Chemical Equilibrium

Goal :

• Predict the evolution of a chemical system

• When a chemical system is at equilibrium predict the

evolution of the system if the equilibrium is modified

100
 Chemical Equilibrium
A chemical system out of equilibrium will evolve
spontaneously toward a state where all intensive variables
(P, T, composition) are constants.
This is the equilibrium state of the system. There are three
possibilities :

• Complete reaction this mean that at least one reactant

have disappeared completely.
• Nothing have happens this mean that the reaction is not
spontaneous at all. (The inverse reaction is
spontaneous),the system was already at equilibrium
• In the final equilibrium state significant fraction of the
product and the reactant are present. The reaction is not
complete.
101
 Chemical Equilibrium

Questions

1. What drive the system toward equilibrium ?

2. At equilibrium are the reactions still occurring or not at all ?
3. Can we modify an equilibrium state
4. Can we determine the composition of a given chemical
system given the initial state?

Avoid confusion between an equilibrium reaction and a

system at equilibrium

102
 Chemical Equilibrium

Exothermic reactions example:

1) Combustion (Oxidation by O2)

2) Neutralization
3) Decomposition of vegetable matter into compost
4) ...

Lots of reactions are producing heat

103
Chemical Equilibrium : exothermic reaction

Energy is released by the system 104

 Exothermic Reactions
What drive the change toward equilibrium :

1) Exothermic reactions have tendency to occur

spontaneously
2) The system in its final state contains less internal
energy U then in the initial state (or enthalpy).
3) This reaction are energy driven.
4) But some endothermic reactions also occurs what is
driving them ?

105
 Endothermic reactions

Some endothermic reactions also occurs spontaneaously :

https://www.youtube.com/watch?v=9kRS8tY7aJY

106
 Endothermic reactions

Endothermic reactions also occur, in this case the system

is taking heat from the surrounding. The system in its
final state contain more energy then in the initial state.

This type of reactions are driven by an increase of

entropy.
Entropy S is a state function that increase when V, T, n ,
are increased.

It is also associated with an increase of disorder so

entropy also increase when gas are produced.
107
 Why is the system evolving

1) Decrease in internal energy (U).

2) Increase in entropy (S)

• If both factors are favourable then the reaction is

always spontaneous.
• If both factors are unfavourable the reaction is not
spontaneous
• If one factor is favourable and the other is not then it
depends on the condition (Temperature) usually the
reaction is not complete
108
 Example 1 :

The following reaction is exothermic :

Mg (s) + 2 HCl (aq) à MgCl2(aq) + H2(g)

Is the entropy factor also favourable ?

109
 Example 2

The following reaction is exothermic:

N2(g) + 3 H2(g) à 2 NH3(g)

Is the entropy factor also favourable ?

110
 Chemical Equilibrium

Two factors are driving the evolution the system

[Internal Energy] and [Entropy]

• If both factors are favourable then the reaction is always

spontaneous.
• If both factors are unfavourable the reaction is not spontaneous but
the inverse reaction is spontaneous !
• If one is favourable and the other is not then it depends on the
condition (Temperature). In this case the reaction occurs in both
direction and a dynamic equilibrium is reached 111
 Exercice

Complete with ->, <- or

1) CaCO3(s) ??? CaO(s)+ CO2(g) (endothermic)

2) C3H8(g) + 5 O2??? 3CO2(g)+ 4H2O(g) (exothermic)

112
Equilibrium distrubance : Le Chatelier Principle

• A system at equilibrium subject to a change will

adjust by counteracting the effect of change.
• Example :
– If a reagent is added the equilibrium will adjust by consuming the
reagent (equilibrium is shifted in the direct direction).
– If a product is added the equilibrium will adjust by consuming the
product (equilibrium is shifted in the indirect direction).
– Increase of temperature, the equilibrium is shifted in the
endothermic direction
– Decrease of temperature the equilibrium will be shifted in the
exothermic direction
– Compression the system will try to lower the pressure by reducing
the quantity of gas

113
 Le Chatelier Principle
Consider the following system at equilibrium in a fixed volume

2 SO2(g) + O2(g) ⇄ 2 SO3(g).

This is an exothermic reaction. What will happen if :

a) If one increase SO2 molar fraction ?

b) If one decrease O2 molar fraction ?
c) If we lower the pressure ?
d) If the temperature is increased ?

