Chemical

concentration
processes Time

Potential energy
aA + bB → cC + dD

Potential energy
v = k.[A]α.[B]β
Reaction progress

Potential energy
Reaction progress

Reaction progress

● Heat of reactions
● Exo- and endothermic reactions
● Rate of chemical reactions
● Chemical equilibrium
1. Heat of chemical reactions.
exo- and endothermic reactions 3
2. Heat of formation. Heat of combustion. Fuels calorific values 12
3. Hess's law 21
● Energy changes during chemical reactions ‒ key points 30
4. Rate of chemical reactions 32
5. Effect of reactants concentration on reaction rate. Rate law 39
6. Effect of temperature on reaction rate
7. Catalysis. Catalysts 49
8. Homogeneous and heterogeneous catalysis 54
9. Reversible and irreversible chemical reactions. Chemical equilibrium 62
10. Effect of concentration, pressure and temperature
on chemical equilibrium 70
● rate of reactions and chemical equilibrium ‒ key points 79

PROJECTS 82
Click on a topic to jump to the page
 Heat of chemical reactions.
1 Exo- and endothermic reactions
key TOPICS
1. Does temperature change when a chemical reaction goes on?
2. What is heat of a chemical reaction?
3. What chemical reactions are exothermic and what ‒ endothermic?
4. How to denote the amount of heat exchanged during a chemical
transformation?
TRANSITION state
Potential energy

key words
Activation
energy

TRANSITION state
●● Heat of reaction
Potential energy

Initial state

∆H < 0 ●● Exothermic reaction

FINAL state ●● Endothermic reaction
Activation
energy

FINAL state
●● Thermochemical equation
Reaction progress ∆H > 0
●● Activation energy
Initial state

Reaction progress
3
Can a chemical reaction be a „generator“ of energy as heat?
Usually, during chemical reactions energy (as heat and/or light) is liberated or absorbed. Temperature
changes accompanying chemical reactions can be measured. This makes it possible to determine the
amount of evolved or absorbed heat. Thermochemistry is the science studying the heat effects
of chemical reactions. The basic quantity is the heat of reaction (also named enthalpy change of a
reaction if the pressure remains constant). It is denoted by ∆H. It strongly depends on the reaction
conditions (temperature and either pressure or volume). The SI unit of the heat of reactions is joule J.

HEAT OF REACTION ∆H is the amount of heat evolved or

absorbed during a chemical reaction undergoing at constant
temperature and at either constant pressure or volume.

When heat is released (lost), ∆H < 0.

When heat is absorbed (gained), ∆H > 0.
The amount of heat evolved or absorbed during a chemical reaction depends on the quantity of
reactants. (If only two logs burn in the fireplace the temperature in the room might be to low and to
assure a pleasant comfort more logs must be burnt.) For this reason, heat of reactions usually refers to
the same amount of reactants and products as in the balanced chemical equations of the reactions*.
Most often heats of reactions refer to 25 0C and 105 Pa. Heats of reactions at these conditions are
denoted as ∆H0.
-------------------------------
*It is often denoted as ∆Hrxn 4
Depending on the heat effects (positive or negative) chemical reactions are classifies as exothermic
and endothermic.

exothermic REACTIONs are chemical reactions that generate heat.

The temperature of the surrounding increases. ∆H < 0

Temperature rises
Well known exothermic reactions are respiration, combustion, neutralization, energy
energy
slaking of lime. Some exothermic reactions release a great amount of heat into
the surrounding over a very short time and they can be explosive. For example,
methane CH4 mixed with pure oxygen O2 or air is highly explosive. Spark or
direct flame can initiate a vigorous reaction and the mixture can explode. At Exothermic reaction
high pressure ethyne C2H2 decomposes into hydrogen and carbon releasing a ∆H < 0
great amount of heat and it can explode too.

Temperature decreases
endothermic REACTIONs are chemical reactions that absorb energy.
The temperature of the surrounding decreases. ∆H >0 energy
energy

Endothermic reactions are thermal decompositions, photosynthesis, cracking of

alkanes, the reaction of ethanoic acid CH3COOH with disodium carbonate Na2CO3,
the synthesis of nitrogen oxide NO from nitrogen N2 and oxygen O2. Endothermic reaction
∆H > 0 5
 Thermochemistry uses thermochemical equations ‒ the amount of energy lost or gained as heat is
denoted after the chemical equation of the reaction. The physical states of reactants and products is
always indicated. The abbreviations (s) is used for substances in solid state, (l) ‒ for substances in liquid
state, (g) ‒ for substances in gaseous state, (aq) ‒ for aqueous solutions of substances. It is important
to indicate the state of reactants and products as additional energy is absorbed or released during
phase transitions (solid-liquid, gas-liquid, etc.) as well as during physical processes as dissolution,
dissociation, etc. For example:
1 mole of H2(g) + 1 mole of Cl2(g)
H INITIAL STATE
H2(g) + Cl2(g) → 2HCl(g) ∆H0 = ‒ 184,6 kJ
∆H0 = ‒ 184,6 kJ The reaction of synthesis of hydrogen chloride HCl an exothermic
reaction ‒ heat is evolved. The graph to the left shows that
2 moles of HCl(g) FINAL STATE energy is lost into the surrounding.
exothermic reaction
2 moles of NO(g)
H FINAL STATE
N2(g) + O2(g) → 2NO(g) ∆H0 = + 180,8 kJ
∆H0 = + 180,8 kJ The reaction of synthesis of nitrogen oxide NO is an endothermic
INITIAL STATE reaction ‒ heat is absorbed. The graph to the left shows that
1 mole of N2(g) + 1 mole of O2(g) energy is gained from the surrounding.
endothermic reaction

6
The heat of a reaction is a very important quantity as it is used to calculate the total amount of heat
transferred to the surrounding or absorbed from the surrounding when a chemical process goes on.

What is the amount of heat dissipated into the surrounding when 5 moles of sodium
PROBLEM! base dissolved in water neutralise 5 moles of nitric acid also dissolved in water?
The heat of this reaction is ∆H0 = ‒ 57,3 kJ.

Solution: 1. Express the balanced chemical equation of the reaction.

NaOH(aq) + HNO3(aq) → NaNO3(aq) + H2O(l) ∆H0 = ‒ 57,3 kJ
2. Calculate the total amount of heat dissipated into the surrounding.
The thermochemical equation shows that ‒ 57,3 kJ are dissipates into the surrounding when 1 mole of
NaOH reacts with 1 mole of HNO3. It is obvious that when 5 moles of water are produced the amount of
heat released is 5 times greater than the amount of energy released when 1 mole of water is produced,
i.e. 5.(‒ 57,3 ) = ‒ 286,5 kJ.

Answer: ‒ 286,5 kJ as heat are dissipated into the surrounding when 5 moles of NaOH neutralise
5 moles of HNO3.

7
Why do some reactions generate heat but otherS ‒ absorb heat?
Generally, when a reaction is going on energy is transferred to the surrounding or energy from the
surrounding is absorbed, i.e. some energy exchange accompanies chemical transformations. But
what does really happen? In chemical transformations chemical bonds of the reacting species break
down to „liberate“ atoms or ions that regroup forming the new chemical bonds of the products. Each
chemical bond „stores“ potential energy and some amount of energy, called activation energy, must
be supplied to the reacting species to overcome forces holding atoms (or ions) bonded to one another.
A transition state of a higher potential energy is achieved ‒ chemical bonds are unstable, they break
down and the chemical reaction goes on.

Activation energy of a reaction is the minimum amount of energy

that must by supplied to initiate the chemical transformation.

Owing to the regrouping of atoms (or ions) the potential energy drops down because of the formation
of the new stable chemical bonds of the products. If the potential energy of the initial state (the
reactants) is high compared to the potential energy of the final state (the products), some amount of
energy as heat (also light can be emitted) is transferred to the surrounding and it temperature rises ‒ the
reaction is exothermic. In contrary, if the potential energy of the initial state is low compared to the
potential energy of the final state, some amount of heat from the surrounding is absorbed and its
temperature decreases ‒ the reaction is endothermic. These energy changes are presented in energy
diagrams.
8
 TRANSITION state TRANSITION state
Potential energy

Potential energy
Activation
energy

Activation
energy
FINAL state
(products)
Initial state
(reactants)
∆H < 0 ∆H > 0
FINAL state
(products)
Initial state
(reactants)

Reaction progress Reaction progress

Energy is transferred to the surrounding. Energy is absorbed from the surrounding.

Exothermic reaction Endothermic reaction

Energy diagrams

9
 As examples:

TRANSITION state TRANSITION state

H ... H Cl ... Cl ...
N .. .. .. N O .. .. .. O
Potential energy

Potential energy
Activation
energy

Activation
FINAL state

energy
NO NO
Initial state
H‒H Cl‒Cl
‒ 184,6 kJ FINAL state +180,8 kJ
HCl HCl
Initial state
N≡N O=O

Reaction progress Reaction progress

H2(g) + Cl2(g) → 2HCl(g) ∆H0 = ‒ 184,6 kJ N2(g) + O2(g) → 2NO(g) ∆H0 = + 180,8 kJ
exothermic reaction Endothermic reaction

10
 CAN YOU ANSWER THESE QUESTIONS
1. What is heat of reaction?
2. What reactions are exothermic and what ‒ endothermic?
3. What is activation energy of a chemical reaction?
4. Why are some chemical reactions exothermic but others ‒ endothermic?
5. How to prove that the reaction of slaking of lime is exothermic?
6. Why can some chemical reactions cause explosions?
7. What is thermochemical equation?
8. Why is it necessary to indicate the state of the reactants and the products in the
thermochemical equations?
9. The heat of the neutralisation of NaOH(aq) and HNO3(aq) is ‒ 57,3 kJ/mol. The same amount
of heat is generated if 1 mole of NaOH(aq) neutralises 1 mole of HCl(aq). Why?
10. In a test tube 0,1 moles of KOH(aq) react with 0,1 moles of H2SO4(aq). In another test tube
0,4 moles of KOH(aq) react with 0,4 moles of H2SO4(aq)? The temperature of which solution
is higher?
 Heat of formation. Heat of combustion
2 Fuels calorific values
key TOPICS ½H
2 +½
1. What does the heat of formation stand for? Cl
2. What does the heat of combustion stand for? 2 →
3. What substances are fuels?
∆Hf0 HC
4. Why is fuels calorific value their important l
characteristic?

key words
●● Formation reaction
●● Heat of formation
∆Hc0 ●●
●●
Combustion reaction
Heat of combustion
For millennia ●● Calorific value
people have been burning
wood to heat.

12
WHAT IS HEAT OF FORMATION OF A COMPOUND?

Chemical reactions forming 1 mole of a compound from its constituent

elements each of the substances being in its standard state are called
formation reactions.

The standard state is the most stable physical state of a simple substance or a compound at 105 Pa
and a specified temperature, most often at 25 oC. For example, hydrogen H2 and chlorine Cl2 are gases
at 25 oC and 105 Pa. Carbon (the most stable form is graphite) is solid. Carbon dioxide CO2 is gaseous,
sodium chloride NaCl is solid, water H2O is liquid, etc.
Each compound can be considered as formed in a direct reaction of its constituent elements even
such a reaction is not really undergoing. For example, the reaction of formation for glucose is:
6C(s) + 6H2(g) + 3O2(g) → C6H12O6(s)
Most of the reactions of formation of chemical compounds from their constituent elements are
exothermic, some are endothermic. The heat of these reactions is called standard heat of formation
and is denoted by ∆Hf0.
STANDARD HEAT OF FORMATION ∆Hf.0 of a compound is the amount of
heat absorbed or evolved at 25 oC and 105 Pa when 1 mole of the compound
is formed from its constituent elements each of the substances being in its
most stable physical state at these conditions.

