Dynamic equilibrium

Aog t Bcop Ccg Dog

Shows that the reactionoccurs in both directions

The reaction between Acg and Bcg to form Ccgs and Digi
medlar

is
called the forward reaction

Madonna
The reaction between Ccg and Dcg to form Acapand Bag is called
the backward reaction

Open and closed systems

 irreversible and Reversible Systems

Mdbmqq
Reversible reactions in a closed
systemeventually reach a situation
where the rate of the forward reaction and the rate of the backward
reaction are equal

at this point there appears tobe no furtherchange to be observer

In the case of a chemical reaction where the reactionappears to
have stopped the system is described as having reachedequilibrium

Explaining Reversibility

When particles collide the energy associated with collisions can

break bonds in the reacting particles allowing them to re arrangeand

form new products

As shown in the energy profile diagram once

products form it is possible for the reverse
process to occur
Therefore if
thenewly
formed product particles collide with
enough energy to break the bonds then it
is possible to reform the reactants
Dynamic State of Equilibrium

The dynamic state of equilibrium where the forward

is a state
and reverse reactions have not ceased Instead the occur
simultaneously at the same rate

During this state the reaction is incomplete

reactantsandproducts arepresentin the

equilibrium minture
bonds are being continuously brokenand

formed

Extent of Reaction
The equi ibrium law

One can define some sort of number that willgiveus an indeuof

how
far towards completion the reaction has This is called
gone
the reaction quotient Qc

For the reaction a Acg tb Begs cCcg d Dogs

the reaction quotient is equal to
d
Qc C ID
Alix B2b
Note The products on top whilst the reactants are at thebottom
go
The higher the Qc the more productscomparedto the reactants
at thegiventime
The concentration ofeach chemical to the
powerof its co
efficient

in the reaction equation

Solids and liquids do not appear in theeupression and Q is

variable with time

a
Hard
It also turns out that for a
given reaction at a given temperate

no matter what the permutation of the concentration of the

reactants and products are the reactionquotient always seems to
approach the same number as the system establishes equilibrium and

actually ends up becoming the same number whenever the system

 pp

We define another quantity called the equilibrium

can

constant Kc and can be found through

Kc C Eg x D deg
A Eq x B beg

Units for equilibrium constants

Example Question

SO
Kc units M
5012 102
The reaction quotient and the equilibrium law rules

If Qc Kc the system favours the backwards reaction in

order to achieve equilibrium and form more reactants

If Qc L Kc the system favours the forward reaction in order

to achieve equilibrium and form more products

If QE Kc the system is at equilibrium

Homogeneous and Heterogeneous Equilibria

Homogeneous reactions All reactants and products are

in the same state or phase

Heterogeneous reactions Reactants and products are in

 He s

Equilibria in heterogeneous reactions

MtfEE
The important feature ofthe equilibrium law for heterogeneous
reactions is that the concentration of a pure solid or a pure liquid
1 This is because these concentrations do not depend
is assinged as

on how much of the pure substance is present

Themeaning of the value of an Equilibrium constant

The equilibrium constant indicates the event of reaction at

equilibrium and the equilibriumyield the amount ofproductspresent

at equilibrium
The effect of temperature on an equilibrium constant

When the temperature increases for an emothermicreaction

the value of Kc decreases and so the amount of products
present at equilibrium decreases

When the temperature increases for an endothermic reaction

the valueof Kc increases and so the amount ofproducts present
at equilibrium decreases

Calculations
involving Equilibrium

Calculations involving the equilibrium constant and concentrations

Example Question

Kc 805
Yaoi O 120
0 694M at 460 C
 Example Question

0.72 C NOD 0.727

0.040 NO 0.17M
0.040

calculating an equilibrium constant using stoichiometry

 Example Question

V 2L N 04 2 NO o Kc CO06032
CO 1453
I 0 350 0
0 02.48M
c nnYYn
T t 0.120
12 0.120 0 060m01

