constants for systems/rxns
2. An industrial chemist who wants to maximise yields
of products from a reversible rxn must use or would
want to use a process/rxn whose equilibrium
constants are very large.
Why??
So that the concns of the products should be big, i.e.,
maximise yield especially if the products may be
isolated from the un-reactated reactants & if the
excess reagent (or by-products) & products have
totally different physical properties such as Mpt, Bpt,
solubility or partitioning coefficient
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Importance of knowing equilibrium
constants for systems/rxns
3. A medical/clinical doctor who specialises in acid-
base imbalances needs to know the equilibrium
constants of weak acids & bases.
4. Knowledge of equilibrium constants of pertinent
(important) gas-phase rxns will give atmospheric
chemists a better understanding of the processes
involved in O3 depletion/destruction in the
stratosphere (3O2(g) 2O3(g).

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Ways of expressing concns of reactants &
products
To calculate equilibrium constants, we use
equilibrium concentrations of both reactants &
products.
However concentrations of either reactants or
products can be expressed in different units such
as molarity (M) or atmosphere (atm) for gaseous
species (pressure).
In addition, the reacting species (& products) may
not always be in the same phase such as;
H2CO3(aq) H2O(ℓ) + CO2(g) or
PbCℓ2 (s) ⇌ Pb2+ (aq) + 2 Cℓ−(aq)
C(s) + H2O(ℓ) CO2(g) + H2(g)
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Ways of expressing concentrations of
reactants & products
Because of the above, there are more than one way of
expressing equilibrium constant for the same rxn.
Let us first consider rxns in which both reactants &
products are in the same phase, i.e., Homogeneous
equilibrium
HOMOGENEOUS EQUILIBRIUM
Homogeneous equilibrium applies to rxns in which all
reacting species are in the same phase, i.e. all are in
either solid, liquid or gaseous.
An example of a homogeneous gas-phase equilibrium
is the dissociation of N2O4(g) to 2NO2(g).
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Ways of expressing concentrations of
reactants & products
The equilibrium constant, K, for the rxn:
[N2O4]
N2O4(g) 2NO2(g), is given as KC =
[NO2]2
Where Kc indicates that the concn of the reacting
species are expressed in molarity (mol/L, M).
The Law of Mass Conservation which states that
“the total mass of substances does not change
during a chemical reaction” applies during
chemical rxn.

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Ways of expressing concns of reactants &
products
However the number of individual substances
may change during chemical rxns and by
definition, their properties must change.
All the same, the total number of matter remains
constant.
Proof??
If a rxn occurs in a sealed container, the total masses
of starting materials before a rxn = total masses of
products after a rxn!!
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The Ideal gas equation, PV = nRT
An ideal gas equation describes the relationship
among the 4 variables related to gases namely; P, V, T
& n.
An ideal gas is a hypothetical gas whose pressure-
volume-temperature behaviour can be completely
accounted (described, explained) by the gas equation.
Molecules of an ideal gas do not attract or repel one
another, and their volume is negligible compared to
the volume of the container.
For non-ideal systems, the partial pressures of
individual gases (activities) are not exactly
numerically equal to concentration.
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Ideal gases
In some cases, the differences are appreciable.
Therefore unless otherwise stated, we will consider all
gaseous systems to be ideal.
Although there is no such thing in nature as an ideal
gas, our approximation for any gas to behave ideally
works rather well at most reasonable temperature &
pressure changes.
We can therefore safely use the ideal gas equation to
solve for many gaseous systems at equilibrium.

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The Ideal gas equation, PV = nRT
From the ideal gas equation; PV = nRT,
n n
P= RT and = concentration in mol/L (M)
V V
R is a constant & at fixed T, T would also be
constant.
n
P P  [ ] in mol/L
V
Concentrations of reactants & products in
gaseous reaction can also be expressed in terms of
their partial pressures.

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Concentrations as partial pressure
Why Partial Pressure?
Because the total pressure of a mixture in a closed
container is contributed by both gaseous reactants &
products.
[NO2]2
From the equation , KC = if we express the
[N2O4]
concentrations in
terms of partial pressure of the reactants & products, then
P2
NO2
Kp =
P
where PNO2 & PN2O4 are the =bium
N2O4partial pressures (in atm) of NO2(g) and
N2O4(g), respectively.
The subscript Kp tells us that the =bium concentrations
are expressed in terms of pressure & in atm.
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The Magnitude of Equilibrium Constant
The magnitude of K tells us whether an =bium rxn
favours the products or reactants, i.e, the size of K
tells us the position of equilibrium of a rxn.
Thus it tells us where the =bium lies: on the products
side or reactants side.
For a rxn aA bB, where a, b = 1, what can we say
about the position of =bium if:
(i) K = 1 (ii) K > 1 or >> 1, (ii) K< 1 or << 1?
If K = 1, then the =bium is on the middle implying
that = bium concns of both reactants & products are
unity.
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Concentrations of (pure) liquids and solids are constant at
constant temperature.
Therefore, the concentrations of solids and liquids do not
appear in the equilibrium expression.
WHY??
Becoz the properties that describe the solid & liquid such
as mole fraction do not depend on the amount taken.
What type of properties are they then?
 Intensive or Extensive?
E.g. For the equilibrium reaction:
PbCl2 (s) ⇌ Pb2+ (aq) + 2 Cl−(aq) and Kc = [Pb2+] [Cl−]2

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Manipulating equilibrium constants
The equilibrium constant for a rxn in the
reverse rxn in the reciprocal of the reaction in
the forward rxn.
[NO2]2
E.g., if for the rxn, N2O4(g) 2NO2(g), K = = 0.212
[N2O4]
Then for the reverse rxn 2NO2(g) N2O4(g),

[N2O4] 1
K1 = = = 4.71698 = 4.717
[NO2]2 0.212

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2
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c. The equilibrium constant for a net reaction made up of
two or more steps can be found from the equilibrium
constants for the individual steps.
E.g. At 1565 K we have these equilibrium constants:
2CO2(g) ⇌ 2CO(g) + O2(g) K1 = 1.6 x 10-11
2H2O(g) ⇌ 2H2(g) + O2(g) K2 = 1.3 x 10-10
CO2(g) + H2(g) ⇌ CO(g) + H2O(g) K3 = ?
[Ans : 0.35]

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Solution
2CO2(g) 2CO(g) + O2(g), K = 1.6 x 10-11 (Eqn 1)
2H2O(g) 2H2(g) + O2(g), K = 1.3 x 10-10 (Eqn 2)
 2H (g)+ O (g)
2 2 2H2O(g) K-2 = 1010/1.3 (Eqn 3)
Add Eqn 1 & 3)
2CO2(g) 2CO(g) + O2(g), K = 1.6 x 10-11 (Eqn 1)
2H2(g)+ O2(g) 2H2O(g) = 1010/1.3 (Eqn 3)

___________________________________________
2CO2(g) + 2H2)g) 2CO(g) + 2H2O(g), K4 = K1 x K3
 4
→ K =1.6 x 10-11
x 1010
/1.3 = 1.6/1.3 x 10 -1
= 1.2308x 10 -1
.
CO2(g) +H2)g) CO(g) +H2O(g) = √12.31 x 10-2 =0.35

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Alternatively
2CO2(g) 2CO(g) + O2(g), K = 1.6 x 10-11
CO (g) 2 CO(g) + ½O2(g), K= (1.6 x 10-11)½
= √16 x 10-12 = 4 x 10-6
Similarly, H2O(g) H2(g) + ½O2(g), K = √1.3 x 10-10
K = 1.14 x 10-5
 H (g) + ½O (g) H2O(g), K = 1/1.14 x 10-5
2 2
= 8.77058 x 104
Sum those in red = 4 x 10-6 x 8.77058 x 104 = 0.3508.