The standard heat of formation always refers to 1 mole of the compound. Its basic unit is joules per
mole, J/mol. 13
 Com- ∆Hf0 Com- ∆Hf0 Com- ∆Hf0 Standard heats of formation of various chemical
pound kJ/mol pound kJ/mol pound kJ/mol compounds can be found in many handbooks. Keep
H2O (l) ‒ 285,8 NH3 (g) ‒ 46,2 NaOH (s) ‒ 425,6 in mind that the value of the heat of formation always
H2O (g) ‒ 241,8 HCl (g) ‒ 92,3 CH4 (g) ‒ 74,9 refers to 1 mole of the compound. As an idea, the
H2SO4 (l) ‒ 814 HI (g) + 26,5 C2H4 (g) + 52,5 thermochemical equations for the formation reactions
HNO3 (l) ‒ 174,1 NaCl (s) ‒ 411,1 C6H6 (l) + 48,7 of HCl, C6H6 and KCl are expressed as:
SO2 (g) ‒ 296,8 SO3 (s) ‒ 395,7 C2H5OH ‒ 277,7
½H2(g) + ½Cl2(g) → HCl(g) ∆Hf0 = ‒ 92,3 kJ/mol
Standard heat of formation for some compounds 6C(s, graphite) + 3H2(g) → C6H6(l) ∆Hf0 = + 48,7 kJ/mol
K(s) + ½Cl2(g) → KCl(s) ∆Hf0 = ‒ 436,7 kJ/mol
If the reaction of synthesis of HCl is expressed as H2 + Cl2 → 2HCl, the amount of heat evolved during
the interaction of 1 mole of H2 with 1 mole of Cl2 is twice as large, i.e. ‒ 184,6 kJ.
As a rule the standard heat of formation of simple substances is 0 J/mol. When a chemical element
has two or more allotropes, one of the forms is considered energetically more stable than the others.
Its heat of formation is considered to be 0 J/mol. For example, among the allotropes of carbon ∆Hf0
of graphite is 0 J/mol. ∆Hf0 (diamond) is 1,88 kJ/mol.
Heats of formation of chemical compounds are used to calculate heats of chemical reactions. You will
become familiar with that matter in the next lesson.

14
 At 25o C and 105 Pa ethanol C2H5OH is liquid. Express its formation reaction. The heat of
PROBLEM! formation of ethanol is ∆Hf0 (C2H5OH) = ‒ 277,7 kJ/mol. What is the heat of the reaction if
5 moles of ethanol are formed?

Solution: 1. Express the formation reaction of ethanol.

2C(s) + 3H2(g) + ½O2(g) → C2H5OH(l) ∆Hf0 = ‒ 277,7 kJ/mol
The heat of formation always refers to 1 mole of the product, i.e. the coefficient before the
product is always 1. Some of the other coefficients in the balanced chemical equation are
not always integers. In this example the coefficient before oxygen is 1/2.
2. Determine the heat of the reaction of formation of 5 moles of ethanol.
‒ 277,7 kJ/mol of heat are evolved if 1 mole of ethanol is formed at standard conditions.
The amount of heat evolved during the formation of 5 moles of ethanol is 5 times greater,
i.e.: ∆H0 = n. ∆Hf0 (C2H5OH) = 5. (‒ 277,7) = ‒ 1388,5 kJ.
Answer: The heat of the reaction of formation of 5 moles of ethanol C2H4OH is ‒1,4 MJ.

15
WHAT IS HEAT OF COMBUSTION OF A substance?

Combustion (commonly known also as burning) is one of the most important chemical reactions.
Generally, combustion reaction is every chemical reaction generating heat and light (as flame). But
more often the term „combustion“ refers to reactions with oxygen (pure or from the air) generating
heat and light. Basic quantity is the heat of combustion ∆Hc. When the process undergoes upon 25 oC
and 105 Pa it is named standard heat of combustion and is denoted as ∆Hc0.

STANDARD HEAT OF COMBUSTION ∆Hc0 of a substance is the amount

of energy liberated when 1 mole of the substance undergoes complete
combustion at 25 oC and 105 Pa and with excess oxygen.

Heats of combustion are evaluated in joules per mole of burning compound. The SI unit is J/mol.
Typical combustion reactions are, for example, the flame tests of many metals ‒ sodium and its salts
burn producing an yellow flame, potassium and its salts turn the flame violet, etc. But the most
important combustion reactions are the reactions of organic compounds with oxygen (pure or from
the air). Especially, the combustion of fuels ‒ compounds that generate great amounts of heat during
their combustion. Fuels are fossil fuels as natural gas, petrol (gasoline), coal but also hydrogen H2,
methanol CH3OH, ethanol C2H5OH and others. The overall equation of the combustion of fuels is:

FUEL + O2 → CHEMICAL PRODUCTS + energy

16
 The chemical products of a combustion reaction of fuels are most often CO2 (or CO, even C,
if the combustion is incomplete) and water vapours. At standard conditions 25 oC and 105 Pa the
thermochemical equations of the combustion reactions for hydrogen, methane and methanol are
expressed as:
H2(g) + ½O2 (g) → H2O(l) ∆Hc0 = ‒ 285,8 kJ/mol
CH4(g) + 2O2(g) → CO2(g) + 2H2O(l) ∆Hc0 = ‒ 891 kJ/mol
CH3OH(l) + 3 2O2(g) → CO2(g) + 2H2O(l) ∆Hc0 = ‒726 kJ/mol
The chemical products of fuels combustion are usually considered as waste (gases evolved into the
atmosphere). The most important „product“ of the combustion of fuels is the generated significant
amount of energy. It is used for heating, for cooking, in the internal-combustion engines, in explosives,
to produce electricity, in rocket propulsion, etc. As a whole, the contemporary civilisation can not
function without fuels.
The amount of energy generated during the combustion of a fuel is
∆Hc0 ∆Hc0
FUEL
kJ/mol
FUEL
kJ/mol
its important characteristic. The standard heats of combustion of
H2 ‒ 285,8 C4H10 ‒ 2874
fuels are used to assess their quality as sources of energy. Here are
values of the heats of combustion for some common fuels.
CH4 ‒ 891 C8H18 ‒ 5470
Pay attention that heats of formation are most often negative but
C2H6 ‒ 1560 CH3OH ‒ 726
can be positive too as some reactions of formation are endothermic.
C3H8 ‒ 2222 C2H5OH ‒ 1370 But heats of combustion are always negative because all reactions
of combustion are exothermic reactions generating energy.
heat of combustion for some fuels
17
 At 25o C and 105 Pa hydrogen and oxygen are gases. Water is liquid. Express the combustion
PROBLEM! reaction of hydrogen. What is the amount of heat liberated during the combustion of
5 moles of hydrogen at 25o C and 105 Pa? ∆Hc0(H2) = ‒ 285, 8 kJ/mol

Solution: 1. Express the combustion reaction of hydrogen.

H2(g) + ½O2(g) → H2O(l) ∆Hc0 = ‒ 285,8 kJ/mol
Keep in mind that the heat of combustion always refers to 1 mole of the fuel (in this example
this is hydrogen H2), i.e. the coefficient before it must be always 1 . Some of the other
coefficients in the balanced chemical equation of combustion are not always integers. In this
example the coefficient before oxygen is 1/2.
2. Determine the amount of energy liberated during the combustion of 5 moles of hydrogen.
‒ 285,8 kJ/mol of heat are evolved if 1 mole of hydrogen burns at 25o C and 105 Pa.
The amount of heat evolved in the combustion of 5 moles of hydrogen is 5 times greater, i.e.:
∆H0 = n. ∆Hc0 (H2) = 5. (‒ 285,8) = ‒ 1429 kJ.
Answer: The heat generated during the combustion of 5 moles of H2 at 25o C and 105 Pa is 1,43 MJ.

18
In chemistry the heat of combustion always refers to 1 mole of burning compound upon standard
conditions. But often it is convenient to compare different fuels using another quantity ‒ their calorific
values.

CALORIFIC VALUE of a fuel is the amount of heat liberated when 1 kg

or 1 m3 of the substance undergoes complete combustion upon standard
conditions and with excess oxygen.

For example:

Commercial Calorific value Commercial Calorific value

fuel MJ/kg fuel MJ/kg
Natural gas 54,0 coal 15,0 - 34,0
Petrol 48,0 ethanol 29,7
Diesel 44,8 Dry wood 14,4 - 17,4
Fuel oils 43,0 - 48,8 Hydrogen 141,8

The highest is the caloricity of hydrogen H2 (141,8 MJ/kg). The lowest is the caloricity of wood.
The calorific values of gaseous fuels are also estimated in J/m3. For example, the caloricity of hydrogen
is 12,7 MJ/m3.
The heat of combustion similarly to the heat of formation of substances can be used to evaluate the
heat of chemical reactions. 19
 CAN YOU ANSWER THESE QUESTIONS
1. What chemical reactions are formation reactions?
2. Is neutralisation a formation reaction? Why?
3. Is the equation of the formation reaction of NaCl correctly written? Why?
2Na + Cl2 → 2NaCl ∆Hf0 = ‒ 411,1 kJ/mol
4. What chemical reactions are combustion reactions?
5. What substances are fuels?
6. Is the equation of the combustion reaction of methane at standard conditions correctly
written? Why?
CH4(l) + 2O2(g) → CO2(g) + 2H2O(g) ∆Hc0 = ‒ 891 kJ/mol
7. The heat of formation of liquid water H2O(l) is identical with the heat of combustion of
hydrogen H2? Why?
8. What is the difference between the heat of combustion and the calorific value of a fuel?
9. Which fuel is more calorific ‒ ethanol or petrol?
10. The heat of combustion of ethanol is greater than the heat of combustion of hydrogen. But
hydrogen is more calorific than ethanol. Why?
3 Hess's law
key TOPICS
1. What does the Hess's law state?
2. How is Hess's law used to determine heats of reactions?
3. How to calculate the heat of a reaction using the heats of formation of
the reaction components?
4. How to calculate the heat of a reaction using the heats of combustion of
the reaction components?

REACTANTS ∆H0 PRODUCTS key words

∆H0 (step 1) ∆H0 (step 2) ●● Hess's law

constituent elements

∆H0 = ∆H0(step 1) + ∆H0(step 2)

21
WHAT does the law of conservation of energy have to do with
chemical reactions?
The law of conservation of energy applies to every process in the Universe. It applies to all chemical
transformations too. When a chemical process is going on the energy, as a whole, can not be lost or
gained. If some amount of energy is lost by the reacting system, the same amount of energy is gained
by the surrounding. The energy change of the reacting system depends only on its initial and final
states no matter how the chemical transformation undergoes. This empirical fact is the basis of the
Hess's* law:
The heat absorbed or generated in a chemical reaction is independent of
the route of the reaction but is determined only by the type and the state of
the reactants and the products.

In other words the heat of a reaction is the same whether the transformation undergoes in one step
or in many successive steps. That will become clearer with the help of a simple example. Carbon burns
transforming into carbon dioxide:
C(s) + O2(g) → CO2(g) ∆Hc0 = ‒ 393,5 kJ/mol
But this transformation can undergo in two steps. First CO is formed and it transforms into CO2:
❶ C(s) + ½O2(g) → CO(g) ∆Hc0 = ‒ 110,6 kJ/mol (‒ 110,6 ) + (‒ 282,9) =
❷ CO(g) + ½O2(g) → CO2(g) ∆Hc0 = ‒ 282,9 kJ/mol ‒ 393,5 kJ/mol
The heat of the overall reaction of transformation of C into CO2 is equal to the sum of the heats of the
two successive reactions of transformation of C into CO and after that ‒ into CO2.
------------------------------- 22
*Germain Henri Hess has formulated the law in 1840.
The successive steps of a chemical transformation are presented with the help of simple graphs. For
the example above Hess's law can be illustrated with each one of the diagrams shown below.