E O 290m01 0 120m01
0
2920 0.145M 0.1221 0.060
Concentration
M

Le Chatelier's principle

changes to an equilibrium system

The relative amounts of reactants and products at equilibrium

daddies

is called the position ofequilibrium

For any equilibrium system the position of equilibrium may be

changed by adding removing a reactant orproduct
or

changing pressure by changing the volume

 g
Le Chantetier's principle

Adding extra reactant or product

Reaction for the example Nacg 73 2NHugs

Hugs
if entra nitrogen were to be added to the
gas
container without changing the volume or temperature the
miuture would momentarily not be in equilibrium
This is what what happen as the compositionof the miature
adjusts to return to a new equilibrium

Me

tr
I
I
 Once the system has re established equilibrium the rates of
the forward reactions and backward reactions will again be
equal However a net forward reaction has occurred with an
increase in the concentration of ammonia at equilibrium The
equilibrium position is said to have shifted to the night

What is also important to note is that even though the

concentrationof Nz decreases as the system moves to establish a
new equilibrium the system doesn't return to the initial
equilibrium position This is shown above in Figure 8 5.4

Note

This graph shows what happens when more products is added

to the system
Adding more NH gas
would result in a net
backwards reaction and the

equilibrium position shifting

to the left reducing the
overall concentrationof
ammonia
General effects of a change to a system at equilibrium

predicting the effect of a change using theequilibrium law

consider the equilibrium formed between nitrogen and hydrogen

as an example
Naog t 3 Haig 2MHzcop

the eupression for the equilibrium law for this reaction can
be written as

Kc NH
3
Nz Hz

If enka nitrogen is added the concentration of Na is increased

so Qc is momentarily less than Kc the forward reaction
will be favoured in order to partially compensate for the
adding of nitrogen gas
Completing Equilibria Carbon Monoxide poisoning

Haemoglobin is alarge protein molecule that is the pigment

in red blood cells It is responsible for the transport of
ouygen from your lungs to the cells in your body The
haemoglobin compleu combines with onygen to form an
equilibrium system with ouyhaemoglobin

haemoglobintouygen Oneyhaemoglobin

When
you inhale onygen from the air combines with
haemoglobin in the small blood vessels in the lining of your
lungs

According to Le chatelier's principle this increase in

concentration of anygem in this environment will cause
a net forward reaction producing greater amounts of
oilyhaemoglobin In your lungs most haemoglobin is converted
to onyhaemoglobin as a result of the continual addition of
Ouygen from each breath you take

Carbon mononide is colourless odourless and tasteless

a
gas
that is formed as a product in the incomplete combustion
of fuels The high tonicity of carbon mononide is a result
 haemoglobin carbon mononide Carbonyhaemoglobin

The for the reaction between

equilibrium constant
carbon mononicle and haemoglobin is nearly 20000
times greater than the reaction between onygen and
haemogloblin The larger equilibrium constant means that the
forward reaction is much more likely to occur Even
small concentrations of carbon monoxide shift theposition
of equilibrium well to the right

The formation of cartoonyhaemoglobin reduces the concentration

of haemoglobin causing the reverse reaction of Onghaemoglobin
formation to occur In entreme cares almost no onyhaemoglobin
is left in the blood and carbon mononide poisoning occurs

The reactions of onygen and carbon monowide with haemoglobin

are described as competing equilibria because both ouygen
and carbon mononide compete for the same substance
haemoglobin The equilibrium reaction with the larger equilibrium
constant has a significant effect on the entent of reaction
of the other reaction
 A
market
common treatment for carbon mononide poisoning is
to give the person pure ouygen This is an attempt to
shift the equilibria between ouyhaemoglobin and
haemoglobin Addition of onygen in this equilibrium

haemoglobin t Okygen i
Oleyhaemoglobin

should shift the reaction in the net forward direction

Note However the large value of the carboxyhaemoglobin

equilibrium constant and the relatively slow rate of
release of carbon mononide means this treatment is not
always successful
Further applications of Le Chatelier's principle