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Equilibrium constant for gases

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Equilibrium constant for gases, Kp
For rxns involving gases, it is easier to measure
pressure than concentration.
Why??
Because the measurement of gas pressure is not as
involving as determination of concentration. If one has
to do is to measure the pressure using a pressure gauge
while concentration measurements may involve
titration, calculation of moles (n) & volume (V)!!!
Since pressure of varies directly proportional to
concentration of a gas, the equilibrium expression may
be written in terms of partial pressures (Px) (instead of
concentration).
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Equilibrium constant for gases, Kp
In this case, the equilibrium constant is denoted
as Kp, implying that partial pressures are used in
deriving the equilibrium constant.
E.g., for the rxn : aA(g) + bB(g) cC(g) + dD(g)
c d
P P
C D
Kp = , where PA, PB, PC & PD are the partial
a b
P P pressures of gases A, B, C & D.
A B

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Relationship between Kc & Kp
In general, Kc ≠Kp because the partial pressures of reactants
& products (Activities) are not equal to their concentrations
expressed in mol/L, M.
However, since pressure is proportional to concentration of
gases, therefore equilibrium constant expression can also
be written in terms of partial pressures (instead of)
concentration.
Consider the following equilibrium in the gas phase:
aA(g) bB(g), where PA & PB are the stoichiometric
coefficients. [B]b [PB]b
Therefore KC = [A]a and Kp = where P A & PB
[P ]a A
are the partial pressures of A & B.
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A simple relationship between Kp & Kc can be
derived as follows:
Assuming an ideal gas behaviour, PV = nRT,
where P = pressure, V = volume of the container
in L, n = no. of moles, R = gas constant & T is in
Kelvin. n
A RT
PAV = nART → PA = . n
V B RT
Similarly, PBV = nBRT → PB = V
Therefore substituting the partial pressures of A
& B in the Kp expression
n RT in terms of
concentration in V ;
2
n b n b
B RT B
[PB]b V V b-a
Kp = = Kp = x (RT)
n a n
[PA]a A RT A a
V V
n n
But B A
= [B] in mol/L and = [A] in mol/L
V V
[B]b
 KP = (RT)n = KC (RT)n , where n = b-a
[A]a
i.e., n = b - a = Mol of gaseous - Mol of gaseous
products reactants
Since P = in atm, R = 0.0821 L. atm.K-1.

However if P = N. M = J, R = 8.314 J. K-1. mol-1
2
Therefore Kp = Kc(RT)∆n
= Kc (0.0821T) ∆n (units for pressure are atm).
To use this equation, the pressures in Kp must be in
atm.
In general, Kp ≠ Kc except in special cases where
∆n = 0, as in the =bium mixture of molecular
hydrogen, molecular bromine & molecular HBr
H2(g) + Br2(g) 2HBr(g).
In this case, the equation is Kp = Kc (0.0821T)0 &
Kp = Kc.

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Tutorial
1. The equilibrium constant (Kc) for the following rxn is
4.63 x 10-3 at 25oC:
N2O4(g) ⇌ 2NO2(g)
Work out the value of Kp at this temperature.
(Answer : 0.113)
2. The equilibrium constant (Kp) for the reaction
PCl5(g) ⇌ PCl3(g) + Cl2(g)
is found to be 1.05 at 250oC. If the equilibrium partial
pressures of PCl5 and PCl3 are 0.875 atm and 0.463 atm
respectively, determine the equilibrium partial pressure
of Cl2 at 250oC. [Answer : 1.98 atm]
2
Solutions
1.
Kp = Kc(RT)n = 4.63 x 10-3 x 0.0821 L.atm x 298 K

K. mol
= 113.13868 x 10-3 = 0.113
2.
PCl PCl P
0.463 atm x Cl2
3 2
Kp = = 1.05 atm = = 1.05 atm
PCl 0.875 atm
5
PCl 1.05 atm x 0.875 atm = 1.984341 atm = 1.98 atm
2
=
0.463 atm

2
2
2
2
2
2
Hence, x = 0.934
↔ Equilibrium concentrations are :
[H2] = 1.00 – 0.934 = 0.0660 M
[I2] = 2.00 – 0.934 = 1.07 M
[HI] = 2 x 0.934 = 1.87
↔ Number of moles are:
H2 = 0.0660 mol/L x 1.00 L = 0.0660 moles
I2 = 1.07 mol/L x 1.00 L = 1.07 moles
HI = 1.87 mol/L x 1.00 L = 1.87 moles

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Another example of a homogeneous
equilibrium
Firstly, let us calculate the molarity of H 2O.
In 1L or 1000g of H2O (ρ of H2O = 1 g/mL
1000 g
(1 kg/L), there are 18.02 g x mol = 55.49 mol/L
(55.5 M)
Thus [H2O] = 55.5 mol/L (55.5 M).
Consider the ionisation of ethanoic acid in H2O:
CH3COOH(aq) + H2O(ℓ) CH3COO-(aq) + H3O+(aq)
[CH1 3COO-] [H3O+]
,K
where
1
C =
K C is used to distinguish equilibrium
constant[CH
to3COOH] [H2O]later.
be derived
2
Dissociation of Acetic acid in H2O
The concentration of H2O (55.5 M) is much larger
compare to the concentration of the other species
(usually 1M or smaller) & we can assume that the
concentration of water does not change appreciably
during the ionisation reaction/process.
How??
Consider the following ionisation of 1 M CH3CO2H in
H2O with a dissociation constant, Ka of 1.8 x 10-5M
Amedeo, explain the meaning of a dissociation
constant!!
The extent to which a species ionises.
2
Dissociation constant & Quadratic Eqn
Also tells the position of equilibrium for a reaction.
Consequently, it tells us the strength of and acid.
The larger the Ka, the more we have the products
(dissociates species)
In the case of acetic acid (Ka = 1.8 x 10-5), calculate the
concentrations of the species at equilibrium.
The quadratic equation is used to calculate concentration
of species at equilibrium, especially for systems with
small Ka values.
The Quadratic eqn = X = -b, where x is
b2 - 4ac
2a
the concn of a species at equilibrium.
2
The calculation of =bium concns
CH3CO2H (aq) + H2O(l) CH3CO2-(aq) + H3O+(aq)
1.00 M 55.5 M 0 0
1- X 55.5-X X X
Ka = 1.8 x 10-5 and Quadratic eqn = X = -b   b2 - 4ac

[CH3COO-] [H3O+] 2a
Ka = -5
= 1.8 x 10
[CH3COOH]
= X2 X2 = 0.000018 (1-X)
= 0.000018
1-X = 0.000018 - 0.000018X
2
X + 0.000018X - 0.000018 = 0
a b c ( a & b are coefficients for X2 & x, resp)
X= - 0.000018   x 1 x -0.000018

2x1
X = - 0.000018  
3.24 x 10-10 + 7.2 x 10-5= -b   72.00032 x 10-6
2
2
X -0.000018  8.485 x 10-3 8.467 x 10-3
= = = 4.23 x 10-3 M
2 2
2
Concns of species at =bium
Therefore at =bium:
[CH3CO2H] = 1- 0.00423 = 0.99577 M ≈ 1.00 M
[H2O] = 55.5-0.00423 = 55.49577 ≈ 55.5 M
[CH3CO2-] = [H3O+] = 0.00423 M.
We therefore treat [H2O] as a constant & re-write
the equilibrium constant as K1c which
encompasses (includes) [H2O].
[CH3COO-] [H3O+]
Thus K1c = Kc [H2O] = [CH3COOH]
2
Equilibrium constant & its units
Note that it is general practice not to include units for
the equilibrium constant.
In thermodynamics, the =bium constant, K, is defined
in terms of activities (behaviour) instead of
concentration.
Thermodynamics is the scientific study of the inter-
conversions of heat & other forms of energy.
For an ideal system, the activity of a substance is the
ratio of its concentration (or partial pressure) to the
standard value which is 1M or 1 atm.
Since the activity is a ratio, then the units cancel out.
2
This procedure (presentation of activity
(behaviour) eliminates all units but does not
alter the numerical parts of the concentration or
pressure.
In addition, the procedure eliminates all units but
does not alter the numerical parts of the
concentration or pressure as when ∆n = 0.
How??
Even if units were included, they would all cancel
out!!
Definitely K will have no units in such cases!!
2
 It is actually more correct to present
concentrations (& pressures) as activities
because species may interact or undergo
reactions (e.g, ionisation & partial dissolving if
they are solids) which may actually affect the
calculated/theoretical & expected
concentrations ( & pressures).
 The following examples illustrate the procedure
for writing =bium constant expressions and
calculating =bium constants & expressions:

2
Exercises
(1) Write expressions for Kc & Kp (if applicable) for the
following reversible reactions at equilibrium:
(a) HF(aq) + H2O(ℓ) H3O+(aq) + F-(aq)
(b) 2NO(g) + O2(g) 2NO2(g)
(c) CH3CO2H(aq) + C2H2OH(aq) CH3CO2C2H5(aq) +
H2O((ℓ).
(2) The following =bium process has been studied at 230 °C.
2NO(g) + O2(g) 2NO2(g).
In one expt, the concns of the reacting species at =bium are
[NO] = 0.0542M, [O2] = 0.127M & [NO2] = 15.5M.
Calculate the Kc, =bium constant of the rxn at this
temperature.
2
Solutions
Strategy
Remember:
(i) the Kp expression applies only to gaseous rxns
(ii) the concentration of solvent (usually H2O) does
not appear in the equilibrium constant
expressions (which is then denoted as K1c)

2
2
Heterogeneous Equilibria
Remember a heterogeneous equilibrium results
from a reversible rxn involving reactants &
products that are in different phases.
Example
When CaCO3(s) is heated at elevated temperatures
in a closed vessel, the foll. =bium is attained:
CaCO3(s) CaO(s) + CO2(g)
The 2 solids & one gas constitute 3 separate phases
(≠ 2 because CaCO3(s) & CaO(s) will have different
structures).
2
Homogeneous equilibria
At =bium, we might write =bium constant as
[CaO] [CO2]
1
K C=
, again the[CaCO
K1C, i.e.,
3]
the K
prime c is to distinguish it from the Kc without any
constant concentration.
However, the concentration of a solid, like its density is
an intensive property & does not depend on how much of
the substance is present.
Examples include density & concentration.
Remember extensive property depends on how much
matter is considered & examples include mass, volume.
The value of an extensive quantity depends on the
amount of matter.
2
Equilibrium constant for Heterogeneous
Equilibria
For this reason, the terms {CaCO3] & [CaO] are constants and are
combined with the equilibrium constant and the resulting K c is
denoted K1c.
[CaO] [CO2]
Therefore the KC = becomes KC x [CaCO3]
[CaCO3]
[CaO]
1
= K C, the new =bium constant
The K1c is conveniently expressed in terms of a single
concentration of CO2(g), K1C = [CO2] or K1p = PCO2.
Note that the equilibrium constant K1c does not depend on how
much CaCO3(s) & CaO(s) are present.
As long as some of each is present at =bium, the activity for each
will be the same (= 1, unity).
2
Equilibria
The situation becomes simpler if we replace the
concns with activities (behaviour).
Therefore concentrations (activities) of CaCO3 & CaO
are both unity.
Similarly, the activity of pure liquids are also = 1.
Therefore if a reactant or product is a solid
or liquid (in a heterogeneous equilibrium),
it is omitted in the equilibrium constant
expression.
2
Equilibria
Alternatively, since the Kc depends on gaseous CO2,
we can express the =bium constant as Kp = PCO2.
What can you say about the relationship between Kp
& Kc?
The equilibrium constant in this case is numerically
equal to the pressure of CO2(g), an easily measurable
quantity.
Thus, Kc = Kp in this case!!

2
Exercise
(a) Write the =bium constant expression, Kc, & Kp if
applicable for each of the following heterogeneous
systems:
(i) (NH4)2Se(s) 2NH3(g) + H2Se(g)
(ii) AgCℓ(s) Ag+(aq) + Cℓ-(aq)
(iii) PbCℓ2(s) Pb2+(aq) + Cℓ-(aq)
 Why if applicable for Kp???
Solutions

2
Solutions

2
What does the =bium K (Kc/Kp) tell us?
Remember that values of Kc/Kp for a given rxn can be
calculated from known equilibrium concentrations.
Therefore once the Kc/Kp is known,
its value can be used to calculate unknown =bium
concentrations while remembering that K has a
constant value only if the T is kept constant for a
reversible rxn.
In general,
(i) The magnitude of Kc/Kp tells us the position of
=bium of a given system

2
What does the =bium K (Kc/Kp) tell us?
(ii) The equilibrium constant helps us to predict the
direction in which a given rxn mixture will proceed to
achieve a new equlibrium (after calculating &
comparing Qc/Qp in conjuction with Kc/Kp) but
Kc/Kp is a constant!!
(iii) Thirdly, =bium constant helps us to calculate the
concns of reactants & products once a new =bium has
been reached (after being disturbed= Le Chatelliers’
Principle.
We will first explore the 2 uses of equilibrium
constant in the following two sections.
2
Predicting the direction of a rxn from
comparing reacting Quotient, Qc and Kc
Let us consider the foll. Reversible homogeneous=bium
rxn:H2(g) + I2(g) 2HI(g), Kc = 54.3 at 430 °C, Thus =bium
constant, Kc, for the formation of HI(g) from molecular H 2(g)
& molecular I2(g) (all species in gaseous phase.
If in a certain expt, we place 0.243 mol of H 2(g), 0.146 mol of
I2(g) & 1.98 mol of HI(g) in a 1L vol flask, will there be a net
rxn to form more H2(g) & I2(g) (reactants) or some more
HI(g) (products)?
In other words, how will the system react to nullify
(counteract) any stress??

2
Solution
Write the Kc expression & insert the indicated initial
concentrations & calculate the value of the ratio.
2 2
[HI] [1.98] 3.9204
o = 110.50  111 = Qc
= [0.243] [0.146] =
[H2] [I2] 0.035478
o o
Note that we write the subscript 0 (or i) to indicate that

they are initial concns & that they are not =bium concns.
Becoz the quotient 111 > 54.3 (the Kc), this system is not
at =bium & consequently, some of the HI(g) will have to
react to form more H2(g) & I2(g) to decrease the value of
the quotient. (WHY???)
The net rxn will therefore proceed from right to left in
order to reach =bium!!
2
Reaction Quotient, Qc or Qp
For rxns that have not reached =bium, such as the
formation of HI(g) considered, we obtain a reaction
quotient instead of of equilibrium constant (K c or Kp)
by substituting the initial concns into the equilibrium
constant expression.
Now to determine the direction in which the net rxn
will proceed to attain =bium, we compare the values
of Qc (or Qp) & Kc/Kp.
Three possible cases may exist:
(1) Qc < Kc ( or Qp < Kp).
→ The ratio of initial concns of products to reactants
is too small as compared to equilibrium concns.
2
Reaction Quotient, Qc or Qp
To reach =bium, reactants must be converted to products &
the system proceeds from left to right (consuming reactants
& forming products to reach =bium.
(2) Qc = Kc ( or Qp = Kp).
The initial concns are =bium concentrations & the system is
at =bium
(3) Qc > Kc ( or Qp > Kp).
The ratio of initial concns of products to reactants is too
large.
To reach =bium, products must be converted to reactants.
The system proceeds from right to left (consuming
products, forming reactants) to reach =bium,
2
The reaction quotient, Q (Qc or Qp) for
Equilibria
This is the value of equilibria obtained for the
equilibrium constant expression when the
amounts substituted in the expression are not
necessary those at equilibrium.
For a rqn: aA + bB cC + dD
c
[C] [D]d where a, b, c & d are the
i i coefficients while [C]ci is
Qc = a b
[A] [B] the concentration of C in
i i
mol/L at a particular
time but not =bium concn.
2
Example
A 50.0-L rxn vessel contains 1.00 mol N 2(g), 3.00 mol H2(g) and
0.500 mol NH3(g). Will more ammonia,NH3 , be formed or will it
dissociate when the mixture goes to equilibrium at 400 oC given
that Kc = 0.500 at 400oC?
Ans:
The rxn is:
N2(g) + 3H2(g) ⇌ 2NH3(g)
Dividing the given moles by 50.0 L gives:
[N2] = 0.0200 M, [H2] = 0.0600 M and [NH3] = 0.0100 M
Since 23.1 is greater than 0.500, the rxn will go to the left as it
approaches equilibrium i.e. ammonia will dissociate.
2
Exercise
The following exercise shows how the value of Q c can
help to determine the direction of net rxn toward
=bium:
For the rxn N2(g) + 3H2(g) 2NH3(g) whose Kp = 1.2
at 375 °C, decide whether or not the system is at
=bium if at the start of a rxn, there are 0.249 mol
N2(g), 3.21 x 10-2 mol H2(g) and 6.42 x 10-4 mol of
NH3(g) in a 3.50L reaction vessel at 375 °C.
If not, predict the direction (which way) the net rxn
will proceed. (Qc = 0.613)