H C(s) + O2(g)
‒ 110,6 kJ/mol CO(g) + ½O2(g) step 1
‒ 393,5 kJ/mol
‒ 282,9 kJ/mol
CO2(g) step 2

C(s) + O2(g) ‒ 393,5 kJ/mol CO2(g)

‒1

ol
/m
10
,6

kJ
step 1 kJ step 2

,9
/m

89
‒2
ol
CO(g) + ½O2(g)

The heat of a reaction is equal to the sum of the heats of its successive steps.

∆H(reaction) = ∆H(step 1) + ∆H(step 2) + ∆H(step 3) + ....

23
HOW TO CALCULATE ∆H0 USING ∆Hf0 OF reaction components?
The Hess's law makes it possible to calculate the standard heat of any reaction if the standard heats
of formation of the reactants and the products are known. It is easy to understand that following the
scheme to the right. Consider the chemical reaction ∆H0
A + B → P + Q. Reactants A and B and the products P A + B P + Q
and Q can be formed from their constituent elements. ‒ ∆H0f(A) ‒ ∆H0f(B) ∆H0f(P) ∆H0f(Q)
The standard heats of formation are ∆Hf (A), ∆Hf (B),
0 0

∆Hf0 (P) and ∆Hf0 (Q). The Hess's law suggests that elemental elemental elemental elemental
composition + composition = composition + composition
instead of the direct transformation of A and B into P of A of B of C of D
and Q a 2-step transformation can be considered.
STEP 1 ‒ decomposition of A and B into their constituent elements
∆H0(step 1) = ‒ (∆Hf 0(A) + ∆Hf0 (B))
The sign „‒“ is used as the reactions of decomposition are the opposite of the formation reactions.
STEP 2 ‒ formation of P and Q from their constituent elements
∆H0(step 2) = ∆Hf0 (P) + ∆Hf0 (Q)
The elemental composition of the reactants and the products is the same as the atoms or the ions of
the reactants regroup to form the products. As a whole:
∆H0 = ∆H0 (step 1) + ∆H0 (step 2) = ‒ ∆Hf0 (A) ‒ ∆Hf0 (B) + ∆Hf0 (P) + ∆Hf0 (Q)

∆H0
REACTANTS PRODUCTS
∆H0 (step 1) ∆H0 (step 2)

constituent elements 24
 Determine the standard heat of the reaction of carbonation of calcium oxide CaO.
PROBLEM! The standard heats of formation of the reactants are: ∆Hf0(CaO) = ‒ 635,1 kJ/mol;
∆Hf0(CO2) = ‒ 393,5 kJ/mol; ∆Hf0(CaCO3) = ‒ 1207,0 kJ/mol;

Solution: 1. Express the thermochemical equation of the reaction of carbonation of CaO.

CaO(s) + CO2(g) → CaCO3(s) ∆H0 = ?
2. Suppose that the reaction is going on in two stages.
❶ Decomposition of reactants into their constituent elements.
CaO(s) → Ca(s) + ½O2(g) ∆H0 = ‒ ∆Hf0(CaO) = 635,1 kJ/mol
CO2(g) → C(s) + O2(g) ∆H0 = ‒ ∆Hf0(CO2) = 393,5 kJ/mol
❷ Formation of the reaction product.
Ca(s) + C(s) + 3/2O2(g) → CaCO3(s) ∆Hf0(CaO) = ‒ 1207,0 kJ/mol
3. Draw a graph of the two stage process.

CaO(s) + CO2(g) ∆H0 CaCO3(s)

‒ ∆Hf0(CaO) ‒ ∆Hf0(CO2)
∆Hf0(CaCO3)

Ca(s) + ½O2(g) + C(s) + O2(g)

4. Calculate the standard heat of the reaction ∆H0.

∆H0 = ‒ ∆Hf0(CaO) ‒ ∆Hf0(CO2) + ∆Hf0(CaCO3) = 635,1 + 393,5 ‒ 1207,0 = ‒ 178,4 kJ
Answer: The reaction of carbonation of CaO is exothermic ∆H0 = ‒ 178,4 kJ. During the formation of
1 mole of solid CaCO3 178,4 kJ of energy as heat are liberated.
25
As a rule ∆H0 of a reaction is equal to the sum of the standard heats of formation of the products
minus the sum of the standard heats of formation of the reactants:
∆H0 = sum of ∆Hf0(products) ‒ sum of ∆Hf0(reactants)
If in the balanced chemical equation the coefficient before a component of the reaction is not 1, the
value of its standard heat of formation has to by multiplied by the value of the coefficient.

Ammonia NH3 reacts with oxygen producing nitrogen N2 and water. Determine the standard
PROBLEM! heat of the reaction. (∆Hf0(NH3) = ‒ 46,1 kJ/mol and ∆Hf0(H2O(l)) = ‒ 285,8 kJ/mol)

Solution: 1. Express the thermochemical equation of the reaction.

4NH3(g) + 3O2(g) → 2N2(g) + 6H2O(l) ∆H0 = ?
2. Calculate the standard heat of the reaction.
∆H0 = [2.∆Hf0 (N2) + 6.∆Hf0 (H2O)] ‒ [4.∆Hf0 (NH3) + 3.∆Hf0 (O)2] =
= [2.0 + 6. (‒ 285,8)] ‒ [4.(‒ 46,1) + 3.0] = ‒ 1714,8 ‒ (‒ 184,4) = ‒ 1530,4 J

Answer: This is an exothermic reaction. The standard heat of the reaction is ∆H0 = ‒ 1530,4 J. When 4 moles
of NH3 react with oxygen at 25 oC and 10 5Pa 1,53 MJ of heat go into the surrounding.

26
HOW TO CALCULATE ∆H0 USING ∆Hc0 OF REACTANTS?
Heat of chemical reactions can be calculated using the heats of combustion of the reactants and the
products. Hess's law is applied. As a rule: ∆H0 = sum of ∆Hc0(reactants) ‒ sum of ∆Hc0(products)

Determine the standard heat of the reaction of hydrogenation of propene C3H6.

PROBLEM! The standard heats of combustion of the reactants and the product are:
∆Hc0(C3H6) = ‒ 2058 kJ/mol; ∆Hc0(H2) = ‒ 285,8 kJ/mol; ∆Hc0(C3H8) = ‒ 2222 kJ/mol

Solution: 1. Express the thermochemical equation of the reaction.

C3H6(g) + H2(g) → C3H8(g) ∆H0 = ?
2. Express the thermochemical equations of the combustion reactions for C3H6, H2 and C3H8.
C3H6(g) + 9/2O2(g) → 3CO2(g) + 3H2O(l) ∆Hc0(C3H6) = ‒ 2058 kJ/mol
H2(g) + ½O2(g) → H2O(l) ∆Hc0(H2) = ‒ 285,8 kJ/mol
C3H8(g) + 5O2(g) → 3CO2(g) + 4H2O(l) ∆Hc0(C3H8) = ‒ 2222 kJ/mol
3. Draw a graph of the process.
C3H6(g) + H2(g) ∆H0 C3H8(g)
4. Calculate the standard heat of the reaction ∆H0.
+ 9/2O2 + 1/2O2 + 5O2
∆H0 = [∆Hc0 (C3H6) + ∆Hc0 (H)2] ‒ ∆Hc0 (C3H8) =
3CO2(g) + 3H2O + H2O(l)
= [‒ 2058 ‒ 285,8] ‒ [‒ 2222] = ‒ 121,8 kJ

Answer: This is an exothermic reaction ∆H0 = ‒ 121,8 kJ. During the hydrogenation of 1 mole of propene
121,8 kJ of energy as heat is evolved into the surrounding.
27
Standard heats of combustion are used to determine the standard heats of formation of organic
compounds as many of the reactions of formation of these compounds are very slow or practically
do not undergo.

The standard heat of combustion of ethane is ∆Hc0(C2H6) = ‒ 1560 kJ/mol. Determine its
PROBLEM! standard heat of formation. The standard heats of combustion of carbon and hydrogen are
∆Hc0(C) = ‒ 393,5 kJ/mol; ∆Hc0(H2) = ‒ 285,8 kJ/mol;

Solution: 1. Express the thermochemical equation of the reaction of formation of ethene C2H6.
2C(graphite, s) + 3H2(g) → C2H6(s) ∆Hf0 = ?
2. Express the thermochemical equations of the combustion reactions for C, H2 and C2H6.
C(graphite, s) + O2(g) → CO2(g) ∆H0 = ∆Hc0(C) = ‒ 393,5 kJ/mol
H2(g) + ½O2(g) → H2O(l) ∆H0 = ∆Hc0(H2) = ‒ 285,8 kJ/mol
C2H6(g) + 7/2O2(g) → 2CO2(g) + 3H2O(l) ∆H0 = ∆Hc0(C2H6) = ‒ 1560 kJ/mol
3. Draw a graph of the processes.
∆Hf0
4. Calculate the standard heat of the reaction ∆Hf . 0 2C(s) + 3H2(g) C2H6(g)
∆Hf0 = [2.∆Hc0(C) + 3.∆Hc0(H2)] ‒ ∆Hc0(C2H6) = + 2O2 + 3/2O2 + 7/2 O2
= [2.(‒ 393,5) + 3.(‒ 285,8)] ‒ (‒ 1560) = ‒ 84,4 kJ/mol 2CO2(g) + 3H2O(l)
Answer: When 1 mole of C2H6 is formed upon standard
conditions, 84,4 kJ of energy as heat are evolved.

28
 CAN YOU ANSWER THESE QUESTIONS
1. What does the Hess's law state?
2. A react with B, yielding C. The standard heat of the reaction is ∆H0. Suppose that the process
undergoes in two steps. The standard heats of the successive reactions are ∆H0(step 1) and
∆H0(step 2). Which of the following equations is correct? Why?
a) ∆H0 = ∆H0(step 1) ‒ ∆H0(step 2)
b) ∆H0 = ∆H0(step 1) + ∆H0(step 2)
c) ∆H0 > [∆H0(step 1) + ∆H0(step 2)]
d) ∆H0 < [∆H0(step 1) + ∆H0(step 2)]
3. Green plants transform carbon dioxide and water into glucose releasing oxygen. How to
calculate the standard heat of this reaction?
4. The formation reaction for methane is C(s) + 2H2(g) → CH4(g). This is a very, very slow
interaction and it is impossible to measure experimentally the heat evolved or absorbed at
25 oC and 105 Pa when carbon reacts with hydrogen to produce methane. How to determine
the standard heat of formation of CH4?
 Energy changes during chemical reactions ‒ key points

● HEAT OF REACTION ∆H is the amount of heat evolved or absorbed during a chemical

reaction undergoing at constant temperature and at either constant pressure or volume. It
is evaluated in joules J.

● exothermic REACTIONs generate heat. The temperature of the surrounding increases.

The reacting system loses energy and ∆H < 0.

● endothermic REACTIONs absorb energy. The temperature of the surrounding decreases.

The reacting system gains energy and ∆H > 0.

● Activation energy of a reaction is the minimum amount of energy that must by supplied
to initiate the chemical transformation.

