Chemical Systems

and Equilibrium
TOPIC 7 AND 17

7.1: Equilibrium

Understandings

A state of equilibrium is reached in a closed system when the

rates of the forward and reverse reactions are equal

The equilibrium law describes how the equilibrium constant

(Kc) can be determined for a particular chemical equation

The magnitude of the equilibrium constant indicates the extent

of a reaction at equilibrium and is temperature dependent

The reaction quotient (Q) measures the relative amount of

products and reactants present during a reaction at a
particular point in time. Q is the equilibrium expression with
non-equilibrium concentrations. The position of the equilibrium
changes with changes in concentration, pressure and
temperature

A catalyst has no effect on the position of equilibrium or the

equilibrium constant

Application and Skills

The characteristics of chemical and physical systems in

a state of equilibrium

Deduction of the equilibrium constant expression (Kc)

from an equation for a homogenous reaction

Determination of the relationship between different

equilibrium constants (Kc) for the same reaction at the
same temperature

Application of Le Chateliers principle to predict the

qualitative effects of changes of temperature, pressure,
and concentration on the position of equilibrium and on
the value of the equilibrium constant

Chemical Equilibria

state of dynamic equilibrium that occurs in a

CLOSED system when the forward and reverse
reactions occur at the same rate

when equilibrium is established, all

MACROSCOPIC properties are constant

Macroscopic Properties are those that can be observed or

measured, such as colour, density, pH, concentration etc)

On a molecular level, there is continual

interconversion of reactants and products

Dynamic Equilibria
Dynamic Equilibrium: a balance
between forward and reverse processes
occurring at the same rate.
CO2 (g) CO2(aq)
Forward Reaction left-to-right
Reverse Reaction right-to-left

Types of Dynamic Equilibria

Solubility Equilibrium: between a solute

and a solvent in a saturated solution in a
closed system

Phase Equilibrium: between different

physical states of a pure substance in a
closed system

Chemical Reaction Equilibrium: between

reactants and products of a chemical reaction
in a closed system

Solubility Equilibrium

most substances dissolve in a solvent to a certain

extent and then appear to stop dissolving

Solubility Equilibrium

at equilibrium, water molecules and ions still

collide with the crystal surface, but the rate of
dissolution equals the rate of crystallization

no observable changes would occur in either the

[ions] or in the qty of solid present

system in dynamic equilibrium

Solubility Equilibrium

a mixture exhibiting solubility

equilibrium must contain both
dissolved and undissolved solute at
the same time

***At equilibrium, the rates of the

forward and reverse reactions are
equal

Phase Equilibrium

in a closed system, a phase change may establish an

equilibirum :
H2O(l) H2O(g)

when liquid is placed in closed container initially only

evaporation occurs (molecules in liquid phase gain
enough energy in collision to move to a gas phase)

as the numbers of molecule in gas phase increases,

more collide with the liquid surface and lose enough
energy to rejoin liquid phase

eventually rate of evaporation and condensation

become equal (both are still occurring but no change is
seen) and the system is at phase equilibrium

Chemical Reaction Equilibrium

Quantiative Reaction: a reaction in which virtually all

of the limiting reagent is consumed; a reaction that goes
to completion

Ex. heating limestone in open kilns

CaCO3 (s)

CaO(s) + CO2 (g)

The reverse reaction cannot occur because the CO2 escapes

if you confined the reaction to a closed container, a state of

equilibrium would be reached

assumed that any closed reacting system with constant

properties in a state of dynamic equilibrium

Chemical Reaction Equilibrium

For a chemical reaction to reach a state of

dynamic equilibrium, it must

Be reversible

Be in a closed system

Initially the forward rate will be higher (as

the concentration of reactants is higher)

As products are formed, the rates of the

forward and reverse will become equal

Example:
N2O4 (g) 2NO2 (g)

Reaction happens quickly at first, then the

concentration change more slowly until
equilibrium is established

Example: N2O4 (g)2NO2 (g)

For a given overall system composition, the

same equilibrium concentration s are reached
whether equilibrium is approached in the
forward of the reverse direction

Percent Reaction at Chemical

Equilibrium

Percent Reaction at Chemical

Equilibrium

Communicating the extent of

a reaction

all reactions are now considered reversible

important to consider to what extent they go one

way or the other (3 categories)

1. Reactions that favour reactants strongly

percent reaction much less than 1%

Communicating the extent of a

reaction

2. Reactions that favour products very strongly

percent reaction more than 99%

observed to be complete; generally written with single

arrow to indicate effect of reverse reaction is
negligible

3. Reactions that achieve noticeable equilibirum

conditions

percent reaction b/w 1% and 99%

If < 50 %, reactants are favoured; If >50%, products

are favoured

Communicating the extent of a

reaction

Equilibrium Constant

Equilibrium Constant (Kc)

equilibrium occurs when the rate of the

forward reaction is the same as the rate of
the reverse reaction

Ex. A + B C + D

Forward rate = kf [A][B]

Reverse rate = kr [C][D]

At equilibrium Forward rate = Reverse rate

kf [A][B] = kr [C][D]

Equilibrium Constant

Equilibrium Constant (Kc)

does not have fixed units

all concentrations have units of mol/L

only gases and aqueous solutions are included in

the equilibrium constant

All solids have a fixed density and therefore are

omitted from the expression.