2
Solution
6.42 x 10-4 mol [NH3]2
[NH3] = = 1.83429 x 10-4 M Qc =
3.50 L [N2][H2]3
0.249 mol
[N2] = = 7.1143 x 10-2M [1.83429 x 10-4]2
3.50 L Qc =
3.12 x 10-2mol [7.1143 x 10-2][9.1714 x 10-3]3
[H] = = 9.1714 x 10-3 M
3.50 L
3.36462 x 10-8 3.36462 x 10-8
Qc = =
-2
[7.1143 x 10 ][771.524 x 10 ] -9 [7.1143 x 10-2][7.71524 x 10-7]
1.2
Qc = 0.613 , But, Kp = Kc (0.0821)n Kc = K p =
(0.0821) n (0.0821)
1.2
Kc = = 1.2 x (0.0821)2 = 0.008085
1
(0.0821)2
Since Qc = 0.613 & < Kc = 0.0081, therefore the rxn will proceed
from reactants to products (from left to right) to increase
[NH3] & decrease concn of both [H2] & [N2].
2
Solution if Kc = 1.2
6.42 x 10-4 mol [NH3]2
[NH3] = = 1.83429 x 10-4 M Qc =
3.50 L [N2][H2]3
0.249 mol
[N2] = = 7.1143 x 10-2M [1.83429 x 10-4]2
3.50 L Qc =
3.12 x 10-2mol [7.1143 x 10-2][9.1714 x 10-3]3
[H] = = 9.1714 x 10-3 M
3.50 L
3.36462 x 10-8 3.36462 x 10-8
Qc = =
[7.1143 x 10-2][771.524 x 10-9] [7.1143 x 10-2][7.71524 x 10-7]
Qc = 0.613
Since Qc = 0.613 & < Kc = 1.2, therefore the rxn will proceed
from reactants to products (from left to right) to increase
[NH3] & decrease concentration of both [H2] & [N2].
2
Practice exercise
For the foll. Rxn: 2NO(g) + Cℓ2(g) 2NOCℓ(g),
Kc at 35 °C = 6.5 x 104. In a certain rxn, 2.0 x 10-2 mol of
NO, 8.3 x 10-3 mol of Cℓ2 & 6.8 mol of NOCℓ were
mixed in a 2.0 L flask, determine the direction in
which the system will proceed to reach equilibrium.
(Qc = 2.8 x 107)
Since Qc > Kc, the rxn will proceed from right to left
(products to reactants side in order to decrease
[NOCℓ] with subsequent increase in concentrations of
both [NO] & [Cℓ2].
2
Solution
2.0 x 10-2 mol [NOCl]2
[NO] = = 1.0 x 10-2 M Qc =
2L [NO]2 [Cl2]
8.3 x 10-3 mol [3.4]2
[Cl2] = = 4.15 x 10-3 M Qc =
2L
[1 x 10-2]2[4.15 x 10-3]
6.8 mol
[NOCl] = = 3.4 M
2L
11.56 11.56 x 107
Qc = =
-4
[1x 10 ][4..15 x 10 ] -3 4.15
Qc = 2.7855 x 107 = 2.8 x 107

2
Uses of the Equilibrium Constant
(a) Judging the extent of a reaction:
The magnitude (size) of the constant K gives an idea of
the extent to which reactants are converted to products.
As already discussed:
 If K is very large , the rxn as written in the balanced
equation proceeds nearly to completion before
equilibrium is reached.
 If K is very small, the rxn as written in the balanced
equation barely proceeds at all before equilibrium is
reached.
 If K is intermediate, the rxn does not proceed to
completion and appreciable concentrations of reactants
and products are present in the rxn vessel when the
rxn reaches equilibrium.
2
(b) Predicting the direction of a reaction:
If known concentrations of products and reactants for a
reversible rxn are mixed in a rxn vessel, you can predict
whether more reactants or more products will form before
the rxn reaches equilibrium if K is known.
To do this, determine the value of Q using the given
concentrations of reactants and products.
 If Qc > Kc the rxn needs to create more reactants (and
use up products) to get to equilibrium, so the rxn will
be going from right to left.
 If Qc < Kc the reaction needs to create more products
(and use up reactants) to get to equilibrium, so the rxn
will be going from left to right.
 If Q = K, the rxn is already at equilibrium.
2
Position of equilibrium
This refers to the proportion of reactants to products in the
equilibrium mixture.
If the mixture is largely composed of products, the equilibrium
position lies to the right. It is shown by
aA + bB cC + dD
fewer more
reactants products
 The value of Kc (or Kp) is large in this case.
If the mixture is largely composed of reactants, the equilibrium
position lies to the left. It is shown by
aA + bB cC + dD
more fewer
 In this case, the value
reactants of Kc (or Kp) is small.
products

2
Factors that affect the position of Chemical
Equilibrium
Chemical =bium represents a balance between the forward &
reverse rxns.
In most cases, this balance is quite delicate as changes in exptal
conditions may disturb the balance (=bium) & shift the =bium
position resulting in more or less of the desired product to be
formed.
Variables that can be controlled exptally & can affect the
position of =bium are:
(i) concentration of reactants (ii) pressure (iii) volume
(iv) temperature.
The effects of these changes on equilibrium are explained by Le
Chatelier’s principle.

2
Lè Chàtelier’s Principle
We will examine how each of these variables
affects a reacting system at =bium.
In addition, we will also examine the effect of a
catalyst on equilibrium
Lè Chàtelier’s Principle is a general rule/principle
is a general rule that helps chemists to predict the
direction in which an =bium system /rxn will move
when changes in concentration, pressure, volume
or temperature (the exptal variables) have been
effected (changed) to a system at equilibrium.

2
Lè Chàtelier’s Principle states that “If an extenal stress is
applied to a system at =bium, the system adjusts in sucha
way that the stress is partially offset as the system reaches a
new =bium position.
The word “stress or disturbance ”means a change in concn,
pressure, volume or temperature that removes (disturbs) the
system from the equilibrium state.
Alternatively, “When a system at =bium is disturbed, the
system adjusts in such a way to nullify (counteract, offset)
the change.
• Le Chatelier’s principle states that if an equilibrium system is
subjected to a change the equilibrium position will move to
oppose the change.
2
The rule/principle is in honour of a French chemist
Henri Louis Lè Chàtelier who lived between 1850-
1936.
He did work on metallurgy, cements, glasses, fuels &
explosives.
He was noted for his skills in industrial management.
We will use Lè Chàtelier’s Principle to assess the
effects of such changes in the factors that affect the
position of =bium.

2
Changes in Concentration of either Reactant(s) or
Product(s)
Iron(III) thiocyanate [Fe(SCN)3)] soubilises in H2O to yield
the red soln of [FeSCN]2+(aq) .
Consider the rxn between undissociated [FeSCN] 2+(aq) and
the Fe3+(aq) & SCN-(aq):
[FeSCN]2+(aq) Fe3+(aq) + SCN-(aq)
Red Yellow Colourless
What would happen if some SCN-(aq) is added inform of
NaSCN to the above =bium system?
Which of the species is introduced/added to the system?
Therefore the stress applied to the =bium system is an
increase in the concn of SCN- the thiocyanate ion.

2
To offset this stress (the increase in [SCN]-(aq), some Fe3+
(aq) ions will react with the added SCN-(aq) ions & the
=bium shifts from right (products’ side) to left (reactants’
side): FeSCN2+(aq) Fe3+(aq) + SCN-(aq)
This shift is due to the added SCN-(aq) resulting in

deepening of the solution due to increase in production
of [Fe(SCN]2+ aq.
What would happen to the same system if Fe3+(aq) is
added inform of [Fe(NO3)3](aq)?
FeSCN2+(aq) Fe3+(aq) + SCN-(aq)