● thermochemical equations are balanced chemical equations. The heat of reactions

and the physical states of the reactants and the products are always indicated.

● standard Heat of a reaction ∆H0 is the heat of the reaction at standard temperature
and standard pressure (25o C and 105 Pa).
● Standard hEAT of formation ∆Hf0 is the amount of heat absorbed or evolved at 25 oC
and 105 Pa when 1 mole of the compound is formed from its constituent elements each of the
substances being into its normal physical state.

● STANDARD HEAT OF COMBUSTION ∆Hc0 of a substance is the amount of energy liberated

when 1 mole of the substance undergoes complete combustion at 25 oC and 105 Pa and with
excess oxygen.

● CALORIFIC VALUE of a fuel is the amount of heat liberated when 1 kg or 1 m3 of the substance
undergoes complete combustion upon standard conditions (25o C and 105 Pa) and with excess
oxygen.

● Hess's law ‒ the heat absorbed or generated in a chemical reaction is independent of the
route of the reaction but is determined only by the type and the state of the reactants and the
products.

● Standard heats of reactions ∆H0 can be calculated using the standard heats of formation ∆Hf0 or
the standard heats of combustion ∆Hc0 of reactants and products.
4 Rate of chemical reactions
key TOPICS
1. Are all chemical reactions instantaneous?
2. How to evaluate the „speed“ of chemical processes?
3. Are rates of disappearance of reactants and rates of
appearance of products identical?
4. Do rates of chemical reactions change over time?
concentration

product
key words
●● Rate of reactions
●● Instantaneous reactions
●● Fast reactions
reactant ●● Slow reactions

time
32
 HOW TO EVALUATE THE „SPEED“ OF CHEMICAL REACTIONS?
Some chemical reactions are instantaneous.
Such are explosions. The neutralisation of an acid
with a base also undergoes instantaneously as Zn
H+ ions combine immediately with OH‒ forming H2
water molecules H2O. Other reactions are just Cl–
fast ‒ products are formed over a short period Cl–
H+ Cl– + Cl
–

of time. For example, the reaction of solid H

Explosion is an Zn2+
zinc Zn with hydrochloric acid HCl(aq) is a fast
instantaneous process
reaction ‒ bubbles of hydrogen H2 rise up in the The reaction of
solution and the zinc piece quickly disappears. Corrosion of metals is a Zn with HCl(aq) is
slow process ‒ during years metals slowly transform into their oxides a fast reaction.
forming layers of rust. But some processes are so slow that they seem to
not undergo. For example, fossil fuels have been formed over millions of O2
years and they are nonrenewable energy resources.
RUST gout of
In chemistry the quantity rate of reaction is used to assess the „speed“ Fe2O3 water
of chemical transformations. It is denote by „v“.
iron Fe
RATE OF A CHEMICAL REACTION is the change in concentration
of a reactant or a product over the change in time. Corrosion of metals
is a slow process.

33
 For example, substances A and B react, yielding substances P and Q:

A+B→P+Q
Data about the change in concentrations of A and B during the first

concentration
product P
10 seconds of the reaction are shown in the table.

Time, s 0 10 The average rate of disappearance of

c(A), mol/ℓ 0,5 0,4 reactant A over the first 10 seconds of
the reaction is: reactant A
c(P), mol/ℓ 0 0,1
0,4 ‒ 0,5 time
v(A) = ‒ = 0,01 mol.l‒1.s‒1
10 Change in concentrations
The sign „‒“ is used as the concentration of reactants always of a reactant and a product
of a chemical reaction over time
decreases as the reaction goes on.
Similarly, the reaction rate can be evaluated from the increase of the concentration of a product. For
example, the rate of appearance of P is:
0,1 ‒ 0
v(P) = = 0,01 mol.l‒1.s‒1
10

34
Most often the coefficients in the balanced chemical equation of the Time, s 0 10
reactions are not 1. For example:
c(A), mol/ℓ 0,5 0,4
2A + 4B → 3P + Q c(B), mol/ℓ 0,5 0,3
The rates of consumption of reactants and formation of products are not c(P), mol/ℓ 0 0,15
identical. Look at the data in the table. At the beginning of the reaction c(Q), mol/ℓ 0 0,05
the concentration of both A and B is 0,5 mol/l. The average rates of
disappearance of A and B are:
0,4 ‒ 0,5
v(A) = ‒ = 0,01 mol.l‒1.s‒1
10
0,3 ‒ 0,5
v(B) = ‒ = 0,02 mol.l‒1.s‒1
10
The rates of appearance of P and Q are:
0,15 ‒ 0
v(P) = = 0,015 mol.l‒1.s‒1
10
0,05 ‒ 0
v(Q) = = 0,005 mol.l‒1.s‒1
10
These values would be identical if divided by the coefficients in the balanced chemical equation. The
average reaction rate over the first 10 seconds is expressed as:
1 1 1 1
v = v(A) = v(B) = v(P) = v(Q) =
2 4 3 1
1 1 1 1
= .0,01 = .0,02 = .0,015 = .0,005 = 0,005 mol.l‒1.s‒1 35
2 4 3 1
In general, the average rate of the reaction

concentration of A
aA + bB → pP + qQ
is expressed as:
c(A)1
∆c(A)=c(A)2‒c(A)1
1 . ∆c(A) 1 . ∆c(B) 1 . ∆c(P) 1 . ∆c(Q)
v= ‒ = ‒ = = c(A)2
a ∆t b ∆t p ∆t q ∆t ∆t=t2‒t1

The symbol „∆“ (delta) is used to express the difference between t1 t2 time
the final and initial values of a parameter: Change in concentration
∆t = t2 ‒ t1 of reactant A over time
∆c(A) = c(A)2 ‒ c(A)1 = concentration of A at time t2 ‒ concentration of A at time t1

→ 2NH at constant
For example, the average rate of the reaction of synthesis of ammonia 3H2 + N2 ← 3
temperature and volume over the time interval ∆t is expressed as:

1 . ∆c(H2) 1 ∆c(N2) 1 . ∆c(NH3)

v= ‒ = ‒ =
3 ∆t 1 ∆t 2 ∆t

36
 Time c(N2O5) c(NO2) c(O2)
At standard conditions N2O5 is a white solid but at 47 oC it sublimates. s mol/l mol/l mol/l
The products of its thermal decomposition are the highly toxic brown- 0 0,0400 0 0
PROBLEM! reddish gas NO2 (used to produce nitric acid HNO3) and O2. A lab report 100 0,0336 0,0128 0,00320
200 0,0283 0,0234 0,00585
presents data about the change in concentrations of N2O5, NO2 and O2
over time at a given temperature and volume. How does the reaction rate change over time?

Solution: 1. Express the balanced chemical equation of the reaction of decomposition of N2O5.
2N2O5 → 4NO2 + O2
2. Calculate the average rate of the reaction during the first 100 seconds of decomposition.
1 . ∆c(N2O5) 1 . 0,0336 ‒ 0,0400 1 . (‒ 0,0064)
v= ‒
2 ∆t
= ‒
2 100 ‒ 0
= ‒
2 100
= 3,2.10‒5 mol.l-1.s-1

1 . ∆c(NO2) 1 . 0,0128 ‒ 0 1 . 0,0128

v= 4 ∆t
=
4 100 ‒ 0
=
4 100
= 3,2.10‒5 mol.l-1.s-1

1 . ∆c(O2) 1 . 0,0032 ‒ 0 1 . 0,0032

v= 1 ∆t
=
1 100 ‒ 0
=
1 100
= 3,2.10‒5 mol.l-1.s-1

3. Calculate the average rate of the reaction over the time interval from t1 = 100 s to t2 = 200 s.
1 . ∆c(N2O5) 1 . 0,0283 ‒ 0,0336 1 . (‒ 0,0053)
v = ‒ 2 ∆t
= ‒
2 200 ‒ 100
= ‒
2 100
= 2,65.10‒5 mol.l-1.s-1

1 . ∆c(NO2) 1 . 0,0234 ‒ 0,0128 1 . 0,0106

v= 4 ∆t
=
4 200 ‒ 100
=
4 100
= 2,65.10‒5 mol.l-1.s-1

1 . ∆c(O2) 1 . 0,00585 ‒ 0,0032 1 . 0,00265

v= 1 ∆t
=
1 200 ‒ 100
=
1 100
= 2,65.10‒5 mol.l-1.s-1

Answer: The reaction slows down over time.

37
 CAN YOU ANSWER THESE QUESTIONS
1. What is reaction rate?
2. Why is it necessary to determine reactions rates?
3. 3 moles of A react with 1 moles of B to produce 2 moles of C. How to express the rate of
the reaction?
4. Consider the reaction of formation of hydrogen iodide H2 + I2 → 2HI. Is it correct to
∆c(H2) ∆c(I2) ∆c(HI)
express the average reaction rate as v = ‒ = ‒ = ? Why?
∆t ∆t ∆t
5. Hydrogen peroxide H2O2 decomposes into water and oxygen. Express the rate of disappear-
ance of H2O2 and the rates of appearance of each of the products.
6. In general, reactions rate changes over time. Can you explain that?
 Effect of reactants concentration
5
on reaction rate. Rate law
key TOPICS
1. Why does reactants concentration affect reaction rate?
2. What does the rate law state?
3. Why to break to pieces solid blocks reacting with liquid or
gaseous substances?

aA + bB → productds key words

●● Rate law
α β Rate constant
v = k.c(A) .c(B)
●●
●● Contact surface

39
DOES REACTION RATE DEPEND ON REACTANTS CONCENTRATION?
Consider the reaction A + B → products. This chemical transformation goes
A B
on when A and B collide. The more reacting species in the reaction volume,
the more likely the collisions between them and the greater the amount of No reaction
products.
Generally, the rate of a chemical transformation is proportional to the
concentration of reactants raised to some power. For the reaction: A B
aA + bB → products
A collision ‒
v = k.c(A) . c(B)
α β
A can react with B.
This postulate is known as the rate law. It states that:

The rate of chemical reactions is directly proportional to the

concentrations of reactants raised to some powers.

The constant of proportionality k is called rate constant. It does not depend on reactants concentration
but it does depend on reaction conditions (temperature, pressure). For example, the rate constant for
the reaction of thermal decomposition of N2O5 is equal to 4,82.10‒3 s‒1 at 64 oC and to 1,68.10‒2 s‒1 at
83 oC. The dimensions of the rate constant depends on the values of the coefficients α and β. Usually
they are not identical with the coefficients a and b in the balanced chemical equation of the reaction.
They are experimentally determined even for simple reactions.
40
For example, the rate law equation (known also as rate equation) for the reaction of synthesis of HBr
from H2 and Br2 (H2 + Br2 → 2HBr) is:
v = k.c(H2). c(Br2)1/2
If the concentration of H2 increases 4 times the reaction rate is also increased 4 times. But if the
concentration of Br2 increases 4 times the reaction rate is only doubled.