Pressure
changing by changing Volume

The pressure of a is inversely proportional to the volume

gas
of its container P the pressure of gases in an
Lv o

equilibrium minture can be changed by increasing or decreasing

the volume of the container while keeping the temperature
constant

Consider the effect of increasing the pressure on the equilibrium

between sulfur dionidegas onygen and sulfur trioxide gas for
the following reaction

2502cg t 02 cgs 2503cg

3 gasparticles 2 gasparticles

The forward reaction involves a reduction involves a

reduction in the number of particles of gas from 3 to 2 This
would result in an overall reduction in pressure of the
system
the number of gas particles from 2 to 3 So a net backwards
reaction causes an overall increase in pressure of the system

Applying Le Chatelier's principle

he Chatelier's principle tells us that an equilibrium system

willrespond to an increase in pressure by adjusting to
reduce the pressure The positionof equilibrium will therefore
move in the direction of the fewer gas particles
In the enample
2502cg t 02cg T
259cg

an increase in pressure will cause a net forward reaction

to occur in order to reduce the overall pressure C 3
gaseous particles become 23 The amount of so present
at equilibrium will increase as represented below
 This is the graphical representation of
the effect of increased pressure

When the system is initially at equilibrium

and there is an increase in pressure the
partial pressures of all gases increase
simultaneously
as do the concentrations

As the system adjusts there is a gradual

change in concentration of each of the species unitil the new

equilibrium is established At the new equilibrium positron the

individual partial pressures and concentrations are different
from at the 1st equilibrium However Kc has not changed
as the ratio remains the same

Applying Equilibrium Law

For the equilibrium system 2502cg t 02cg I

259cg

Kc SO suppose thevolume of thesystemis halved

son On the partial pressures of all reactants and
products double as does their
 a o s

Momentarily Qc becomes

2 SO
240.34 cos 2 fo take

E Qc Ltc accordingly there will be a net forward reaction

to increase the value of Qc until it becomes to Kc

martlet
Pressure changes
do not affect the equilibrium position of
the systems in solid or liquid phases Particles in these
systems are too tightly packed for an increase in pressure
to have a noticeable effect on volume This means there is a

negligible change in the concentration of the species involved

and no effect on the concentration fraction

What happens when the number of gaseous particles on both

sides of the equilibrium system are equal

When there are equal numbers of reactant and product

particles a change in pressure will not shift the

position of equilibrium This is the case forthe equilibrium below

2 gas particles 2 gas particles
Hacgst In cgs 2 HI Cgs
It doesn't matter which way the system shifts the
 of p co ar w ma
This is as the system is unable to oppose the change applied

Example Question

doubling the volume would have the pressure of all

species at equilibrium To oppose this change the system
shifts to the left which increases the amount oh
Cle

Changing Pressure By adding an Inert gas

The total pressure of an equilibrium minture of

moths

gases
without changing the volume of
may also be changed
the container
by adding a non reacting gas such as
helium neon or
argon
Because the presence of the
additional gas does not change

any of the concentrations of the

reactants and products there
is no effect on the position of
Dilution

For an equilibrium occurring in a solution dilution by

adding water reduces the number of particles per volume
This results a shift in the position of equilibrium towards the
side that produces the greatest number of dissolved
particles Consider this equilibrium system for euample
2 particles l
particle
Ferdteag SCN caq Fe SCN cag
in solution in solution

The addition of water momentarily lowers the concentration

of each species In terms of he Chateliers principle a

net reverse reaction will occur increasing the total

concentration of particles in solution
ChangingTemperature

Consider this reaction 2NOmg Nz04cg energy

When the temperature of this system increases this is

what happens
Effect of a catalyst on Equilibrium

acatalyst lowers the activation

energy of the forwardand
backward reactions by the
same amount

A lower activation energy

causes an increase in the number of effective collisions As a
result there is an increase in the rate of both forward
and backward reactions

Equilibria in a swimming pool

Swimming pools are chlorinated to prevent the growth of harmful

Micro organisms Chlorination produces hypochbrous acid CHOU
which is a ethicient antibacterialagent and algicide
very