2
The red colour will also deepen because the added
Fe3+(aq) ions from [Fe(NO3)3] would shift the
=bium from left to right.
Note that both Na+(aq) & NO3-(aq) are colourless
spectator ions.
NB: Lè Chàtelier’s Principle simply explains or
summarises the observed behavoiur of =bium
system.
It is therefore incorrect to say that a given
equilibrium shift occurs because of Lè Chàtelier’s
Principle!!
2
Practice exercise
At 720 °C, the Kc for the rxn:
N2(g) + 3H2(g) 2NH3(g) is 2.37 x 10-3.
In a certain expt, the =bium concns are [N2] = 0.683 M,
[H2] = 8.30 M & [NH3] = 1.05 M.
If some NH3(g) is added to the mixture to increase its
concn from 1.05 M to 3.65 M:
(a) Use Lè Chàtelier’s Principle to predict the shift in
direction of the net rxn to reach a new =bium.
(b) Confirm your prediction by calculating the rxn
quotient, Qc, & compare its value with Kc
(Clue: Use the [NH3] of 3.65 M!!!)
2
Changes in Volume & Pressure
Changes in pressure ordinarily do not affect the
concentrations of reacting species in condensed phases such
as aqueous solutions & solids.
Why not??
Becoz liquids & solids are virtually incompressible.
However concentrations of gases are greatly affected by
changes in pressure.
Let us re-consider the ideal gas eqn, PV = nRT.
At constant Temp (& R), n 1
RT, i.e.,
P= P
V V
At fixed n, the greater the pressure, the smaller the volume &
the greater the volume, the smaller the pressure.
2
Remember that n = concentration of a gas
in mol/L. V
Therefore P α n = [gas].
V
Let us consider the following =bium system
N2O4(g) 2NO2(g) being in a
cylinder fitted with a frictionless
piston & we increase the external
N2O4(g)
pressure by pushing the piston
2NO2(g)
downwards at constant pressure
2
Since the volume decreases, what happens to the
concns of both N2O4(g) & 2NO2(g)?
n
 Since the volume decreases, then ( & the concn) for
V
both N2O4(g) & 2NO2(g) increase.
The[NO2] is squared in the =bium constant expression.
Consequently, the increase in pressure increases the value
for the numerator more than the denominator.
Therefore the system is no longer at =bium and we write:
[NO2]2o
Thus
Qc= c
Q >Kc & net rxn will shift to the left until Qc = Kc.
[N2O4]o
2
Since Qc > Kc & what is the net direction of the
shift of equilibrium?
Conversely, a decrease in pressure (due to increase
in volume) would result in Qc < Kc & the net rxn
would shift to the right until Qc =Kc.
This conclusion is also predicted by Lè Chàtelier’s
Principle.
Looking at the stoichiometry of the =bium system,
N2O4(g) 2NO2(g), increasing volume & reducing
pressure would allow the system to increase the number
of gaseous molecules resulting in a net shift from left to
right and the converse is true.
2
In general, an increase in pressure (& decrease in
volume) favours the net rxn that decreases the total
number of moles of gases (& the reverse in this case).
A decrease in pressure (or increase in volume) favours
the net rxn that increases the total number of moles
of gases (the forward rxn in the cited rxn).
For rxns in which there is no change in the number of
moles o gases (∆n = 0), a pressure or volume change
has no effect on the position of =bium.

2
Partial Pressure of a gaseous component
Partial pressure of a gaseous component A, P A, is the pressure
gas A would exert if it occupied the given space (volume)
alone.
In a given mixture of gases A & B, their total pressure, P t, is
given by adding the partial pressure of gas A & gas B,
i. e., Pt = PA + PB.
If there are nA mole of gas A and nB moles of gas B, then the
mole fraction of gas A (XA) is given by:
nA
XA = , where XA is the mole fraction of gas A
NA + NB
Similarly, nthe mole fraction of gas B (X B) is:

B
XB = , where XB is the mole fraction of gas B
NA + NB
2
2
Tutorial
 In the equilibrium system
2SO2(g) + O2(g) ⇌ 2SO3(g)
at 700 0C, the partial pressures of the gases in the
equilibrium mixture are partial pressure of SO2(g) = 0.09
atm, partial pressure of SO3(s) = 4.5 atm and partial
pressure of O2(g) = 0.083 atm. Calculate Kp.
(Ans: 3 x 104)
Solution
P2
SO3 (4.5)2
Kp = = = 3.012 x 10 4
= 3 x 10 4
P2 P (0.09)2(0.083)
SO2 O2

2
Change (increase) in the pressure of a system
without changing its volume
It is possible to change the pressure of a system
without changing its volume.
Suppose for the N2O4(g) 2NO2(g) system is
contained in a non-compressible stainless steel vessel
whose volume is constant.
The total Pressure, Pt, in the vessel can be increased
by adding an inert gas such as He to the =bium
system.
Addition of He to the equilibrium system increases
the total gas pressure & decreases the mole fraction of
both NO2(g) & N2O4(g).
2
Change (increase) in the pressure of a system
without changing its volume
The partial pressure of each gas is given by the
product of its mole fraction & the total pressure
Partial pressure of nA
x total pressure
a gaseous component ntotal
E.g. 1 x3=1 & 1 x4=1
3 4
Therefore the partial pressure of each gas does not
change.
Therefore the presence of an inert gas in such a
case does not affect (change) the equilibrium.
2
• The pressure in a container can also be increased by adding
an inert gas, such as Helium, to the equilibrium mixture.
 This does not change the partial pressures of the
gases.
 As such the equilibrium position is not affected.
Tutorial
In which direction does the equilibrium position shift if
pressure is decreased in each of the following systems? :
i. 2A(s) + 3B(g) ⇋ 2C(s) + 2D(g)
ii. A(g) ⇋ B(g) + C(g)
iii. A(g) + B(g) ⇋ C(g) + D(g)

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202202 TEACHING NOTES 116
22
Solutions
Since pressure is decreased, then the system will
favour the direction that increases pressure!!
i. 2A(s) + 3B(g) ⇋ 2C(s) + 2D(g)
From products (right) to reactants (left)
ii. A(g) ⇋ B(g) + C(g)
From reactants (left) to products (right)
iii. A(g) + B(g) ⇋ C(g) + D(g)
No net change since ∆n = 0!!!

2
Exercises
The following exercises illustrate the effect of a
pressure change on the equilibrium position of a
reversible system.
Predict the direction of the net rxn in each case as a
result of increasing the pressure (decreasing volume)
in each of the following systems at constant pressure:
(i) 2Pb(s) + 3O2(g) 2PbO(s) +2SO2(g)
(ii) PCℓ5(g) PCℓ3(g) + Cℓ2(g)
(iii) H2(g) + CO2(g) H2O(ℓ) + CO(g)
(iv) A(s) 2B(s), (v) 2A(ℓ) B(ℓ)
(vi) A(s) B(g)

2
Solutions
(i) 2Pb(s) + 3O2(g) 2PbO(s) +2SO2(g)
From Left to Right to reduce the pressure as less
gaseous molecules will be produced.
(ii) PCℓ5(g) PCℓ3(g) + Cℓ2(g)
From Right to Left, why???
(iii) H2(g) + CO2(g) H2O(ℓ) + CO(g)
From left to right, why???
(iv) A(s) 2B(s), (v) 2A(ℓ) B(ℓ)
No effect/change, Why?? No change. Why??
(vi) A(s) B(g) From Right to left, Why??
2
Changes in Temperature
Discuss endothermic/exothermic rxns & their ∆H
signs.
Changes in concentration, pressure or volume may
alter/change the equilibrium position, i.e., the relative
amounts of reactants & products but does not change the
value of the equilibrium constant, Kp or Kc.
Only a change in temperature can alter/change the value
of equilibrium constant.
Let us consider our usual rxn to appreciate this fact:
N2O4(g) 2NO2(g).
The forward reaction is endothermic (i.e, absorbs heat &
∆H > 0 (+ve).
2
What would happen if external heat is added to the rxn?
 Thus Heat + N2O4(g) 2NO2(g), ∆H = + 58.0 kJ/mol
Therefore the reverse rxn: 2NO2(g) N2O4(g) is
exothermic and releases heat where ∆H < 0.
Thus, 2NO2(g) N2O4(g) + Heat, ∆H = -58.0 kJ/mol.
At =bium & at a fixed temperature, the heat effect is zero
because there is no net reaction.
Why??
Because any heat evolved = heat absorbed.
If we treat heat as though it were a chemical reagent, then
a rise in temperature “adds” heat to the system.

2
Conversely, a drop /decrease/fall in temperature
“removes” heat from the system.
As with a change in any other variable, the system shifts
to reduce the effect of the change.
Therefore any continuous temperature increase favours
the endothermic direction (from left to right of the =bium
to remove the added heat) & any continuous temperature
decrease favours the exothermic direction (from right to
left of the =bium equation to replenish the heat).
Consequently, the equilibrium constant given by:
[NO2]2 increases when the system is heated
K =
& c [N2O4] decreases when the system is cooled.
2
(c) Effect of changes in temperature
Consider the reaction
N2 (g) + 3 H2 (g) ⇋ 2NH3 (g) ΔH = -92.2 kJ.
As written, the forward rxn is exothermic and the reverse
rxn is endothermic.
Since an exothermic rxn releases heat, we can think of heat
as a “product” in the rxn.
As we increase the temperature of the system, we
increase the “concentration” of this “product” and the
rxn shifts from right to left (towards the reactants).
The new equilibrium will have less products and more
reactants, giving a smaller value of Kc.