Consider the reaction of thermal decomposition of dinitrogen pentoxide N2O5→ 2NO2 + ½O2.
The rate equation for the reaction is v = k.c(N2O5) and k = 1,7.10‒3 s‒1. The initial concentration
PROBLEM! of N2O5 is 0,04 mol/l. It drops to 0,0336 mol/l after 100 s, to 0,0283 mol/l after 200 s and to
0,02 mol/l after 400 s. What is the initial reaction rate and the reaction rate after 100 s, after
200 s and after 400 s?
Solution: 1. Write down the rate law for the reaction.
v = 1,7.10‒3.c(N2O5)
2. Calculate the reaction rates for the concentrations of N2O5 given above.
v(t=0) = 1,7.10‒3.0,04 = 6,8.10‒5 mol.l‒1.s‒1
v(t=100 s) = 1,7.10‒3.0,0336 = 5,7.10‒5 mol.l‒1.s‒1
v(t=200 s) = 1,7.10‒3.0,0283 = 4,8.10‒5 mol.l‒1.s‒1
v(t=400 s) = 1,7.10‒3.0,02 = 3,4.10‒5 mol.l‒1.s‒1

Answer: The reaction slows down over time. Over a period of 400 s the concentration of N2O5 drops
twice. Over this period the reaction rate also decreases twice as it is directly proportional to the
concentration of N2O5.
41
the effect of the surface area of a solid ‒ Is it better to use powdered
solid rather than solid lumps when a solid reacts witH a liquid or a
gas?

Zinc reacts with hydrochloric acid HCl, yielding

the soluble salt ZnCL2 and gaseous H2. H2 H2
Zn(s) + 2HCl(aq) → ZnCl2(aq) + H2 (g)↑ HCl HCl
This is a fast reaction. But zinc Zn and hydrogen Zn
ions H do not react instantaneously as the
+

reaction undergoes when H+ ions collide with The reaction of Zn(s) with HCl(aq) speeds up when
the surface of the solid Zn. More H+ ions are the surface area of solid Zn increases.
present in the liquid phase (the concentration of
hydrochloric acid is higher), faster solid Zn disappears and more H2 bubbles rise up. But the rate of
the reaction can be increased also by breaking the Zn lump into small pieces. The surface area of the
Zn particles accessible for H+ ions is larger and the reaction speeds up.
In industrial processes granulated solids or powders of solids are used instead of big solid blocks when
solid substances react with liquid or gaseous substances. The surface area of the solid contacting
the liquid or gaseous reactants is larger and reactions speed up. If a gas bubbles in a liquid, special
devices are used to sparge the gas thus increasing the gas-liquid interface area and consequently ‒ the
reaction rate.

42
 CAN YOU ANSWER THESE QUESTIONS
1. Why does reactants concentration affect reactions rate?
2. What is rate equation of a reaction?
3. Are the coefficients in the balanced chemical equation of a reaction identical with the
coefficients in the rate equation of the reaction?
4. The rate equation of the reaction of decomposition of hydrogen peroxide into water and
hydrogen is expressed as v = k.c(H2O2). If the concentration of H2O2 is doubled what is the
rate of the reaction?
a) The reaction rate does not change.
b) The reaction rate is doubled too.
c) The reaction rate is twice as slow.
d) The reaction is four times faster.
5. Look at the values of the reaction rates for the N2O5 thermal decomposition calculated on
p. 37 and p. 41. Why aren't they identical?
6. In two test tubes there are 200 ml of 1 M HCl. A piece of 1 g of magnesium is put in the first
test tube. To the solution in the second test tube is added 1 g of powdered magnesium. In
which test tube magnesium will disappear first?
 Effect of temperature
6
on reaction rate
key TOPICS
1. Why does temperature affect reaction rate?
2. Why do many reactions undergo only at high temperature?
3. Why do both exo- and endothermic reactions speed up with
increasing temperature?
4. What does the van't Hoff's empirical rule state?
Rate constant

k2 key words
k1 ●● van't Hoff's rule

T1 T2 Temperature
44
 N2
O2
DOES TEMPERATURE AFFECT CHEMICAL REACTIONS RATE?

The Earth atmosphere (the air) is composed mainly of gaseous O2 N2

nitrogen N2 and oxygen O2. These two gases can react to produce
nitrogen oxide NO. In the atmosphere at normal temperature this
reaction does not really undergo. But during lightning discharge, At normal conditions
when temperature dramatically rises, nitrogen and oxygen combine nitrogen N2 and oxygen O2 in
and form NO molecules. Oxygen and hydrogen do not react at 25 oC the atmosphere do not react.
too. But if the mixture is heated up to 400 oC oxygen combines with
hydrogen forming water but the reaction is very slow. It speeds up
with increasing temperature and at 800 oC the mixture explodes.
Many chemical reactions undergo only at high temperature whether N2 + O2 → 2NO
they are exothermic or endothermic. For example, the formation of
nitrogen oxide NO is an endothermic reaction that undergoes only at
very high temperature. The synthesis of ammonia NH3 from nitrogen
N2 and hydrogen H2 is an exothermic process carried out at high
At very high temperature
temperature as at standard conditions the interaction is to slow.
(as during lightning discharge)
nitrogen N2 and oxygen O2
combine to form
nitrogen oxide NO.
45
In general, chemical reactions speed up when temperature
increases. But why? What does really change in a reacting

Rate constant, k
system when temperature rises? The rate law gives a very
simple explanation of that phenomena.
The rate equation for the reaction aA + bB → products is k2
v = k.c(A) α. (B) β. Reactants concentrations are not affected
by changes in temperature. As the coefficients α and β k1
remain constant, the rate constant k is the only parameter
that changes with increasing temperature. The higher the T1 T2 Temperature
temperature, the higher the value of the rate constant as the
energy of the reacting species increases with temperature. The rate constant of a reaction
increases with increasing temperature
On one hand, the higher the energy of reactants, the more
likely the collision between A and B. On the other hand, not all collisions result in the formation of a
new substance. Some minimum of energy (the activation energy of the reaction) is needed to initiate
the reaction. The higher the temperature, the greater the amount of reacting species capable to
overcome this „barrier“. Both factors cause chemical transformations to speed up.
Jacobus van't Hoff* formulated an empirical rule generalising the effect of temperature on reactions
rate:
The rate constant of a chemical reaction gets doubled to
quadrupled for each rise of 10 oC in temperature.

For example, when the temperature rises from 25 oC to 35 oC the rate constant of the hydrolysis of
methyl ethanoate CH3OOC2H5 almost doubles, while the rate constant of the hydrolysis of saccharose
C12H22O11increases a little bit more than four times.
------------------------------- 46
*Jacobus Henricus van't Hoff was the first winner of the Nobel Prize for chemistry in 1901.
 Consider the two energy diagrams shown below. The rate of which reaction rises more rapidly
PROBLEM! with increasing temperature?

TRANSITION state TRANSITION state

Potential energy

Potential energy
Activation
energy

Activation
energy
Initial state
(reactants)

∆H < 0

FINAL state Initial state FINAL state

(products) (reactants) ∆H < 0 (products)

Reaction progress Reaction progress

Reaction ❶ Reaction ❷
Answer: Both reactions need some additional energy (supplied, for example, as heat) to start. But the energy
barrier that reactants in reaction ❷ have to overcome is high compared to the energy barrier
for reactants in reaction ❶ ‒ the activation energy of reaction ❷ is greater than the activation
energy of reaction ❶. The number of reacting species with an energy equal to or greater than the
activation energy rises more quickly when the energy barrier is high. It may be concluded that the
rate of reaction ❷ rises more rapidly with increasing temperature.

47
 CAN YOU ANSWER THESE QUESTIONS
1. Does temperature affect reaction rate?
2. Why do both exo- and endothermic reactions speed up with increasing temperature?
3. Hydrogen and oxygen do not react at 25 oC but the gaseous mixture explode at 800 oC.
Why?
4. Why does combustion need some external energy to start (for example, a lit match or a
spark) but further the reaction undergoes without supplying external energy?
5. The activation energy of the reaction of nitrogen oxide NO with ozone O3 is low compared
to the activation energy of the reaction of synthesis of nitrogen oxide from nitrogen N2 and
oxygen O2. At a given temperature which of the reactions is faster? Why?
6. Why are foods stored in refrigerators?
7 Catalysis. Catalysts
key TOPICS
1. What is catalysis?
2. What are catalysts?
3. What substances are catalysts?
4. How do catalysts accelerate chemical reactions?

cont. CH4
o-
Ni, C key words
Cu/ZnO CH3OH
CO + H2 ●● Catalysis
Co-cont
. ●● Catalyst
ZnO alkanes
, Cr ●● Intermediate
2O
3
Higher ●● Inhibitor
alcohols

49
What is catalysis?

Potential energy

Potential energy
Chemical industry needs huge investments and Ea Ea
chemical products must „pay“ these investments.
∆H < 0 ∆H < 0
Accelerating chemical transformations is a key
point for many industrial processes to make them
Reaction progress Reaction progress
paying. Generally, both increasing temperature
❶ ❷
and reactants concentration speed up chemical Exothermic reactions
interactions as more molecules overcome
the energy barrier of the reaction and more

Potential energy

Potential energy
intermolecular collisions result in the formation of
reaction products. But both factors do not alter the Ea Ea
∆H > 0 ∆H > 0
activation energy Ea of the chemical reaction. The
lower the activation energy, the faster the reaction
for both exo- and endothermic transformations. At Reaction progress Reaction progress
a given temperature and reactant concentrations ❸ ❹
reaction ❷ is faster than reaction ❶ and Endothermic reactions
reaction ❹ is faster than reaction ❸. Lowering A reaction speeds up
the energy barrier of a reaction, i.e. its activation if its energy of activation Ea lowers.
energy, is a promising way to accelerate chemical
reactions. To make it possible chemists have launched the idea of adding to the reacting system some
special substances changing the route of the chemical reaction without themselves being consumed, i.e.
they remain unchanged after the completion of the reaction. These substances are called catalysts and
the process itself is known as catalysis (in greek language it means „destruction“).
50
 CATALYSIS is the acceleration of the rate of CATALYSt is a substance that increases
a chemical reaction by adding substances not the rate of a reaction without itself being
consumed during the reaction. consumed.

Catalysts are solid, liquid and gaseous substances. Solid catalysts are most often metals or their oxides,
sulfides and halides. Also oxides, sulfides and halides of silicon, boron and aluminum. For example, iron Fe
catalyses the synthesis of ammonia NH3. Divanadium pentaoxide V2O5 catalyses the transformation
of SO2 into SO3 ‒ a key intermediate for the production of sulfuric acid H2SO4. The hydrogenation of
unsaturated hydrocarbons is a process catalysed by nickel Ni, platinum Pt and palladium Pd. The slow
process of esterification is catalysed by H+ ions.
Some processes, as for example corrosion of metals, must be slowed down. Substances that lower the
reaction rate are called inhibitors.
Catalysts are very useful when it is necessary to accelerate one of
- cont. CH4
several simultaneously undergoing chemical reactions. It is often Ni, C
o
the case in organic synthesis. For example, when carbon monoxide Cu/ZnO CH3OH
CO is mixed with hydrogen H2 different products form depending
CO + H2 Co-cont
on the type of catalyst. Nickel Ni, cobalt-containing catalysts .
accelerate the synthesis of methane CH4. Methanol CH3OH is the ZnO alkanes
, Cr
2O
main product if the catalyst is CuO/ZnO. Higher alcohols form if 3
Higher
a mixture of ZnO and Cr2O3 is used to catalyse the reaction. If the alcohols
catalyst is a cobalt-containing substance alkanes are produced.
Enzymes are proteins that accelerate many biochemical reactions. They are naturally occurring catalysts.
The transformation of glucose C6H12O6 into ethanol C2H5OH and carbon dioxide CO2 is catalysed by the
enzyme zymase. The burning of glucose in the human body is catalysed by the hormone insulin. More 51
than 800 enzymes are known up to day.
HOW do catalysts act?
Catalysts accelerate chemical reactions by changing the their mechanism. They create another route
for the transformation of reactants into products thus lowering the activation energy of the reaction.
Catalysts chemically react with some of the reactants (or with all reactants) and form intermediate
substances which easily react to form the products. During the reaction catalysts regenerate.
For example, consider the slow transformation of a substance A into the substance B. The reaction is
undergoing in one step A → B. A catalyst X is added to accelerate this transformation. The rout of
the reaction is changed. It is carried out in 2 steps:
Step 1. Reaction of A with the catalyst X resulting in the formation of an intermediate AX.
A + X → AX (intermediate)
Step 2. Transformation of the intermediate AX into the product B.
AX → B + X
The overall transformation is not affected as the intermediate is chemically transformed into the
product and the catalyst is regenerated. The sum of the two steps gives:
A + X + AX → AX + B + X
The intermediate AX and the catalyst X in both sides cancell out and the overall equation of the
catalysed process is identical with the equation of the uncatalysed reaction, i.e. A → B but the
process is accelerated as the activation energy of the two stages process is lower.
52
 CAN YOU ANSWER THESE QUESTIONS
1. What is catalysis?
2. Why is catalysis so important for industry?
3. Why are enzymes catalysts?
4. How do catalysts accelerate chemical reactions?
5. The activation energy of an uncatalaysed reaction is Ea. The reaction is speeded up by
adding a catalyst. What is the activation energy of the catalysed reaction?
a) It is identical with Ea.
b) It is greater than Ea.
c) It is lower than Ea.
d) It is greater or lower than Ea.
6. Can you give examples of reactions that must be slowed down but not speeded up?
 Homogeneous catalysis.
8
Heterogeneous catalysis
key TOPICS
1. What is homogeneous catalysis and homogeneous catalyst?
2. What is heterogeneous catalysis and heterogeneous catalyst?
3. Why does the catalysed pathway differ from the uncatalysed
pathway of a reaction?
4. Why is catalyse of huge importance for life and industry?

