Chapter 1
RATE OF CHEMICAL REACTION
AND CHEMICAL EQUILIBRIUM
YOU COME ACROSS different types of chemical
reactions in your daily life. You have also studied
a few such reactions in your previous classes.
Iron rusts if exposed to humid atmosphere.
During summer, milk left at room temperature
for a few hours becomes sour and is converted
into a curdy thick mass. A freshly cut apple
exposed to atmosphere becomes brown after
some time. When dilute sulphuric acid, H2SO4,
is added to barium chloride solution, a thick
white precipitate of barium sulphate is obtained.
Some of the reactions are slow and some are fast.
Some of the reactions that you come across in
the laboratory, are very fast. For example, when
HCl is added to NaOH solution, the reaction
occurs immediately. In this Chapter, you will
learn about the rates of reactions and various
factors which them. You will also learn the
reactions which are reversible in nature and do
not go to completion. The extent to which such
reactions proceed, is of immense industrial
importance, and you will learn this aspect of
reversible reactions as well.
1.1 SLOW AND FAST REACTIONS
If a clean magnesium wire is heated in a Bunsen
flame, it catches fire and is burnt down with a
flash in a few seconds. Here, magnesium is
oxidised in air.
2 Mg (s) + O2 (g) 2 Mg O(s)
Contrary to this, rusting of iron, which is also
a process of oxidation, takes place in several
hours or even days (and rust is chemically
represented as Fe 2 O 3 .xH 2 O). The reaction
between an acid and a base [such as,
HCl (aq) + NaOH (aq) NaCl (aq) + H2O(l)] takes
place in microseconds. The reactions that lead
to the contraction of muscles and that transmit
nervous impulses, are still more rapid. Contrary
to this, weathering of rocks takes place in
millions of years.
We may say that in certain cases, rate of
conversion of reactants into product(s) is fast,
and in certain cases, slow. Sometimes, we
increase or decrease the rate of a reaction to
suit our requirements. For example, the pressure
cooker is used to reduce the time needed to cook
food, and the food is kept in a refrigerator to
avoid spoilage.
The rates of chemical reactions are very
important in industries. Industrialists and
chemical engineers are not satisfied with merely
converting one substance into another. In most
of the cases, they want to obtain the product
rapidly, easily and as cheaply as possible. Time
and money are important in industry. It is often
necessary to accelerate reactions so that they
are economically worthwhile.
You will learn later in this Chapter that
temperature, pressure/concentration, and
catalyst affect the rates of reactions. At normal
temperature and pressure, and in absence of a
catalyst, ammonia cannot be obtained from
nitrogen and hydrogen. Fortunately, chemical
engineers have found that a reasonable reaction
rate results when the process is carried out at
250 atmospheric pressure and 723 K in presence
of a catalyst.
Catalyst (250 atm,723 K)
N 2 (g) + 3 H 2 (g) 2 NH3 (g)
Biological reactions in our body also depend
on the presence of catalysts. It is really very
interesting to know that almost every chemical
reaction in our body is controlled by one or more
catalysts. Catalysts are involved in simple
reactions like hydrolysis of starch to glucose.
These biological catalysts are called enzymes.
These enzymes are basically proteins which you
will study in your higher classes.
1.2 RATE OF A CHEMICAL REACTION
During a chemical reaction, reactants are
converted into products. The rate of a chemical
 Science and Technology
2
reaction tells us how fast the reaction is taking