114
 Le Chatelier Principle

Consider the following system at equilibrium in a fixed volume

N2(g) + 3H2(g) ⇆ 2NH3(g)
This is an exothermic reaction.
To increase (NH3) production is it better to work at :

a) Low pressure or high pressure?

b) High temperature or low temperature?

115
 Reaction Quotient
For a given reaction we define Q the reaction quotient as

ν1 A1 + ... + ν i Ai → .... + ν k Ak + ... + ν N AN ∑ν A = 0

i i
i=1

νi
∏a ( products) νi
Q= i
νi
= ∏a i
∏a (reac tan ts)
i
Where the ai are the dimensionless activities and the ni stoichiometric
coefficients
116
 Activities

• Definition : ai=activity of i = gixi where :

• gi = Activity coefficient= varies between 0 and 1; gi = 1 for
ideal system (Ideal gas or ideal solution)
• Pure solid pure liquid : xi=1
• Gas xi=Pi/P° P°=1 bar=105 Pa
• Solution : xi=1 for the solvent
• Solution xi=Ci/C° for the solute and C°= 1 mol.L-1

117
 In ideal cases

In most cases and for us in the scope of this lecture :

• gi = 1
• solid : ai=1
• gaz : ai= Pi/P°
• solution ai= Ci/C° solute
• ai= 1 solvent or pure liquid
• Liquid ai= xi molar fraction

This is an approximation in particular for ionic solutions.

More complexes expressions can be derived and are
useful. P° = standard Pressure: P°= 105 Pa = 1 bar
C° = 1 mol.L-1 118
 Activities in ideal case

Substance Activity* Comment

Ideal gas, X(g) a = PX/P° PX is the partial pressure of the gas and P° = 1 bar.
When pressure is expressed in bar, a = PX
Pure solid or liquid, a=1 The activity of a pure solid (or a pure liquid) is equal to 1
X(s) or X(l)
Solute in an ideal a = [X]/c° [X] is the concentration in mol/L and c° = 1 mol/L.
solution, X(aq) When concentration is expressed in mol/L, a = [X]
*To incorporate deviations from ideal behavior, we would write a = γPX/P° for a gas and a = γ [X]/c° for a
solute in solution, where γ is an experimentally determined correction factor called the activity coefficient.

• All activities are unitless. Because of the use of activities, the equilibrium constant is also unitless.
• Pure solids and liquids are not included in equilibrium constant expressions.
 Exercise

Write the reaction quotient of the following reactions :

1. H2(g)+1/2O2(g)->H2O(g)
2. CaCO3(solid)->CaO(solid)+CO2(g)
3. CH3COOH(aq) + C2H5OH(aq) -> CH3COOC2H5(aq) + H2O(l)
4. CH3COOH(aq) + H2O (l) -> CH3COO- (aq) + H3O+ (aq)
5. Fe(s) + 2H3O+(aq) = Fe2+(aq) + H2(g) + 2H2O(l)

120
 Chemical Equilibrium
Law of Mass action or Guldberg and Waage Law

At chemical equilibrium :
Qeq = K°(T)

Where:
Qeq reaction Quotient at equilibrium
K°(T) equilibrium constant dimensionless and only Temperature
dependant
If K and the initial system composition are known then we can predict
the final (equilibrium) composition

121
 Chemical Equilibrium
• Spontaneous change, if we start in a given state
define by Q0

- If Q0 < K° : the system will evolve in the direct, direction Q

will increase until Q= K°
- If Q0 = K° : the system is at equilibrium: no evolution.
- If Q0 > K° : the system will evolve in the indirect direction, Q
will decrease until Q=K°

122
 Chemical Equilibrium

Q - If Q < K° : the system will evolve

in the direct, direction Q will
Reactants
increase until Q= K°
- If Q = K° : the system is at
Products
equilibrium: no evolution.
- If Q > K° : the system will evolve
K°
in the indirect direction, Q will
decrease until Q=K°
xeq x
123
 Chemical Equilibrium

Different situations can occur :

- K°(T) >>104 : Almost complete reaction, one of the reactant will fully
dissapear

- 10-4<K°(T) <104 : Reversible or equilibrium reaction, product and

reactant will coexist

- K°(T) <10-4 ; almost no reaction in direct direction, but the reaction is

almost complete in the indirect direction

124
 Chemical Equilibrium :
Equilibrium Constant and units !

• The dimensionless equilibrium constant can be noted

K°(T) or K° or K
• In many books and exercices you will find equilibrium
constant with unit (Kc Kp etc …) it still a constant but it
is no longuer expressed in term of activities but in
term of partial pressure, concentration etc …