key words
H2
●● Homogeneous catalysis
●● Homogeneous catalyst
C2H4 ●● Phase
●● Heterogeneous catalysis
●● Heterogeneous catalyst

54
The mechanism of acting of catalysts is very complex. But, in general, the mechanism of catalysis when
catalysts and reacting species are in the same phase is completely different compared to the mechanism
of acting of catalysts that are not in the same phase* with reactants. The first type of catalysts are called
homogeneous catalysts and the process itself ‒ homogeneous catalysis. the second type of catalysts
are called heterogeneous catalysts and the process is known as heterogeneous catalysis.
HOW DO HOMOGENEOUS catalysts act?
Like all catalysts homogeneous catalysts reduce the activation energy of chemical reactions. The catalyst
and the reactants are in the same phase and the catalyst forms intermediates with some of the reactants (or
with all reactants). As reactants and catalysts are present in the same phase the rate of the homogeneous
catalytic reactions increases with the increase of the catalysts concentration. The intermediates easily
react with one another or with other reactants. The average rate of the reaction is high compared to the
uncatalysed reaction because the reactants overcome a lower energetic barrier ‒ the activation energy
of the catalysed reaction is lower than the activation energy of the uncatalysed reaction. The potential
energy of reactants and products remain unchanged.
uncatalysed reaction uncatalysed reaction

Potential energy
Potential energy

catalysed reaction catalysed reaction

Ea Ea Ea Ea
∆H > 0
∆H < 0

Reaction progress Reaction progress

Exothermic reaction Endothermic reaction 55
-------------------------------
*A phase is matter that is uniform throughout its chemical composition and physical state.
A simple example of homogeneous catalysis is the decomposition of hydrogen peroxide H2O2:
2H2O2(aq) → 2H2O(l) + O2(g)
This reaction is very slow but different catalysts speed it up. For example, bromine Br2 is a homogeneous
catalyst that accelerate this transformation. First Br2 reacts with H2O2.
Step 1. Br2 (aq) + H2O2(aq) → 2Br‒(aq) + 2H+(aq) + O2(g)
The next step is the reaction of bromide ions Br‒ with other molecules of H2O2 and H+. ions.
Step 2. 2Br‒(aq) + 2H+(aq) + H2O2(aq) → 2H2O(l) + Br2(aq)
The overall equation of the catalysed reaction (step 1 + step 2) is:
Br2(aq) + H2O2(aq) + 2Br‒(aq) + 2H+(aq) + H2O2 (aq) → 2Br‒(aq) + 2H+(aq) + O2(g) + 2H2O(l) + Br2(aq)
Finally: 2H2O2(aq) → 2H2O(l) + O2(g) uncatalysed
reaction

Potential energy
The two steps catalytic decomposition of H2O2 catalysed
Ea reaction
is much faster than the one step uncatalysed Ea(1) Ea(2)
reaction. Bromine molecules Br2, acting as a
2Br‒(aq)
catalyst, are regenerated during the reaction. The + 2H+(aq)
energy diagram for the catalysed process clearly + H2O2(aq)

shows that the activation energy of the two steps

Reaction progress
reaction is low compared to the activation energy
Uncatalysed and catalysed decomposition of H2O2
of the uncatalysed reaction.
56
iodide ions I‒(aq) also catalyse the decomposition of H2O2. The rate constant of the reaction increases
2 000 times as the activation energy drops from 76 kJ/mol to 57 kJ/mol. The enzyme catalase is much
more effective ‒ the activation energy drops to 8 kJ/mol and at 25 oC the reaction of decomposition
is 1015 times faster.
Hydrogen ions H+ and hydroxide ions OH‒ can act as homogeneous catalysts. For example, the hydrolysis
of saccharose C22H11O11 is catalysed by H+ ions. This is an example of acid catalysis. If OH‒ ions act as
a catalyst, the process is called base catalysis.
An example of homogeneous catalysis undergoing in gaseous phase
is the destruction of the ozone layer in the stratosphere. Ozone O3
spontaneously transforms into oxygen O2 under the action of sunlight.
This reaction is very slow but chlorine atoms Cl‒ (products of the
decomposition of freons like CF2Cl2, CFCl3, CHFCl2, C2Cl2F4, C2Cl3F3, etc.,
upon the action of the cosmic uv-radiation) accelerate this process
dramatically. Chlorine atoms are very reactive and „attack“ ozone
molecules:
Cl(g) + O3(g) → ClO(g) + O2(g) The formation of ozone
holes over the Earth's poles
ClO is an intermediate. It reacts with nascent oxygen O present in the is an example of undesired
homogeneous catalytic
stratosphere (under the action of uv-radiation oxygen molecules are reactions.
broken down: O2 uv 20).
ClO(g) + O(g) → Cl(g) + O2(g)
Chlorine atoms are regenerated like all catalysts. The overall reaction is O3(g) + O(g) → 2O2(g). Ozone
molecules are destroyed and transform into molecules of oxygen O2. One chlorine atom Cl destroys
one ozone molecule O3. As it is regenerated, it reacts with another molecule of O3 and so on. One 57
chlorine atom can repeat this cycle 100 000 times.
HOW DO Heterogeneous catalysts act?
Homogeneous catalysts and reactants are always in the same phase. Oppositely, heterogeneous
catalysts and reactants are in different phases. For example, solid catalysts accelerates reactions in
solutions or in gaseous phase. As the catalyst and the reactants are in different phases, they are
separated from one another by some boundary. If the catalyst is solid this boundary is its surface. All
successive steps of a heterogeneous catalysis undergo onto this surface. The pathway of this process
is very complex but the following steps are common for all processes catalysed by solid catalysts:
❶ Attachment of molecules of reactants to the solid surface. The process is known as adsorption.
❷ Activation of the adsorbed species.
❸ Chemical reaction of the absorbed species.
❹ Detachment of the products from the catalyst surface. The process is known as desorption.
The hydrogenation of alkenes is a heterogeneous catalytic process. The hydrogenation of ethene, i.e.
the adding of one molecule of hydrogen H2 to one molecule of ethene C2H4, is expressed with the
simple equation:
H2C = CH2 + H2 → C2H6
ethene ethane

The gases practically do not react unless a catalyst (for example, nickel Ni) is added to the mixture.

58
 H2
The catalysed pathway of this reaction is illustrated to the right.

❶ Molecules of both reactants are absorbed onto the catalyst C2H4

surface. ❶

❷ One of the sheared electron pair of the double carbon-carbon

bond of ethene H2C = CH2 disrupts. The hydrogen-hydrogen
bond in the H2 molecule also breaks down thus liberating lone ❷
hydrogen atoms H.

❸ Hydrogen atoms are mobile and easily move across the metallic
surface. When a hydrogen atom collide with an absorbed
activated ethene molecule a new carbon-hydrogen bond forms. ❸
Molecules of ethane C2H6 are produced.

❹ Molecules of ethane C2H6 are desorbed from the catalyst

surface ‒ they are not strongly attached to metal atoms of the
catalyst surface and easily quit the catalyst. The catalyst surface
is free and can adsorb other C2H4molecules. 59
❹
A key factor for the catalyst efficiency is the surface area available for the adsorption of reactants.
The rate of the heterogeneous catalytic reactions increases with the increase of the surface area of
catalysts. But not all atoms on the surface of a catalyst are capable to trap the reactants molecules.
The catalytic efficiency of an ideal metallic surface (as shown in the figure on the previous page) is not
very high. Surfaces with defects like ridges, „terraces“, kinks and others are much more efficient.
To increase their surface area, solid catalysts are often produced in the form of small granules (some
of them are porous solid substances), even as fine powders dispersed on a suitable support. For
example, the catalytic convertors for motors vehicles contain palladium Pd and rhodium Rh dispersed
on a ceramic support that resembles a honeycomb. Palladium catalyses the oxidation of the exhaust
carbon monoxide to carbon dioxide:
2CO(g) + O (g) Pd
2
2CO (g)
2

Rhodium catalyses the reaction of the unburned hydrocarbons with excess oxygen. They are
transformed into CO2 and water. For example, for octane:
2C H (g) + 25O (g) Rh
8 18 2
16CO (g) + 18H O(g)
2 2

Rhodium catalyses also the removal of exhaust NO. It reacts with the exhaust CO and transforms into
CO2 and N2.
2CO(g) + 2NO(g) Rh 2CO (g) + N (g)
2 2

This is an example of how catalysis can help to safeguard the environment. Catalytic processes are
also of huge importance for maintaining life as enzymes are biological catalysts regulating many
biochemical processes in nature and in the human body. A lot of industrial process are realised thanks
to the development of efficient catalysts. The production of new or improved catalysts itself is a very
important and rapidly growing branch of the chemical industry.
60
 CAN YOU ANSWER THESE QUESTIONS
1. Why are homogeneous and heterogeneous catalysis considered as the two main types of
catalytic processes?
2. Do homogeneous and heterogeneous catalysts affect the heats of reaction?
3. Are both homogeneous and heterogeneous catalysts regenerated during the reaction?
4. How does a homogeneous catalyst act?
5. How does a heterogeneous catalyst act?
6. Why does the rate of a heterogeneous reaction rise with the increase of the surface area?
7. Why is citric acid added when preparing at home a fruit jam or a jelly?
8. Why is the production of new catalysts a rapidly growing industry?
9. There Is not an universal catalyst, i.e. a substance that can accelerate all known chemical
reactions. Why?
10. Is it possible to initialise a reaction that is not undergoing at all by adding a catalyst?
 Reversible and irreversible chemical
9
reactions. Chemical equilibrium
key TOPICS
1. What reactions are reversible and what ‒ irreversible?
2. What is equilibrium?
3. Why is equilibrium a dynamic state?
4. What is equilibrium constant? key words
●● Reversible reaction
Concentration Irreversible reaction
of a product
Concentration

●●
in equilibrium Concentration ●● Forward reaction
of a reactant ●● Backward reaction
EQUILIBRIUM
●● Dynamic state
●● Equilibrium constant
Concentration
in equilibrium

EQUILIBRIUM
teq Time
teq Time
 What is chemical equilibrium?
In the everyday life the word „equilibrium“ is used to indicate that something does not change
over time (for instance, an object that does not move). Chemical reactions always deal with visible
changes as reactants transform into products. So what has to do an equilibrium state with chemical
transformations? Consider the thermal decomposition of limestone CaCO3, yielding calcium oxide
CaO and carbon dioxide CO2 (the oldest technological process invented by man):
to
CaCO3(s) CaO(s) + CO2(g)

Amount of CO2 If the gaseous product CO2 is swept away, the thermal
Amount of CO2

in equilibrium
decomposition continues until the heated solid limestone is
completely consumed. But if the reacting system is closed
EQUILIBRIUM
(no reactants are added and none of the products quit the
system), after a period of time the reaction seems to stop.
The heated solid limestone is not completely consumed
but for time t > teq the amount of CO2 does not increase
any more over time if the temperature and the pressure
teq Time (or the volume) remain unchanged. This is the equilibrium
state of the system.
Change in the amount of CO2
produced during the thermal
decomposition of CaCO3 over time
(closed system)
63
In general:

Chemical equilibrium is a state of a reacting system in which both reactants and

products are present but their concentrations do not change over time.