place by indicating how much of a reactant is
consumed, or how much of a product is formed
in a given time.
Therefore,
Change in concentration of a
Reaction rate = substance (reactant or product)
Time taken
Thus, we can define reaction rate as the rate
of change of concentration of a particular
reactant or product. From the above expression
of the reaction rate, we can see that unit in
which rate can be expressed depends on the unit
of concentration of the reacting substances or
of products formed, and on the unit of time. For
example, if we express concentration in terms of
number of molecules produced in seconds, we
will write rate in the unit of molecules/second;
if we express concentration in molarity* M, and
time in second, we express rate in unit
of M/s or (mol L-1)/s or mol L-1s-1. Normally,
we express concentration in moles per litre in
aqueous reactions.
Let us take some specific examples of
reactions feasible in a laboratory. When acidified
hydrogen peroxide (H2O2) is added to a solution
of potassium iodide (KI), iodine is liberated
H2O2 (aq) + 2 KI (aq) + H2SO4 (aq) 2 H2O (l)
+ I2 (aq) + K2SO4 (aq)
Here, concentration of iodine is zero initially.
With the passage of time, it increases and the
reaction solution becomes brownish.
Concentration of iodine can be measured at
different intervals of time by titration against
sodium thiosulphate. If concentration of iodine
rises from 0 to 10-5 mol L-1 in 10 seconds, we
write
[I 2 ] 10 5 mol L1
reaction rate = = = 10 6 mol L1s 1
t 10 s
Here, symbol (delta) represents a change
and [I2], molar concentration of iodine.
This change in concentration of the product
(iodine) takes place in ten seconds, therefore,
* Molarity is the unit of concentration. It can be calculated if we know the amount of a substance (mole) in a known
volume of solution expressed in litre, i.e.
Number of moles of a substance dissolved
Molarity =
Volume of solution in litres
If 1 mol of the substance is present in 1 L of solution, we say that the solution is one molar or concentration of the
solution is 1 M or 1 mol per litre or 1 mol L-1.
we say that the rate is the average reaction
rate. If we measure change in concentration over
shorter time interval, we can obtain an accurate
estimate of reaction rate at any moment.
Rate of a reaction depends on the
concentration of the reactants. With lapse of
time, concentration of reactant(s) decreases, and
therefore, rate of the reaction also decreases.
In order to determine the rate at a particular
instant, one should make the time interval
almost zero, i.e.
[ I 2 ] d[ I 2 ]
=
t dt
t 0
d[I 2 ] denotes very small change in
concentration of I2, and dt denotes very small
change in time.
d I2[ ]
Thus, rate of reaction =
dt
This rate is instantaneous rate and you will
study about this in your higher classes.
You have seen that rate is expressed in terms
of change in concentration of iodine liberated
during the reaction. One can also think of
expressing the rate in terms of change in
concentration of H2O2 or KI consumed during
the course of reaction as well.
Concentration of iodine increases with time,
but concentration of H2O2 decreases with time,
and therefore, rate in terms of H2O2 and KI is
expressed as,
rate of reaction =
[
H2O2 ] = 1 [ KI]
t 2 t
Here, the negative sign indicates that
concentration of H2O2 and KI will decrease with
time. In the above reaction, rate of consumption
of KI is twice the rate of consumption of H2O2,
therefore, in order to make the two rates equal,
we divide by two (stoichiometric coefficient) and
1 [ KI]
write .
2 t
 Rate of Chemical Reaction and Chemical Equilibrium
3