125
 Chemical Equilibrium
Example Consider the following reaction in a fixed
volume :
CO (g) + H2O (g) ⇆ CO2 (g) + H2 (g)

a) We start with 1.00 mole of CO and 1.00 mole de H2O in 20L fixed volume.
The temperature is increased to 1700 °C. At equilibrium 0.32 mole of H2
have been produced. What is the value of K°.

a) At the same temperature we start with 1.000 mole of CO, 1.000 mole of
H2O, 1.000 mole of CO2, 1.000 mole of H2. What is the equilibrium
composition ?

126
 Chemical Equilibrium
Example Consider the following reaction in a fixed volume :

2NO2 (g) ⇆ N2O4(g)

In 2,00 L volume , 0,100 mole of N2O4(g) is placed at 25°C. At equilibrium 0,032

mole of NO2 have been obtained.

a) What is the value of K°.

b) How will K evolve if the total pressure is increased ?

127
 Chemical Equilibrium

A 100mL solution containing initially 1,50.10-3 mol of Fe3+ and

2,5.10-4 mol SCN- is prepared. The following reaction occurs :
Fe3+ +SCN- -> FeSCN2+
At equilibrium the solution contains 2,0.10-4 mol de FeSCN2+
What is K value ?

128
 Chemical Equilibrium

Example Consider the following reaction in a fixed volume :

2 HI (g) ⇆H2 (g) + I2 (g).

1,00 mole of HI(g) is introduced in 2,00 liters. The Temperature is increased to

444°C, only 0,78 mole of HI are left at equilibrium.

a) What will be the equilibrium (for the same volume and temperature)
composition of a system containing initially 1,00 mole of HI, 8,00 moles of
H2 et 3,00 moles of I2 ?
b) At this point we add 1,00 mole of I2 (g). What will happen ?

129
 Chemical Equilibrium : Examples

• Acid base equilibrium

• Solubility equilibrium
• Redox equilibrium
• Complex formation

130
IC4

131
 Acid-base Equilibrium

• Bronsted :
– Acid = proton H+ donor
– Base = proton H+ acceptor

• Reaction Acid ->Base + H+

• Acid-base pair A/B : A->B+H+ B is the conjugated base of A
• Acid-base reaction : A1+B2->B1+A2

In the following only aqueous solutions will be considered in

water H+ exists only as hydroniums ions H3O+
 Acid/Base in aqueous solutions
• Water can act as acid or base :
– A+H2O -> B+H3O+
– B+H2O -> A +OH-

• Acidity constant Ka : For a given acid/base pair

the acidity constant is the equilibrium constant of the
following reaction : A+H2O -> B+H3O+
⎡ B⎤⎡ H O + ⎤
⎣ ⎦⎣ 3 ⎦
Ka =
⎡ A⎤
⎣ ⎦
• Ka taking value in the range 10-20 - 1010 the use of a
logarithmic scale is more convenient:
pka=-logKa and pH=-log [H3O+]
 Acid/Base in aqueous solutions

• Basicity constant : Kb is the equilibrium constant of

the following reaction : B +H2O->A+OH-

[ ][
A OH −
]
Kb =
[ B]

• Water autoprotolysis or autoionization:

2H2O->H3O+ +OH- kw=[H3O+ ][OH- ]=10-14 at 25°C this
€
implies for pure water :[H3O+ ]=[OH- ]=10-7 and pH=7
 Acid/Base in aqueous solutions

• Water autoprotolysis or autoionization : In water the

following reaction also occurs :
• 2H2O->H3O+ +OH-
• kw=[H3O+ ][OH- ]=10-14 at 25°C
• This implies for pure water : [H3O+ ]=[OH- ]=10-7 and
pH=7
• We can also show that In presence of an acid pair in
water : KaKb=Kw pKa+pKb=pKw and pH+pOH=pKw
Acid and base
Acid/base strength
 Solubility equilibrium

• When a solid is dissolved in a solvent the following

(heterogeneous) equilibrium is established :
AB(sol)->Ax+ + Bx-
• With the following equilibrium constant :Ks=[Ax+] [Bx-]
solubility constant or solubility product constant