The equilibrium state is a dynamic state ‒ the forward reaction continues to go on but the backward
reaction (transformation of the products into the reactants) also undergoes. The concentration of
the components of the reaction do not change over time because the rate of the forward reaction is
equal to the rate of the backward reaction.

! In equilibrium: Rate of the forward reaction = Rate of the backward reaction

For example, in equilibrium the rate of the thermal decomposition of CaCO3 (CaCO3 → CaO + CO2) is
equal to the rate of the backward reaction of synthesis of CaCO3 (CaO + CO2 → CaCO3). If 10 molecules
of CaCO3 decompose in the same time 10 molecules of CaCO3 are synthesised from CaO and CO2.
The reaction is reversible. It undergoes in both directions ‒ forward and backward. For all reversible
reactions the one way arrow → in the chemical equation has to be replaced with an equilibrium
arrow → . For the reversible decomposition of CaCO3 in a closed system:
→
to
CaCO3(s) CaO(s) + CO2(g)

64
 If the produced CO2 goes away in the air (the system is open) the equilibrium state can not be reached
and the chemical transformation is irreversible. In closed systems most of the reactions are reversible.
But if in equilibrium the concentrations of the reactants are very small compared to the concentrations
of the products, the reactions are considered as irreversible. For example, the neutralisation reaction
NaOH(aq) + HNO3(aq) → NaNO3(aq) + H2O(l) is practically irreversible.
In the example above (the thermal decomposition of CaCO3), in 2NO2 ← N2O4
equilibrium reactants and products are in different phases ‒ CaCO3
Backward reaction
and CaO are solid, CO2 is a gas. Equilibrium can be established
also in one phase. For example, at room temperature dinitrogen
tetraoxide N2O4 (a colourless gas), placed in a flask with a stopper,
gradually darkens
as it transforms into
Concentration of N2O4 and NO2

NO2 N2O4
nitrogen dioxide NO2 N2O4 and NO2
[NO2]
(a brown gas). The
reaction is reversible. N2O4 → 2NO2
EQUILIBRIUM
→ 2NO2(g)
N2O4(g) → Forward reaction
The colourless N2O4 is
N2O4
[N2O4]
not completely consumed. An equilibrium is established
and the colour of the gaseous mixture does not change
teq Time over time ‒ the gaseous phase is a a mixture of N2O4
Change in the concentrations of and NO2 that concentrations [N2O4] and [NO2] remain
N2O4 and NO2 in a closed system unchanged over time.
N O (g) →
2 4 → 2NO (g) 2
65
HOw to quantify chemical equilibrium?
Equilibrium mixtures composition changes with temperature, pressure and concentrations of reactants. But
at a given temperature the reaction quotient of products concentrations over reactants concentrations,
raised to powers equal to their coefficients in the balanced chemical equation, is constant*. It is denoted
by Kc and is called equilibrium constant. For the reaction aA + bB →→ cC + dD it is expressed as:
[C] .[D]
c d
Kc =
[A]a[B]b
Equilibrium constants are dimensionless, i. e. they are expressed without units. The equilibrium
concentrations of the components of a reversible reaction are most often expressed in mol/l.
The equilibrium constant value changes with temperature but is unaffected by changes in pressure or in
concentrations of products or reactants. For example, the equilibrium constant of the reversible reaction
[NO2]2
N2O4(g) →
→ 2NO2(g) is expressed as Kc = . Its value does not change if an additional amount of
[N2O4]
N2O4 is pumped into the gaseous mixture provided that the temperature remains unchanged.
If both products and reactants are gases the amount of the reaction components in equilibrium can
be expressed by their partial pressures** instead of their concentrations. This equilibrium constant is
p NO
2

denoted by Kp. For the above reaction Kp = . 2

pN O 2 4

-------------------------------
*This relationship has been established experimentally by C. Guldberg and P. Vaage over the period 1864 ‒ 1879.
It is based on the empirical law of mass action that is only of historical significance today. The modern science
has proved that this expression is correct, for example, for dilute aqueous solutions of week acids or bases and
slightly soluble salts. 66
**The pressure that a gas would exert if it was alone in the reacting space.
 Ethanoic acid CH3COOH is a week acid. In water it partially dissociates liberating CH3COO‒
PROBLEM! ions and H+ ions. In equilibrium in the liquid phase are present CH3COO‒ ions, H3O+ ions
and molecules CH3COOH. What is the expression for the equilibrium constant Kc?

Solution: The chemical equation of the reversible dissociation of ethanoic acid is expressed as:
CH3COOH(aq) + H2O(l) →
→ CH3COO‒(aq) + H3O+(aq)
[CH3COO‒].[H3O+]
The equilibrium constant Kc has to be expressed as . But the concentration
[CH3COOH].[H2O]
of the pure water does not change during the reaction. For this reason it is omitted in the
expression for the equilibrium constant and the expression for Kc is:
[CH3COO‒].[H3O+]
Kc =
[CH3COOH]
COMMENTS: At 25 oC the equilibrium constant of the dissociation of ethanoic acid in water is 1,74.10‒5.

67
 Given the reversible reaction CaCO3(s) →
→ CaO(s) + CO2(g). What are the expression for
PROBLEM! the equilibrium constants of the reaction Kc and Kp?

[CO2].[CaO]
Solution: The equilibrium constant Kc has to be expressed as . But the concentrations of
[CaCO3]
the pure solid CaO and CaCO3 do not change during the reaction. For this reason they are not
included in the expression for Kc and the value of the equilibrium constant is determined only
by the concentration of CO2 in equilibrium:
Kc = [CO2]
By analogy, Kp = pCO 2
.

As a rule:
Concentrations or partial pressures of pure liquids and pure solids are not included in the expressions
for the equilibrium constants.

68
 CAN YOU ANSWER THESE QUESTIONS
1. What reactions are reversible?
2. Why is esterification a reversible reaction but neutralisation of a strong base with a strong
acid is an irreversible reaction?
3. How does the rate of the forward reaction change over time till equilibrium is achieved?
4. What is true?
a) In equilibrium the rate of the forward reaction is greater than the rate of the backward reaction.
b) In equilibrium the rate of the forward reaction is lower than the rate of the backward reaction.
c) In equilibrium the rate of the forward reaction is equal to the rate of the backward reaction.
d) In equilibrium both the forward and the backward reactions stops.
5. Nitrogen N and hydrogen H react to form NH : N (g) + 3H (g) →
2 2 3 2 2 → 2NH (g). The reaction is
3
reversible. What is the composition of the equilibrium gaseous mixture?
a) It is composed of N2 and H2.
b) It is composed of N2, H2 and NH3.
c) It is composed of N2 and NH3.
d) It is composed of pure NH3.
6. What is the equilibrium constant Kc of the reaction of synthesis of ammonia?
7. Powdered CaCO3 is put into a closed container. The air is swept away and the container
is heated to a high temperature (for example, 800 oC). CaCO3 decomposes into CaO and
CO2. Does the pressure of CO2 in equilibrium depend on the initial amount of CaCO3 in the
container?
 Effect of concentration, pressure
10 and temperature
on chemical equilibrium
key TOPICS
1. What does the Le Chatelier's principle stand for?
2. How is equilibrium affected by changes in reactants and products
concentration?
3. How is equilibrium affected by changes in temperature?
4. How is equilibrium affected by changes in pressure?
5. What are optimal conditions of a reversible reaction?

key
A + 3B →
→ 2C ∆H < 0 A + 3B →
→ 2C ∆H > 0 words
●● Le Chatelier's
p to
p to
principle

70
what does the le chatelier's principle stand for?
In equilibrium the concentration of reactants and products do not change over time as the forward
and the backward reactions undergo with equal rates. Changes in concentrations of reactants or
products (by adding or removing them), in pressure (by compressing or decompressing the system)
and in temperature disturb the equilibrium state. The equilibrium shifts to the reactants or to the
products thus overcoming these disturbances. As a rule:

A system in equilibrium, when subjected to a disturbance,

responds in a way that tends to minimise the effect of the disturbance.

This empirical rule is known as the Le Chatelier's principle*.

How do changes in reactants and products concentration affect

chemical equilibrium?
When some amount of a reactant or a product is added to the equilibrium mixture, or removed from
it, the value of the equilibrium constant does not change provided that the temperature is constant.
But the concentrations of reaction components change and a new equilibrium is established.
A good example to explain how the Le Chatelier's principle works when concentration of reactants or
products changes is the already well known reversible reaction of thermal decomposition of CaCO3
in a closed container.
71
-------------------------------
*The principle has been formulated by Henri Louis Le Chavalier over the period 1884-1914.
If heated in a closed container, calcium carbonate CaCO3 decomposes ‒ CO2
and the amount of the liberated CO2 increases over time until the
→ CaO(s) + CO (g)
CaCO3(s) →
equilibrium state is achieved. The equilibrium constant is expressed 2
as Kc = [CO2]. If some amount of CO2 is removed from the container Equilibrium shifts to the right
the system reacts by producing an additional amount of CO2 until the
equilibrium concentration of CO2 is achieved. The value of Kc does not change if the temperature is
maintained constant. The only change in the system is the decomposition of some additional amount
of CaCO3. The forward reaction of thermal decomposition CaCO3(s) → CaO(s) + CO2(g) is favored. The
equilibrium shifts in the direction of production of CO2.
+ CO2 If some amount of CO2 is pumped into the container, the system reacts
by consuming CO2 ‒ an additional amount of CaCO3 is produced until
CaCO3(s) →→ CaO(s) + CO2(g) the equilibrium concentration of CO2 is achieved. The value of Kc does
not change if the temperature is maintained constant. The only change
Equilibrium shifts to the left
in the system is the formation of some additional amount of CaCO3.
The backward reaction of synthesis of calcium carbonate CaO(s) + CO2(g) → CaCO3(s) is favoured. The
equilibrium shifts in the direction of consumption of CO2.
AS A RULE:
Changes in concentrations of reactants or products affect equilibrium. If a component of the reaction
is added to the equilibrium mixture, the equilibrium shifts towards the reaction decreasing its
concentration. If some amount of a component of the reaction is removed from the equilibrium
mixture, the equilibrium shifts towards the reaction increasing its concentration.
At a given temperature the value of the equilibrium constant does not change.
72
HOW do changes in pressure affect chemical equilibrium?
When gases are involved in a reversible reaction the composition of the equilibrium mixture can
change with increasing or decreasing pressure if the system is compressed or decompressed.
According to the Le Chatelier's principle the system reacts in a way to minimise the disturbance. The
already well known reaction of transformation of N2O4 into NO2 (N2O4(g) →→ 2NO2(g)) is a good example
[NO2]2
to show how this principle works. The equilibrium constant is expressed as Kc = .
[N2O4]
If the gas mixture is compressed the equilibrium state is
→
N2O4(g) → 2NO2(g) disturbed. The pressure is increased and the system react
p by decreasing the number of molecules thus reducing the
Equilibrium shifts to the left
pressure. The backward reaction is favoured as 2 molecules of
NO2 form 1 molecule of N2O4. The equilibrium shifts to the left.
Oppositely, if the gas mixture is decompressed (the pressure
→ 2NO (g)
N2O4(g) →
is decreased) the system reacts by increasing the number of p 2
molecules thus increasing the pressure. The forward reaction is Equilibrium shifts to the right
favoured as from 1 molecule of N2O4 are produced 2 molecules
of NO2. The equilibrium shifts to the right.
In both cases the value of Kc does not change provided that the temperature is constant. The ratio
[NO2]2/ [N2O4] does not change. But the values of [NO2] and [N2O4] change, i.e. the composition of
the equilibrium mixture changes.