Pure liquids also have a fixed density (ex. water)

and are omitted

only included when pure liquids are mixed

Equilibrium Constant

equilibrium constant depends on temperature

equilibrium constant, Kc of a forward reaction

and the equilibrium of the reverse reaction are
reciprocal quantities

Kc, f = Kc, r-1

Ex. AB and BA

Calculating K

Heterogeneous Equilibria

concentration of a pure liquid cannot change (simply the

density rewritten in units of mol/L instead of g/L)

since [H2O(l)] is a constant;

K = [H2(g)]2[O2(g)]

In general, concentrations of entities in solid or liquid

state are not included as variables

Magnitude of K

Qualitative Changes in
Equilibrium Systems

Change in Conditions

If temperature, pressure or concentrations of

species is changed under equilibrium
conditions, then the rates of forward and
reverse will no longer be equal

equilibrium has been disturbed

Concentrations of species will change until

equilibrium is reestablished

LeChateliers Principle

When a chemical system at equilibrium is

disturbed by a change in a property, the
system adjusts in a way that opposes the
change.

Changes in concentration or pressure, will

not change the value of Kc

Change in temperature, will shift the position

of equilibrium and change the value of K c

Change in Concentration

Temperature Change

Endothermic: reactants + energy products

Exothermic: reactants products + energy

Effect of Pressure

Recall Boyles Law : P1V1 = P2V2

Effect of Pressure/Volume

Effect of Inert Gas

if an unreactive gas is added to a fixed

volume of the equilibrium, so all
concentrations remain constant, then
there is no effect

if it is added at constant pressure (so

volume must increase) then all
concentrations will decrease and the
effect is similar to reducing pressure

Effect of a Catalyst

presence of catalyst reduce the Ea of

both the forward and reverse reactions
by the same amount

both forward and reverse are speeded

up by the same amount
the

equilibrium is established more rapidly

but the position of the equilibrium is not
effected

Catalyst

Application of Kinetics and Equilibrium to

Industrial Processes

Many industrial processes involve

equilibria

Goal is to produce desired product as

efficiently as possible

Rapidly but with minimum waste and

minimal energy input

Well look at the Haber process and the

Contact process

Haber Process

Production of ammonia

1st patented in 1908

Significant because countries no longer

depended on importing nitrates from
S. America and could manufacture
artificial fertilizers

Haber Process
3H 2 ( g ) N 2 ( g )
2 NH 3( g )
140

H 92 KJmol

million tons manufactured per

year
80%

20%

used to make fertilizers

nitric acid, polymers (nylon) etc.

Nitrogen

obtained from air, hydrogen

from natural gas

Pressure
3H 2 ( g ) N 2 ( g )
2 NH 3( g )

H 92 KJmol

Rate: increasing pressure (increase [reactant

gases]), increases rate

Reaction faster as more collisions per second

Yield: increasing pressure also increases yield

Reaction proceeds forward towards fewer moles of gas

to lower pressure and reach equilibrium

Temperature
3H 2 ( g ) N 2 ( g )
2 NH 3( g )

More molecules have Ek > Ea

Yield: increasing temp, decreases yield

H 92 KJmol

Rate: increasing temperature, increases rate

Exothermic reaction; reaction proceeds left

(reverse) to decrease temp

OPTIMUM Temp needed: high enough for

reasonable rate but low enough for
reasonable yield

Catalyst

Rate: necessary to increase rate at which

equilibrium is reached

Iron metal powdered to increase surface

area

Promoter such as KOH added to keep catalyst

efficiently working

Yield: no effect on position of equilibrium,

therefore no effect on yield

Actual Conditions

Vary from plant to plant

High pressure is desirable but very

expensive to build

Generally: T b/w 350-450 oC

P b/w 150-250 atm

under these conditions, 15 % yield

Actual Conditions
3H 2 ( g ) N 2 ( g )

Fe( s ) , 450o C , 200atm

2 NH 3( g )

H 92 KJmol 1

Only 15% yield BUT, ammonia is separated

from mixture via cooling and unreacted
gases are recycled

Process repeated so that a total yield of up

to 98% is possible

Contact Process

2 SO2 ( g ) O2 ( g )
2 SO3( g )

H 196 KJmol

Sulphuric acid production

Essential reaction converts SO2 to SO3

Source of SO2, combustion of S and roasting

(comb.) of sulfide ores in air

Exothermic and involves reduction in volume,

so same arguments used for Haber process
apply

Contact Process Conditions

V2 O5 , 450o C , 2 atm

2 SO2 ( g ) O2 ( g )

2 SO3( g )

H 196 KJmol 1

High yield favoured with high P and low T

Add catalyst to use high T

Optimum T must be used (~450 oC)