Let us take one more example of a chemical rate of change of concentration of cisplatin
reaction. Cisplatin, Pt(NH 3 ) 2 Cl 2 is used in
chemotherapy of cancer. It reacts with water and ( 0.0094 0.0100 ) m ol L 1 0.0006 m ol L 1
= =
releases chloride ion bound to central platinum ( 40 0 ) m in 40 m in
metal. The reaction is represented as 5 1 1
= 1.5 10 mol L min
Pt(NH3)2Cl2 + H2O Pt(NH3)2Cl+ + Cl
where negative sign indicates that the
The rate at which this reaction can occur is concentration of cisplatin, Pt(NH 3 ) 2 Cl 2 , is
found by measuring the amounts of Pt(NH3)2Cl2 decreasing with lapse of time. It is supported by
consumed, or the amount of Cl released per unit the curve shown in Fig.1.1. As concentration of
volume of the reaction mixture per unit time. cisplatin decreases, concentration of chloride ion
Someone measures the amount of cisplatin per (Cl ) increases. Here, the rate of change of
unit volume at different intervals of time. Data
obtained is plotted in Fig.1.1. A part of the data
chloride ion concentration, i.e. is
[ ],
Cl

is also provided in Table 1.1.

t
Table 1.1 positive. The reaction rate is defined as the
rate of decrease of concentration of a
Time/min Concentration of cisplatin/mol L-1
reactant, or the rate of increase of
0 0.0100 concentration of a product, and is always
20 0.00970 given as a positive number. This means that
40 0.00940 [ reactant]
when rate is expressed in terms of ,
80 0.00887 t
which is a negative quantity, a minus sign is
0.0100 always used to make the rate positive.
Therefore, rate of reaction (average) between
I
0.0080 t1 = 0 min. and t2 = 40 minutes will be
Concentration(mol/L)

Cl

[ . 105 mol L1 min 1

= 15 ]
0.0060
5 1 1
= 1.5 10 mol L min
0.0040
Pt(NH3)2Cl2 Questions
0.0020 1. Explain the difference between average
II
reaction rate and instantaneous reaction rate
0.0000 with an example.
0 200 400 600 800 1000 1200 1400 2. Using Table 1.1, calculate the rate of reaction
Time (minutes)
of cisplatin with water between t 1 = 20
minutes and t2 = 40 minutes.
Fig.1.1: Change of concentration of cisplatin
[Pt(NH3)2Cl2] and chloride ion [Cl ] as function of time. 1.3 ENERGY CHANGES DURING A CHEMICAL
Graph clearly shows that concentration of cisplatin
REACTION
decreases with time (Curve II), whereas concentration
of chloride ion increases with time (curve I). Most of the chemical reactions are accompanied
by energy changes. In some reactions, energy is
given in form of heat and in some cases, in the
Rate of change of concentration of cisplatin form of light. The chemical reactions which