• The solubility of AB is the amount of AB that can be

dissolve here :

s = ks
• S expression can change depending on the number
of species formed during dissolution

€
 Solubility equilibrium

Solubility product constant in water at 25°C

How many of table salt (NaCl) can we dissolve in water ? What

happens if you add more ?
 Complex formation equilibrium

• In solution metal ions can form complex by reacting

with one or several Ligand :
M+nL->MLn

• The equilibrium constant of this reaction is the

constant of complex formation (or stability constant) :
⎡ ML ⎤
⎣ n⎦
Kf = n
⎡ M ⎤.⎡ L⎤
⎣ ⎦⎣ ⎦
• This constant are usually very big (around 1010)
Complex formation constants
 Redox Reaction

• Oxidation = electron loss

• Reduction = electron gain
• During oxidation oxidation number increased
• During reduction oxidation number decreased
• Half reactions :
Re duction
Ox + né " " "
"→ Re d
Oxydation
Re d ⎯ ⎯⎯⎯
→ Ox + né
€
 Oxidation number
Type Oxidation number
Atome alone 0
Simple Ion charge
Molecule and molecular ion Charge carried if the
bounding electrons are
affeceted to the most
electronegative partner

Exemple Na+; Al3+,N2, HCl,HF,Br2, H2C=O

 Redox reaction

Two half reactions are combined :

aOx1+bRed2-> cRed1+dOx2

• Example : Cu2++Zn->Cu +Zn2+

• If a piece of Zn is dropped in a Cu2+solution , some
Cu appear on the Zn piece and some Zn2+ in the
solution. The reverse reaction is not spontaneous.
 Chemical Kinetics

• Up to now we have only discussed how to determine

the equilibrium state. We did not study the time
needed to reach this state. This will be the goal of the
next chapter : chemical kinetics.

145
 Reaction rate

• We define the reaction rate as the time derivative of

the extent of reaction:

dx
v=
dt
• This becomes for any constituent:

dx 1 dn i
€ v= =
dt υ i dt

146
 Reaction rate

• Example : A+2B->3C
• The reaction rate or rate of reaction
dx dn a 1 dn b 1 dn c
=− =− =
dt dt 2 dt 3 dt
• In solution we can replace ni by Ci the rate are
therefore in mol.L-1s-1
€ • In gas phase if V=cste we can use the partial
pressure
• Check the units !

147
 Reaction rate

What change the reaction rate :

• Temperature
• Reactant concentration but usually not product
concentration

The reaction rate have to be determined experimentally

148
 Reaction rate in solution

For a given reaction A+B-> C the rate law can be

written as follow
a b
v = k [ A] [ B ]
Where
• A and B are the reactants
• K is the rate constant or rate coefficient
• a and b are the partial order with respect to A and B
• a+b is the overall order of reaction

149
 0 order reactions

dx
v = k [ A] ° = k =
dt

Solution [A]=A0-kt

150
 First order reaction

• For A->B with a first order reaction:

dx
v = k [ A] =
dt
• We get [A]=A0exp(-kt)
• We can define a reaction half-time
• €We have similar law for
1. Nuclear reaction
2. A reaction of the type : A+B-> C were one of the
reactant is in large excess

151
 Second order reaction rate

• For A->B with a second order rate

2dx
v = k [ A] =
dt
• It gives
1 1
= + kt
A0 − x A0
ۥ This is also the case for A+B->C with a first order law with
respect of both reactants and in equimolar proportion.

€ 152
 How to simplify a reaction law

• Excess of one of the reactants

• Work in stoichimetric conditions

153
 Arhenius law

• The rate constant increase with T following Arhenius

law :
−Ea
k = Arr exp( )
RT

• Where Ea is the activation energy and Arr a constant.

Ea et A are T independant.