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22
In an endothermic reaction, heat will be a “reactant” so
increasing the temperature will shift the reaction from
the left to the right, increasing the value of Kc.
Overall,
 Exothermic rxn : T  then KC/Kp 
 Endothermic rxn : T  then KC/Kp 

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22
Another example
Consider the =bium between the following ions:
2-(aq) + 6H O(l)
Exo
COCl4 2 Co(H2O)62+ + 4Cl-(aq)
Blue Endo Pink
The formation of [CoCℓ4]2-(aq) the reverse rxn is
endothermic.
Therefore on heating, the equilibrium shifts to the
left & the solution turns blue.
Cooling favours the exothermic rxn (the forward rxn),
i.e, the formation of [Co(H2O)6]2+ & the solution
turns pink.
In summary, a temperature increase in =bium system
favours an endothermic rxn & a temperature decrease
favours an exothermic rxn.
2
The Effect of a Catalyst
A catalyst enhances the rate of a rxn by lowering the
reaction’s activation energy, Ea.
A catalyst however lowers the activation energy of the
favoured & the reverse rxn to the same extent.
Therefore the presence of a catalyst does not alter the
=bium constant nor does it shift the shift of an –bium
system.
Adding a catalyst to a rxn mixture that is not at =bium
will simply cause the mixture to reach =bium sooner.
The same =bium mixture could be obtained without
the catalyst, but we might have to wait much longer for
it to happen
2
Tutorial

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22
Solutions
(a) No change only that the =bium [CO] will be arrived
at quicker!!
(b) The reverse rxn will be endothermic so to
counteract (reduce) the added heat, [CO] will
increase.
(c) [CO] will decrease as the forward rxn reduces no. of
gaseous species.
(d) No change as the partial pressure will remain
constant
(e) [CO] will decrease to reduce the extra O2(g)!! Le
Chatelier’s Principle!!
2
Chemistry in Action
The following slides contains two Life/Biological
Processes that illustrate the effects of changed
condition on =bium processes
1. Life at High Altitudes & Haemoglobin (Hb)
Production
In the human body, countless chemical equilibria
must be maintained to ensure physiological well
being.
When environmental conditions change, the body
must adapt to keep functioning.
The consequence of a sudden change in altitude
illustrate this fact.
2
Chemistry in Action
For example a person from living near the sea (lake)
and travelling to Sapitwa/ Mt. Kirimanjaro/Everest
may experience hypoxia, a deficiency in the amount of
oxygen reaching body tissues.
Symptoms include headache, nausea, extreme fatigue
& other discomforts.
In serious cases, the victim may slip into a comma &
die if not treated quickly.
However, a person living at high altitude for weeks or
months gradually recovers from altitude sickness &
adjusts to the low oxygen content in the atmosphere
& functions normally.
2
Simplified Haemoglobin-Oxygen Complex
The combination of O2(g) with Hb molecule which
transports O2 thru the blood is a complex rxn but for our
purposes may be simplified thru the foll reversible rxn:
Hb(aq) + O2(aq) HbO2(aq), where HbO2(aq) is the
oxy-haemoglobin complex that transports O2 to tissues.
[HbO2]
The =bium constant expression is Kc =
[Hb] [O2]
At an altitude 3 km above sea level,
the PO2 = 0.14 atm while at sea level = 0.2 atm.
According to Le Chatelier’s Principle, a decrease in [O2]
(PO2) will shift the =bium to the left from right, resulting
in the depletion of the supply of HbO2, causing Hypoxia.
2
Haemoglobin-Oxygen Complex
Given enough time, the body copes with this problem by
producing more Hb molecules & gradually the =bium
shifts back towards the production of HbO2.
It takes 2 or 3 weeks for the increase in Hb production to
satisfy adequately the body’s basic needs.
A return to full capacity may take several years.
Studies indicate that long-time residents of high altitude
areas have high Hb levels in their blood-sometimes as
much as 50% more than individuals living at sea level.
Why??
To enable provision of HbO2!!!

2
The Haber Process: The procedure for NH3
Knowledge of factors that affect chemical =bium may be
harnessed (used to the advantage) in industry such as in the
Haber Process, the production of NH3.
 The Haber process entails (involves) reacting H2(g) & N2(g)
in the presence of a catalyst (in a heterogeneous equilibrium
to speed up the rxn) to produce NH3(g) as follows:
3H2(g) + N2(g)
Let us consider
2NH3(g) H = -92.6 kJ/mol
which factors could be manipulated to
increase yield (production of NH3(g)) considering the
stoichiometry & conditions of the rxn.
An industrial chemist uses a procedure that maximises yield
with minimum cost & time (cost effective method).

2
The rxn N2(g) +3H2(g) 2NH3(g), ∆H° = -92.6 kJ/mol
is an exothermic one.
From the stoichiometry of the equation, what would
be the effect of increasing pressure & decreasing
temperature?
Increasing pressure (reducing volume) will push the =bium
to the products side resulting in high yield of the required
NH3(g).
In addition, since the forward rxn is exothermic, decreasing
temperature would favour result in increase the production
of NH3(g).

2
The Bpt of NH3(g) = -33.5 °C, so a temperature of
-53 ° C (220 K) would be desirable becoz any NH3(g)
produced would condense & be conveniently removed
from the reacting vessel & facilitate more production
as the =bium would be disturbed due to its removal.
Both H2(g) & N2(g) would still be gases at -53 °C.
On paper, increasing pressure & reducing temperature
would indeed maximise yield.
Indeed during industrial production of NH3, the
operating pressures are between 500 atm & 1ooo atm in
tandem with the requirement of high pressures.
2
However contrary to the expectation of low temperature
requirement, the operating temperature is 500 ° C in
industry, .
Why??
Becoz despite the high temperature operation being costly
(as may require steam of heat generation, the justification of
the high temperature usage is that the rate of NH 3
production increases with temperature.
In industry, faster production of NH3 is preferable despite the
lower yield & high operating cost.
For this reason, a combination of high pressure, high
temperature conditions & usage of proper catalyst is the
most efficient way to produce NH3 on industrial scale!!
2
Solubility Equilibria
Precipitation rxns are important in industry, medicine
& everyday life.
For example, the preparation of many essential
industrial chemicals such as Na2CO3, BaCℓ2, K2SO4,
myonnaise is based on precipitation rxns,
The general rules for predicting the solubility of ionic
compounds in water were introduced last semester.
Although the rules are useful, they do not enable us to
make quantitative predictions about how much of a
given ionic compound will dissolve in water.
To develop a quantitative approach, we start with
what we already know about chemical =bium.
2
Solubility Product
Unless otherwise stated, in the subsequent discussion, the
solvent is water & the temperature will be 25 °C (298 K).
If we keep on adding a solute to a solvent at a particular
temperature, a point will be reached whereby no more
solute dissolves and some solid remains in the solution.
When this point is reached the solution is said to be
saturated.
In saturated solutions, some of the insoluble compounds
still have some but very small solubility.
At this point a solubility equilibrium exists between the
un-dissolved and dissolved solute.