73
If the balanced chemical equation shows that the number of moles of the gaseous reactants is equal
to the number of moles of the gaseous product, the equilibrium is not affect by any changes in the
pressure. For example, at a given temperature, the equilibrium state of the reaction
H2(g) + I2(g) →
→ 2HI(g)
is not affected by any changes in the pressure.

As a rule:
Changes in pressure affect equilibrium in gaseous phase if as a result of the chemical transformation
the overall number of moles in the system changes. At a given temperature the value of the
equilibrium constant does not change.
If the system is compressed (the pressure rises) the equilibrium shifts towards the reaction reducing
the number of moles.
If the system is decompressed (the pressure lowers) the equilibrium shifts towards the reaction
increasing the number of moles.

74
HOW do changes in TEMPERATURE affect chemical equilibrium?
When the temperature changes, the
equilibrium, generally, moves towards the Endothermic reaction
products or towards the reactants depending → 2NO2(g) ∆H0 = + 57 kJ
N2O4(g) →
on the heat of the reaction.
Exothermic reaction
if the forward reaction is exothermic, the
backward reaction is endothermic and the
heats of both reactions are equal in value but
differ in their sign. For example, the reaction of to to
transformation of N2O4 into NO2 is endothermic
and ∆H0 = + 57 kJ. The reverse reaction of
synthesis of N2O4 from NO2 is exothermic and
N2O4 N2O4 N2O4
∆H0 = ‒ 57 kJ. and NO2 and NO2 and NO2
If the temperature rises, according to the Le
Chatelier's principle, the system reacts in N2O4 ← 2NO2 N2O4 → 2NO2
a way to decrease the temperature. As the
forward reaction N2O4→ 2NO2 is endothermic, When temperature decreases When temperature rises
the exothermic backward reaction the endothermic forward reaction
i.e. during the reaction heat is absorbed, the is favored. The equilibrium mixture is favored. The equilibrium mixture
equilibrium shifts towards the product ‒ the contains more colourless N O . 2 4
contains more brown NO . 2

brown NO2, and the mixture darkens.

If the temperature decreases, the system tends to produce heat to overcome the disturbance. Now
the exothermic backward reaction of formation of the colourless N2O4 (N2O4← 2NO3) is favoured and
the gaseous mixture lightens. 75
In both cases the value of the equilibrium constant Kc changes when the temperature of the gaseous
mixture is increased or lowered. The forward reaction is endothermic (∆H > 0) and Kc increases
with increasing temperature. The backward reaction is exothermic (∆H < 0) and Kc decreases with
increasing temperature.

As a rule:
The effect of temperature on equilibrium depends on the heats of reactions. When temperature
rises equilibrium shifts in favour of the endothermic reaction. When temperature lowers equilibrium
shifts in favour of the exothermic reaction.

Remember that:
catalysts do not affect chemical equilibrium!
They can not cause the equilibrium to shift towards the desired products. Catalysts only accelerate
reactions and equilibrium is achieved over a shorter period of time but the yield does not change.

76
HOW to choose the optimum conditions to carry out a reversible reaction?
In many industrial processes equilibrium is shifted in favour of the desired product taking into
consideration the effects of concentration, pressure and temperature on equilibrium compositions.
But the impact of these parameters on the reactions rate is also considered. Most often, some optimal
conditions are fixed to make the industrial process profitable.
The synthesis of ammonia NH3 is an example of how the Le Catelier's principle is considered
simultaneously with factors affecting the rate of the reaction in a way to obtain a sufficient amount
of NH3 over an acceptable period of time, i.e. to choose the optimum conditions for this synthesis.
The reaction undergoes in gaseous phase as the reactants and the product are gases. In a closed
system the reaction is reversible:
N2(g) + 3H2(g) →
→ 2NH3(g) ∆H0 = ‒298 kJ
The reaction is exothermic and the amount of molecules in the system decreases during the reaction
(from 1 molecule N2 and 3 molecules of H2 only two molecules of NH3 are formed). Lowering the
temperature and compressing the gas mixture (increasing the pressure) shift the equilibrium in
favour of the reaction of formation of ammonia NH3 (the forward reaction). But at low temperature
the rate of the reaction is to slow. At normal conditions nitrogen and hydrogen practically does not
react. The reaction rate can be increased by increasing temperature but this lowers the yield of NH3
as the equilibrium shifts towards the backward endothermic reaction of ammonia decomposition
(at temperature equal to or greater than 1000 oC the yield of ammonia is practically 0). This negative
effect is partially overcame with the help of a catalyst (iron Fe and small amounts of Al2O3 and K2O).
In industry the synthesis of ammonia is realised at 30 MPa and 450 oC. The yield is only about 22 %. The
gaseous mixture leaving the reactor is cooled to the temperature of liquefying of NH3. It is collected
and the unused hydrogen and nitrogen are returned back into the reactor. 77
 CAN YOU ANSWER THESE QUESTIONS
1. How do systems in equilibrium react when subjected to a disturbance?
2. Hydrogen iodide HI is synthesised from hydrogen H2 and iodine I2. The reaction is
exothermic and reversible. How to increase the yield of HI?
3. Ethanoic acid is a weak acid dissociating in water. In an aqueous solution an equilibrium
between CH3COO‒ ions, H3O+ ions and CH3COOH molecules is established. What will happen
if water is added to the solution?
4. The reaction of synthesis of nitrogen oxide NO from nitrogen N2 and oxygen O2 is reversible.
Is it possible to generate more NO by compressing the reacting gases? Why?
5. The thermal decomposition of CaCO3 in a closed container is reversible. Is it possible to
increase the amount of decomposed CaCO3 by pumping an inert gas into the container or by
decreasing the volume of the container? Why?
6. If temperature rises, the yield of a reversible endothermic reaction is increased. Why?
7. The thermal decomposition of Ag2CO3 is an exothermic reaction. In a closed system the
process is reversible. The value of the equilibrium constant is 1,4.10‒2 at 127 oC. What is the
value of the equilibrium constant at 77 oC?
a) 4.10‒4 b) 1,9.10‒1
8. The reaction of synthesis of ammonia NH3 from nitrogen N2 and hydrogen H2 is reversible and
exothermic. Why is the industrial process of production of NH3 from N2 and H2 realised at
high temperature? Is it possible to increase the yield of NH3 by adding catalyst to the reacting
mixture?
rate of reactions and chemical equilibrium ‒ key points

● RATE OF A CHEMICAL REACTION is the change in concentration of a reactant or a product

over the change in time.

● The RATE LAW states that the rate of a chemical reaction is directly proportional to the
concentrations of reactants raised to some powers: v = k.[A]α[B]β.... . The constant k is called
rate constant of the reaction.

● If reactants are not present in the same phase, reaction rate increases with the increase of the
surface area (solid-liquid, solid-gas or liquid-gas).

● According to the van't Hoff's rule, the rate constant of a chemical reaction gets doubled
to quadrupled for each rise of 10 oC in temperature.

● CATALYSIS is the acceleration of the rate of a chemical reaction by adding substances not
consumed during the reaction.

● CATALYSt is a substance that increases the rate of a reaction without itself being consumed.
They create another route for the transformation of reactants into products thus lowering the
activation energy of reactions. inhibitor is a substance that lowers the rate of a reaction.
● homogeneous catalytic reactions speed up if the concentration of the homogeneous
catalyst is increased.

● heterogeneous catalytic reactions speed up if the surface area of the catalyst

available for the adsorption of reactants is increased.

● CATALYSts can not initialise a reaction that is not undergoing.

● Reactions undergoing in both forward and backward direction are reversible reactions. In
their chemical equations an equilibrium arrows → is used instead of an one way arrow →.
→
Reaction that undergo only in one direction (i.e. products can not react to produce the reactants)
are IRreversible. In closed systems most of the chemical reactions are reversible.

● Chemical equilibrium is a state of a reacting system in which both reactants and products
are present but their concentrations do not change over time. In equilibrium the rate of
the forward reaction is equal to the rate of the backward reaction.
[C]c.[D]d
● The equilibrium constant of the reaction aA + bB →
→ cC + dD is expressed as Kc =
[A]a[B]b
Concentrations of pure liquids and pure solids are not included in the expressions for the
equilibrium constants. If the reaction undergoes in gaseous phase the equilibrium constant
can be expressed in terms of the partial pressure of gases and is denoted by Kp.
● Chemical equilibrium is dynamic. According to the Le CHATELIER's PRINCIpal a system in equilibrium,
when subjected to a disturbance, responds in a way that tends to minimise the effect of the
disturbance.

● Equilibrium constant does not depend on reactants and products concentration. But adding reactants
or removing products shifts the equilibrium towards products. Removing reactants or adding products
shifts the equilibrium towards reactants.

● Equilibrium constant does not depend on pressure. But the equilibrium mixture composition changes
if the overall number of moles in the system changes. A rise in pressure favours the reaction reducing
the number of moles. A decrease in pressure favours the reaction increasing the number of moles.

● Equilibrium constant value changes with temperature. The composition of the equilibrium mixture also
changes. If temperature increases equilibrium shifts towards the endothermic reaction. If temperature
decreases equilibrium shifts towards the exothermic reaction.

● Catalysts do not affect equilibrium. They only accelerate reactions and reduce the period of time over
which the equilibrium is achieved.

● In industry all factors that affect the efficiency of chemical process are considered in terms of profit
from investments, energy consumption and environmental protection. Chemical processes undergo
at optimal conditions.
 PROjECTS
1. Calorific values of fuels and global environmental
issues
Compare the caloricity of different fuels. Discuss the impact of fuels combustion on the
environment. Are low molecular weight fuels less harmful for man and nature?

2. Caloricity of foods
What is foods caloricity? Why is it important to balance the everyday menu by choosing
foods assuring the indispensable for the body functioning energy? What foods are the most
calorific?

3. rate of reactions in the everyday life

Give examples of chemical reactions in the everyday life (in cooking, cleaning, painting, etc.)
What does their rate depend on? Give examples of processes that should be slowed down.

4. production of ammonia. THE HABER-BOSCH process

Learn more about the industrial production of ammonia. Pay attention to the reaction conditions.
Why is this process so important for industry?