Commercially availible pool chlorine powder consists of calcium

hypochlorite
y e
hypochlorite ions Oct The hypochlorite ions then react with
hydronium ions in the water to form hypochlorous acid

Ca OCI es F Ca't ca t 20cL cap

OCI cap t Hgotcag F HOCIcag H2O

The HzOt is available from the self ionisation of water

another equilibrium reaction this time between water
molecules forming HzOt and OH ions

H2O t H2O F Hz Ot cag t OH cap

The relative amounts of HOG OCI and HzOt in a

swimming pool need to be controlled carefully This is
done by monitering the pH of the swimming pool and
either adding more pool chlorine or more acid as needed
to maintain a
pH in the range 7.2 7.8

pH measures the concentration of HzOt ions As pH increases

the concentration of Hooters decreases

On the other hand as pH falls the concentration of Hgoteag

increases
Summary

Optimising the yield of industrial processes

Chemists to manimise the reaction rate

try and product
yield of chemical reactions by manipulating the position of
equilibrium and controlling reaction rate

Conditions that favour fast reaction rates and those that

favour high equilibrium yields
PercentageYield

The mass eupected to be termed if all

of product that is
reactants react fully according to the equation is known
as the theoretical yield and can be calculated
using
stoichiometry

However the actual yield obtained for industrial processes

is often less than the theoretical yield because of

formatron of an equilibrium
a slow reaction rate
loss of reactants and products during transfers between
reaction vessels and in separation and purification stages

The percentage yield compares the actual yield to the

theoretical yield A high percentageyield is desirable in
to reduce waste and
industry in order manimise profits It
can be calculated by

Percentage yield actual yield 100

theoreticalyield
 Summary

Increasing the concentration of one species Cadding or removing

reactant or product

Le Chatelier's principle changes to Qc andKc Relativereactionrates

We increase the We increase the Weincreasethe
concentration of one concentration of one concentration of one

species System changesspecies Kc doesn't species There will be

as to partraly change Qc initially more fruitful collisions
Qcneeds between this species
decrease theconcentration changes since

ofthespecies System to equal Kc Qc will and its other reactant

favours reaction that subsequently offset this The rate of this macho
consumes thisspecies change will increase and be
4 than the backward
reaction The position of
equilibrium changes until

the rate of both reactions

are equal again

Note that reciprocal changes occur if you decrease the

concentration of one species instead
 Decreasing the volume of the container Cincreasing thepressureof
the system

Le Chatelier's principle changes to Qc andKc Relativereactionrates

We increase the We increase the Weincrease the

pressure inside the concentrationof all concentration of all
vessel Thesystem speciesby the same thespecies The rate
changes to partially factor Kc doesn't of both the forward
decrease the pressure change Qc initially and backward
and i favours the changes as theside reactions will both
reaction that numerator or increase by dittent
produces fewer denominator with amounts Thepositron
particles more particles will of equilibrium will
increase more since change onto the
Qc wants to equal rates of forward
Kc Qc will subsequently and backwardreaction
offset the change are equal

Note Reciprocal changes occur if we increase the volume

of the container
Increasing the temperature Cenothermic forward reaction
Le Chatelier's principle changes to Qcandke Relativereactionrates

We increase the Weinereau the If youincrease the

temperature The temperature Kc temperature the
system changes as decreased as Qc rate at both the
to partially decrease always attempts to forward and the
the temperature equal Kc Qe backward reactions
and favours decreases subsequently will both increase
the endothermic For Qe to decrease by different amounts
reaction back the back seaction Equilibriumposition
reaction must be favoured changes until both
rates are equal
Increasing the temperature endothermic forward reaction

Le Chatelier's principle changes to Qc andKc Relativereactionrates

We increase the We increase the Ifyou increasethe

temperature The temperature and no temperature the

system changesas As Qcalways rate of both the

increases

to partrally attempts to equal forward and the

decrease the temperature ke Qc increases backward reactions
and favours the subsequently For will both increase by
endothermic reaction Qc he increase the different amounts
the forward forward reaction Equilibrium position
reaction must be favoured Changes until both
rates are equal