154
IC5

155
Chemical Reactions vs Nuclear Reactions

160
The Nucleus

163
The Nucleus

164
The Nucleus

165
Nucleus Model

166
 Nuclear stability : Mass defect

Nucleus binding energy : E=Dmc2

Where :
Dm = (Sum of the mass of proton neutrons and electron)-atomic Mass= Mass defect
c= speed of light

Example : for Litium-7 : Dm = 7,3079.10-29 kg

7 Li
3 DEl = Dmc2 = 7,3079.10-29 kg * (3.108)2 = 6,5577.10-12 J

167
Nuclear Stability and Binding Energy

168
Radioactive Decay and Nuclear Equations

169
Radioactive Decay and Nuclear Equations

170
Radioactive Decay and Nuclear Equations

The three main decays are Alpha, Beta and Gamma

171
Radioactive Decay and Nuclear Equations

Penetrating Abilities

Alpha particles may be

completely stopped by a sheet of
paper

Beta particles by aluminum

shielding

Gamma rays, can only be

reduced by much more substantial
obstacles, such as a very thick
piece of lead 172
 Radioactive Decay and Nuclear Equations

Balancing Nuclear Equations

1) Conserve mass number (A)
Sum of protons plus neutrons in the products must equal sum of protons plus
neutrons in the reactants

235 + 1 = 138 + 96 + 2x1

1)2) Conserve atomic number (Z) or nuclear charge

Sum of nuclear charges in the products must equal sum of nuclear charges in the
reactants

92 + 0 = 55 + 37 + 2x0 178
n/p ratio and Nuclear Stability
Stable nuclei located in an area known
as the belt of stability.

Above the stability belt, the nuclei have

higher n/p ratios than those within the
belt (for the same number of protons).

To lower this ratio (move down toward

the belt of stability), these nuclei undergo
the process, called beta-particle
emission.

Below the stability belt the nuclei have

lower neutron-to-proton ratios than those
in the belt (for the same number of
protons).

To increase this ratio (move up toward

the belt of stability), these nuclei either
emit a positron or undergo electron179
capture.
Radioactive Decay and Nuclear Equations

Neutron-rich Nuclei

β- emission

Z increases by 1
N decreases by 1
A unchanged

Above Stability Belt 180

Radioactive Decay and Nuclear Equations

Neutron-poor Nuclei

1) Positron emission

Z decreases by 1
N increases by 1
A unchanged

Below Stability Belt 181

Radioactive Decay and Nuclear Equations

Neutron-poor Nuclei

2) Electron capture

Z decreases by 1
N increases by 1
A unchanged

Below Stability Belt 182

Radioactive Decay and Nuclear Equations

Neutron-poor Nuclei (heavy ones!)

3) α emission

Z decreases by 2
N decreases by 2
A decreases by 4

Below Stability Belt 183

Radioactive Decay and Nuclear Equations

Nuclei with Z > 83 Beyond Stability Belt

α emission
Z decreases by 2
N decreases by 2
A decreases by 4

Few decay by β emission, positron emission or e capture

Transuranium Elements decay by Nuclear Fission

184
Rates of Radioactive Decay and Half-Life

Nuclear decay is a random process; the decay of any nucleus is

not influenced by the decay of any other

Radioactive decay is a first order process, ie, the number of

decays/s is proportional to the number of nuclei present
Nuclides
Rate of decay α N
Rate of decay = A = λ N

Activity
[atoms/time]
185
Rates of Radioactive Decay and Half-Life

Nuclear decay is a random process; the decay of a given nucleus

is not influenced by the decay of the other

Radioactive decay is a first order process, ie, the number of

decays/s is proportional to the number of nuclei present
Nuclides
Rate of decay α N
Rate of decay = A = λ N

Activity Decay constant

[atoms/time] [time-1]
186
 Rates of Radioactive Decay and Half-Life
Kinetics Nuclear decay

[A]0 Ln (N°/N)=lt
ln = kt
[A]

Concentration Number of Nuclides

[A] =[A]° exp(- kt) N=N°exp(- lt)

A= A 0 e− λ t

187
Activity
Rates of Radioactive Decay and Half-Life

−λt
N=N°exp(- lt) A= A 0 e

188
Rates of Radioactive Decay and Half-Life

ln 2 0,693
Half-Life t1 /2 = =
λ λ

189
Rates of Radioactive Decay and Half-Life

ln 2 0,693
Half-Life t1 /2 = =
λ λ

190
 Radioactive Decay and Nuclear Equations
Activity units

SI: Becquerel (Bq) 1 Bq = 1 disintegration / s

Common unit is MBq

Older: Curie (Ci) 1 Ci = 3,7 x 1010 disintegrations / s

Originally defined as the activity of 1 g of radium

Common unit is mCi or μCi

191
 Uses of Radionuclides

Radioactive Dating

Medical Uses

Agricultural and Industrial Uses

Research Aplications

192
193
194