2
Solubility Product Constant
Slightly soluble (often called insoluble) ionic compounds have a
relatively low solubility, so they reach solubility equilibrium with
relatively little solute dissolved.
Consider a saturated AgCℓ(aq) solution that is in contact with
AgCℓ(s).
The solubility =bium can be represented as
AgCℓ(s) Ag+(aq) + Cℓ-(aq)
Since aqueous solns of ionic salts such as AgCℓ(aq) are
considered as strong electrolytes, all the AgCℓ(aq) in H 2O is
assumed to fully dissociate into Ag+(aq) & Cℓ-(aq).
Since this is a heterogeneous reversible =bium, concentrations of
solids is a constant and the equilibrium constant expression does
not have the [AgCℓ(s)] component.
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22
Solubility Product constant
Thus
For AgCl(s) Ag+(aq) + Cl-(aq)
+ -
KC [AgCl(s)] = KSP = [Ag (aq)] [Cl (aq)]
Therefore the Kc[AgCℓ(s)] = Ksp, where KSP is

called “the solubility product constant” or simply
the “solubility product”.
In general, solubility product of a compound =
the product of the molar concentrations of
constituent ions, each raised to the power of its
stoichiometric coefficient in the –bium equation.
2
Solubility Product constant
The equilibrium constant for the solubility
equilibrium of a slightly soluble (or nearly
insoluble) ionic compound is called the solubility
product constant, Ksp.
Exercise
Write the Ksp expressions for the following:
1. MgF2(s) Mg2+(aq) + 2F-(aq)
2. Ag2CO3(s) 2Ag+(aq) + CO32-(aq)
3. Ca3(PO4)2(s) 3Ca2+(aq) + 2PO43-(aq)
2
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Example

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22
Solubility product, KSP
The value of KSP indicates the solubility of an ionic
compound.
The smaller the value of KSP, the less soluble is the
compound in H2O.
However in using KSP values to compare solubilities,
we choose compounds that have similar chemical
formulas, such as, AgCℓ(s) & ZnS and CuF2 &
Fe(OH)2.
Why??
Becoz their soluble species will have similar
exponents!!
2
Ion Product, Qsp
When ionic solids dissolve in water to form aqueous
solutions, any of the following 3 conditions may exist:
1. The solution may be unsaturated.
2. The solution is saturated
3. The solution may be supersaturated (You have >2
phases, solid, liquid & vapour (gas) since we use
boiling water).
For concentrations of ions that do not correspond to
equilibrium conditions, we use the reaction quotient
in this case called ION PRODUCT, QSP to predict
whether a pptate will form or not.
2
Ion Product, QSP
Note that QSP has the same form as KSP, except that
the concns of ions are not =bium concentrations.
For example, if we mix a solution containing Ag +(aq)
ions with one containing Cℓ-(aq), then
QSP = [Ag+]o[Cℓ-]o, the zero subscript to indicate that
they are initial concentrations & not =bium
concentrations.
QSP & KSP
The possible relationship between Q & K SP are:
1. Q < KSP, [Ag+]o[Cℓ-]o < 1.6 10-10 → Unsaturated
solution, no precipitation (Ksp at an eleveated
temperature).
2
Ion Product, QSP
2. QSP = KSP, [Ag+]o[Cℓ-]o = 1.6 10-10 → Saturated solution, no
precipitation
3. QSP > KSP, [Ag+]o[Cℓ-]o > 1.6 10-10 → Supersaturation
solution, AgCℓ will precipitate out until the product of
ionic concentrations = 1.6 x 10-10.
Molar solubility (mol/L) & Solubility (g/mg/L)
There are 2 other ways of expressing a substance’s solubility.
These are Molar solubility & solubility.
Molar solubility = the number of moles of solute in 1L of a
saturated solution in mol/L.
Solubility = the number of grams of solute in 1L of
saturated solution in g/L.
2
Molar solubility (mol/L) & Solubility (g/mg/L)
Both these expressions refer to the concns of saturated
solns at some given temperature, usually 25 °C.
Both molar solubility & solubility are convenient to use in
the laboratory & can be used to determine KSP as follows:
Solubility of Molar solubility Concns of cations KSP of

a compound of a compound & anions compound
(a) Sequence for calculating KSP from solubility data
KSP of a Concns of cations Molar solubility Solubility of

compound & anions of a compound a compound
(b) Sequence for calculating solubility from KSP data

2
Exercises
1. The solubility of CaSO4 is 0.67 g/L at 25 °C.
Calculate the KSP for CaSO4 at this temperature.
( Ans = 2.4 x 10-5)
Solution
The Mr of CaSO4 = 136.2 g/mol → The molarity of
Ca2+ & SO42-(aq) which are in solution = 0.67 g/136.2
g/mol = 4.919 x 10-3 M
→ [Ca2+][SO42-] = (4.919 x 10-3)2
→ KSP = 24.196 x 10-6 = 2.4 x 10-5.
2. Calculate the solubility of CaF2 given that its
KSP = 4.0 x 10-11 (Hint: Use the equilibrium of CaF2
which is CaF2(s) Ca2+(aq) + 2F-(aq)).
(Ans = 1.7 x 10 -2
g/L)
2
Solution
CaF2(s) Ca2+(aq) + 2F-(aq)
x 2x
KSP = [Ca2+][F-] = [x][2x]2 = (x)(4x2)
40
3
= 4x = 4.0 x 10 -11
= 40 x 10 -12 3
x = x 10-12 = 10 x 10-12
4
3
x= 10 x 10-12 = 2.154 x 10-4
Molar solubility of CaF2(s) = 2.154 x 10-4 M
Mr of CaF2 = 78.074 g/mol

Therefore solubility of CaF2 in g/L = 2.154 x 10-4 mol
x 78.074 g
= 168.2053 x 10-4 g/L = 1.7 x 10-2 g/L L mol
2
Solubility (mol/L , g/L , mg/L)
Note that Ksp is expressed in terms of the molar
concentrations of ions in the saturated solution.
These ion concentrations are in turn related to the
solubility of the ionic compound. A more soluble ionic
compound gives a higher concentration of the ions than a
less soluble compound.
Solubility (in g/L) is the number of grams of the
compound that dissolve to give a liter of saturated solution.
 In all calculations the volume (or mass) of solution is equal to
the volume (or mass) of water used to dissolve the compound.
Converting g/L to mol/L gives molar solubility - number of
moles of the compound that dissolve to give a liter of
saturated solution.
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22
The larger the value of Ksp, the more soluble the compound is
at that particular temperature
Example 1.
The solubility of silver sulfate, Ag2SO4 (Mr = 311.799) is
4.68 g/L. Calculate the solubility product of Ag2SO4 .
Solution 4.68 g
Molar solubilty of Ag2SO4 = x mol = 1.5 x 10-2 M
311.799 g
The for the solubility of AgSO4(s) & ionisation of AgSO4(aq) is:
Ag2SO4(s) 2Ag+(aq) + SO42-(aq)
From the rxn equation, if molar solubility of Ag2SO4 = x,
then [Ag+] = 2x = 2(1.5 x 10-2M) = 3.0 x 10-2M & [SO42-] = x = 1.5 x
10-2M
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22
Therefore KSP = [Ag+]2[SO42-] = (3.0 x 10-2)2(1.5 x 10-2)
= 1.4 x 10-5.
Example 2
Calculate the molar solubility of silver carbonate,
Ag2CO3 if its KSP at 25 °C = 8.1 x 10-12. (Ans = 1.3 x 10-4 M)
Let x be the molar solubility of Ag2CO3(s).
The =bium eqn is Ag2CO3(s) 2Ag+(aq) + CO32-(aq)
[initial] - 0 0
Change -x +2x +x
=bium - 2x x
KSP = [Ag
3
]
+ 2
[CO 3
2-
] = (2x) 2
(x) = 4x 2
.x = 4x 3
= 8.1 x 10 -12
8.1 x 10-12 = 3 -4
→x= 4
2.025 x 10-12 = 1.265 x 10 M

2
Predicting the formation of a precipitate
Using the solubility rules, we can predict
whether a precipitate will form or not when two
solutions are mixed or when a soluble compound is
added to a solution.
In addition, using the same solubility rules, the
type of precipitate to form may be predicted.
To quantitatively establish whether a precipitate
will form or not, the following steps are followed.
1. Calculate the concentrations of the constituent
ions. This is possible because the number of moles
of each ion in each original solution and the total
volume of the combined solution can be calculated.
2
2. Nextcalculate the reaction quotient (ionic product, Q sp) and
compare the value of the QSP with the KSP of the precipitate
to be formed as before.
When the solution is saturated, Qsp = Ksp.
If Qsp ˃ Ksp, the solution is momentarily supersaturated, and
some solid precipitates until the remaining solution becomes
saturated (Qsp = Ksp).
If Qsp ˂ Ksp the solution is unsaturated, and no precipitate
forms at that temperature (more solid can dissolve).
In short:
 Q = K : solution is saturated and no change occurs.
sp sp
 Q › K : ppt forms until solution is saturated.
sp sp
 Q ‹ K : solution is unsaturated and no ppt forms.
sp sp

2
Example
Determine if a precipitate will form when exactly 200 mL of
0.0040M BaCℓ2 is mixed with exactly 600 mL of 0.0080 M K2SO4.
Strategy
(i) Under what conditions will an ionic compound precipitate from
a soln??
When Qsp > Ksp
(ii) Which are the ions involved/available?
Ba2+, Cℓ-, K+ & SO42-
(iii) From the ions involved, which precipitate would form & what
is its KSP at 25 °C?
BaSO4(s) & 1.1 x 10-10