Catalyst is vanadium(V)oxide

Only 2 atm P is used, gives yield of over 98% (high P isnt

necessary)

To form sulfuric acid, react with water

Used for chemical feedstock, paints, fertilizers, detergents,

soaps, electrolyte in batteries

CHEMISTRY LIFE
LESSONS
WITH MRS TULI

Equilibrium in Life

Stress /
Anxiety

Procrastinati
on

Productivity

Happiness
/ Peace

Productivity includes work, hobbies, exercise,

SLEEP but beware hobbies/exercise can turn into
procrastination if used in place of finishing work

Equilibrium in Life

CHANGE : IB PROGRAM (Increases

Stress / Decreases Happiness???)

Stress /
Anxiety

Procrastinati
on

Productivity

Happiness
/ Peace

17.1 : The equilibrium

law

Understandings

Applications and Skills

Equilibrium Calculations

stoichiometry is straightforward when

reactions go to completion

Equilibrium calculations are more

complicated but are simplified with ICE
tables

Initial, Change, Equilibrium

Example 1

Example 2

Example 3

Reaction Quotient, Q

similar to K

calculated at any concentrations, not just

equilibrium

used to determine whether or not the

system is at equilibrium

can calculate Q and compare it to K

Reaction Quotient
If

Q = K, system is at equilibrium

If

Q>K, system must shift left to reach

equilibrium (too much product has
been formed)

If

Q<K, system must shift right to

reach equilibrium (too much reactant
is present)

Using Reaction Quotient

For the synthesis of ammonia gas at 500 oC in a

closed vessel from gaseous nitrogen and
hydrogen, the equilibrium constant, Kc, is 6.01 x
10-2. For each of the following initial conditions,
determine if the given concentrations represent an
equilibrium. If not, predict the direction in which
the reaction will proceed to reach equilibrium.
[NH3(g)]initial
(mol/L)
[N2(g)]initial
(mol/L)
[H2(g)]initial
(mol/L)

(a)
1.00 x 10-3

(b)
2.00 x 10-4

(c)
1.00 x 10-4

1.00 x 10-5

1.50 x 10-5

5.00

2.00 x 10-3

3.54 x 10-1

1.00 x 10-2

Calculating Equilibrium Concentrations

(Using K, all initial concentrations and
one equilibrium)

Phosphorous pentachloride gas decomposes to form phosphorus

trichloride gas and chlorine gas. A 2.00 L sealed flask at 30 oC
initially contains 0.298 mol of phosphorous trichloride gas, 8.70 x
10-3 mol of phosphorous pentachloride gas, and no chlorine gas.
At equilibrium, the flask contains 2.00 x 10-3 mol of chlorine gas.
Calculate the equilibrium concentrations of all entities and the
value of K.

Calculating Equilibrium
Concentrations (Using K and initial
concentrations)

Carbon monoxide gas reacts with steam to

produce carbon dioxide and hydrogen. At 700 K,
the equilibrium constant is 5.10. Calculate all
equilibrium concentrations if 1.250 mol of each
entity is initially placed in a 500.0 mL seal flask

Calculating Equilibrium
Concentrations (using assumptions
about magnitude of x)

At 2000 oC, K is 6.40 x 10 -7 for the decomposition

of carbon dioxide gas, into carbon monoxide and
oxygen. Calculate the concentrations of all entities
at equilibrium if 0.250 mol of carbon dioxide is
placed in a 1.000L closed container and heated to
2000 oC.

*** when Kc < 10-3, approximations are justified

Calculating Equilibrium
Concentrations (rejecting
assumption about magnitude of x)

If 0.500 mol of dinitrogen tetroxide gas is placed in

a 1.00 L closed container at 150 oC, what will be
the concentrations of dinitrogen tetroxide gas and
nitrogen dioxide gas at equilibrium. The
equilibrium constant is 4.50 under these
conditions.

Free Energy and

Equilibrium

Gibbs Free Energy

Recall :

G is a measure of work that is available from the

system

Sign is used to predict spontaneity

G is negative, spontaneous in forward direction

G is positive, spontaneous in reverse direction

G is zero, reaction is at equilibrium

Free energy during a reaction

Equilibrium
System

is at equilibrium when it

has
Maximum
Minimum

entropy
free energy

Kc calculated from
Thermochemical Data

Example

The esterification reaction that produces ethyl

ethanoate has a free energy change of G =-4.38
kJ/mol. Calculate the value of the equilibrium
constant at 298 K.

Relationship between K and G

G

Ln K

Equilibrium
Mixture

Negative

positive

K>1

Mainly products

Positive

Negative

K<1

Mainly reactants

K=1

Appreciable
amounts of both
reactants and
products