2
Solution
Moles of Ba2+ = 0.0040 mol x 200 mL = 8.0 x 10 mol of Ba
-4 2+
1000 mL
2+ 8.0 x 10-4 mol x 1000 mL
Since the total volume = 800 mL, [Ba ] =
800 mL x L
= 1.0 x 10-3 M
Moles of SO42- =0.008 mol x 600 mL = 4.8 x 10 mol of SO4

-3 2-
1000 mL
-3
2- 4.8 x 10 mol x 1000 mL
Since the total volume = 800 mL, [SO4 ] =
800 mL x L
= 6.0 x 10-3 M
BaSO4(s) Ba2+(aq) + SO42-(aq), KSP = 1.1 x 10-10
QSP = [Ba2+][SO42-] = (1.0 x 10-3)(6.0 x 10-3) = 6.0 x 10-6
Now compare QSP & KSP
2
Solution
Since QSP > KSP, the solution is supersaturated &
consequently, some BaSO4 will precipitate out of the
solution until QSP = KSP, i.e., [Ba2+][SO42-] = 1.1 x 10-10.
Another Example
Does a precipitate of CaF2 (KSP = 3.2 x 10-11) form when a
0.100L of 0.30M Ca(NO3)2 is mixed with 0.200L of 0.060 M
NaF?
Solution
Total volume = (0.100 + 0.200)L = 0.300 L
Moles 2+
of Ca2+ = 0.3M x 0.100L
2+ = 0.030 mol Ca
2+
[Ca ] = 0.030 mol Ca = 0.10 M Ca 2+

→
0.300 L
2
Solution
Moles of F- = 0.060M F- x 0.200 L = 0.012 mol F-
-
-0.012 mol F
→ [F ] = = 0.04 M F-
0.300 L
Substituting into the solubility product

expression & comparing QSP with KSP,
QSP = [Ca2+][F-]2 = (0.10) (0.040)2 = 1.6 x 10-4.
Since QSP > KSP (1.6 x 10-4 > 3.2 x 10-11), CaF2 will
precipitate until QSP = 3.2 x 10-11.

2
The common Ion Effect
Let us consider 1 M CH3CO2H(aq) which will have
the following –bium:
CH3CO2H(aq) CH3CO2-(aq) + H+(aq).
If 1.0 M of CH3CO2Na(s) is dissolved in the above
mixture at =bium, CH3CO2Na(aq) being a strong
electrolyte, will dissociate completely in H2O(ℓ) &
there will be a common-ion effect becoz the
[CH3CO2-] will be above that at =bium.
CH3CO2H(aq) CH3CO2-(aq) + H+(aq)

2
What will be the consequence of the addition of
CH3CO2Na(aq) to the equilibrium
CH3CO2H(aq) CH3CO2-(aq) + H+(aq)?
The ionisation of CH3CO2H(aq) will be
suppressed as the =bium will shift from right to
left resulting into a decrease in [H+(aq)] with
subsequent increase in CH3CO2H(aq).
Thus a solution containing both CH3CO2H &
CH3CO2Na will be less acidic than the equimolar
soln of only CH3CO2H(aq).
2
This is the “common ion effect” which is the shift
in =bium caused by the addition of a compound
that has an ion in common with the dissolved
substance.
Introduction of a common ion causes salts to become less
soluble – think of Le Chatelier’s Principle.
For the equilibrium PbCrO4(s) ⇋ Pb+2(aq) + CrO42-(aq)
 adding K2CrO4 which is very soluble increases [CrO42-]
 The equilibrium position shifts to the left.
 PbCrO4(s) becomes less soluble.

2
The Common Ion Effect
The pH of a solution can also affect solubility if H+ or OH-
ions can interact with the salt’s ions.
 Would magnesium hydroxide (milk of magnesia) be
more soluble in an acid or a base? Why?
Mg(OH)2(s) ⇋ Mg2+(aq) + 2 OH-(aq)
Acid (H+) as it will remove the OH-(aq) & increase
solubility of Mg(OH)2(s).
Example
The solubility of AgCℓ(s) in pure water is 1.3 x 10-5
M. Work out the solubility of AgCℓ(s) in seawater
where the [Cℓ-] is 0.55M (KSP of AgCℓ = 1.8 x 10-10).
Wednesday,
Wednesday,December
December7, 7,
22
Example

Wednesday,
Wednesday,December
December7, 7,
22
Wednesday,
Wednesday,December
December7, 7,
22
Practice exercise
Calculate the solubility of CaF2 in 0.01M Ca(NO3)2 if the KSP
(CaF2) = 3.9 x 10-11.
Equilibrium eqn = CaF2(s) Ca2+(aq) + 2F-(aq)
(Ans = 3.1 x 10-5 M)
Solution: Let the molar solubility of CaF2 = x
3 3
 4x 3
= 3.9 x 10 -11
x = 39 x 10-12
= 9.75 x 10-12
4
x = 2.136 x 10-4 M = 2.1 x 10-4 M
At =bium [Ca2+] = 2.1 x 10-4 M, [F-] = 4.2 x 10-4 M
Equilibrium eqn = CaF2(s) Ca2+(aq) + 2F-(aq)
Initial - 2.1 x 10-4 4.2 x10-4
Change -x x + 0.01 2x
=bium - 0.01 2x
2
Solution
Therefore (0.01)(4x2) = 3.9 x 10-11
3.9 -11
→ 0.04x = 3.9 x 10 , → x =
2 -11 2 x 10 = 97.5 x
0.04
10-11
9.75 x 10-10 = 3.12 x 10-5

→ = 9.75 x 10-10, x =
END OF TOPIC

2

1 Chemical Equilibrium Notes Ech 1201

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MZUNI CHEMISTRY DEPT ECH 1201

Wednesday, December 7, 202 TEACHING NOTES 1

Dynamic and non-dynamic equilibrium

Law of Mass Action

Relationship between Kp and Kc

The equilibrium constant and its uses

Le Chatelier’s principle, factors affecting equilibrium

position and equilibrium constant

prediction MZUNI CHEMISTRY DEPT ECH 1201

The starting crystals are blue in colour while the products

In eqns for reversible rxns, reactants and products are

 No movement is required to maintain balance.

MZUNI CHEMISTRY DEPT ECH 1201

 If Amedeo walks upwards at the same speed as the

As the rxn progresses, the concentration of reactants

MZUNI CHEMISTRY DEPT ECH 1201

E.g. N2O4(g) 2NO2(g)

MZUNI CHEMISTRY DEPT ECH 1201

As such, although the forward and reverse rxns are

Rates become equal Concentrations become constant

MZUNI CHEMISTRY DEPT ECH 1201

[NO2] [N2O4] [NO2] [N2O4] [NO2] [NO2]2

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

In this form, the Law of Mass Action relates to the

MZUNI CHEMISTRY DEPT ECH 1201

The value of K for a reversible rxn indicates whether

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

PbCl2 (s) ⇌ Pb2+ (aq) + 2 Cl−(aq) and Kc = [Pb2+] [Cl−]2

MZUNI CHEMISTRY DEPT ECH 1201

Then for the reverse rxn 2NO2(g) N2O4(g),

MZUNI CHEMISTRY DEPT ECH 1201

E.g. At 1565 K we have these equilibrium constants:

2CO2(g) ⇌ 2CO(g) + O2(g) K1 = 1.6 x 10-11

2H2O(g) ⇌ 2H2(g) + O2(g) K2 = 1.3 x 10-10

CO2(g) + H2(g) ⇌ CO(g) + H2O(g) K3 = ?

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

Since P = in atm, R = 0.0821 L. atm.K-1.

MZUNI CHEMISTRY DEPT ECH 1201

Kp = Kc(RT)n = 4.63 x 10-3 x 0.0821 L.atm x 298 K

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

Ka = 1.8 x 10-5 and Quadratic eqn = X = -b   b2 - 4ac

X= - 0.000018   x 1 x -0.000018

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

MZUNI CHEMISTRY DEPT ECH 1201

Note that we write the subscript 0 (or i) to indicate that

MZUNI CHEMISTRY DEPT ECH 1201

Qc = 2.7855 x 107 = 2.8 x 107

MZUNI CHEMISTRY DEPT ECH 1201