=
[Pt( NH )3 2 Cl 2 ]at t [Pt( NH )
2 3 2 Cl 2 ]at t 1
release heat are exothermic reactions. All
combustion reactions are exothermic reactions.
(t 2 t1 ) Methane on combustion releases heat energy.
If we consider concentrations at t1=0 min. CH4 (g) + 2O2 (g) CO2 (g) + 2H2O (l) +
and t2=40 min., then, Energy (890.4 kJ mol-1)
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4
One striking example of an exothermic
reaction is thermit reaction. Here, Fe 2O3 is
reduced to iron. The reaction has been used to
weld iron rails.
2 Al (s) + Fe2O3 (s) Al2O3 (s) + 2 Fe (l)
There is another category of reactions which
absorbs heat. Such reactions are called
endothermic reactions. When barium
hydroxide, Ba(OH) 2 .8H 2 O, and ammonium
thiocynate, NH4SCN, are mixed together in a
beaker or boiling tube, the reaction mixture
becomes so cold that moisture from the air forms
a layer of frost on outer surface of the beaker.
(Reaction starts in solid state initially and
gradually picks up with the formation of water).
Reaction is written as,
Ba(OH)2.8H2O (s) + 2 NH4SCN (s) Ba(SCN)2(aq)
+ 2 NH3 (aq) + 10 H2O (l)
However, most of the endothermic reactions
absorb only a small amount of heat. So, there is
probably not much future for chemical
refrigerators.
Activity 1.1
Take 10 g of barium hydroxide in a boiling
tube. Insert a thermometer graduated from
10 to 100 C. Now, add 5 g of NH4Cl and
mix with the help of a glass rod. Record the
temperature. Write the equation for the
reaction*.
There are certain reactions which take place
in presence of light. Such reactions are called
photochemical reactions. Photosynthesis by
plants is a photochemical reaction. Photographic
films which are normally coated with silver bromide
(and very small amount of silver iodide) undergo
chemical reaction when exposed to sunlight. This
basic reaction is used in photography.
1.4 FACTORS AFFECTING THE RATE OF A
REACTION
We are aware that in order to cook food faster,
we use pressure cooker. In the cooker, the
temperature of water is higher than its normal
boiling point, which is taken at one atmospheric
pressure. By raising pressure inside the
pressure cooker (by putting weight on its vent),
we increase the boiling point of water, or in other
words, raise the temperature of the cooking
* In place of NH4Cl, we can take NH4NO3.
** When gases or aqueous solutions react, reacting substances normally occur as individuals.
medium (which is water), and therefore, make
the cooking faster. Cooking is a chemical change
which is enhanced by raising the temperature.
One can conclude that temperature is one of the
factors responsible for enhancing the rate of a
reaction. In addition to temperature,
concentration/pressure and catalyst are other
factors which influence the rate of reactions. Let
us discuss them briefly.
1.4.1 Effect of Concentration
For a reaction to take place between two
molecules, it would be needed that they must
collide or come into contact (and this is the
reason that most of the chemical reactions are
carried out either in gaseous form or in aqueous
solutions). The probability of such collisions
increases with increasing the concentration of
the reacting molecules. It would be relevant to
remember that different reactants can affect the
rate of a particular reaction in different ways.
For example, when nitrogen oxide (NO) reacts
with oxygen (which is a homogenous system** ),
2 NO (g) + O2 (g) 2 NO2 (g)
the reaction rate doubles when oxygen
concentration doubles. However, doubling the
concentration of NO quadruples the rate of
reaction.
In case of heterogeneous systems (when
reactants and products are in different states),
the area of contact between the reacting
substances influences the rate considerably. For
example, magnesium powder reacts much more
rapidly than magnesium ribbon with dil. H2SO4.
In case of gases, the pressure is indicator of
concentration. We know that greater the number
of gaseous molecules per unit volume, greater
will be the pressure of the gas.
Activity 1.2
To study the effect of concentration, take
6 g of granular zinc and 10 mL each of 1 M
HCl and 2 M HCl. Attach a graduated
syringe with a boiling test tube as shown
in Fig. 1.2. Now, carry out the reaction
taking 3 g of zinc and 5 mL of 1 M HCl in
the first instance, and then 3 g of zinc and
5 mL of 2M HCl. Note the volume of the gas
at time intervals of 20 s, 40 s and 60 s in
 Rate of Chemical Reaction and Chemical Equilibrium
5

each case. What is your observation about 1.4.2 Effect of Temperature

the volumes of the gas produced? Plot a We are aware that perishable food like milk go
graph between time elapsed and volume of bad much more rapidly in summer than in
hydrogen produced in each case. The curve winter. In summer, when temperature goes from
obtained in these two cases will be of the 313 to 319 K (40 to 46 C), the chemical reaction
type shown in Fig.1.3. in the deterioration process occurs more rapidly
and we keep our food in freeze. We know that
marble chips (CaCO 3 ) on reaction with
hydrochloric acid give CO2,
CaCO3(s) + 2 HCl(aq) CaCl2(aq) + CO2(g) +
H2O (l)
When the above reaction is carried out at
Syringe 273 K, it is extremely slow. We can see only a
few bubbles of CO2, and amount of CO2 collected
in this process is very small. However, when we
raise the temperature to 323 K (50 C) or slightly
Hydrogen
more, we find that there is rapid evolution of CO2
gas and we can collect more volume of gas in a short
time. By increasing the temperature and
collecting the CO2 gas, we can have an idea of
the effect of temperature on this reaction. In
general, increasing the temperature increases
the rate of chemical reactions. How
temperature affects the rate of reaction is
HCl depicted in Fig.1.4.

Zinc
Fig. 1.2 : A simple method for following the course of a
Reaction rate

Reaction rate

chemical reaction when one product happens to be a

gas. In this case, the tube contains granular zinc
and hydrochloric acid :
Zn (s) + 2 HCl(aq) ZnCl2(aq) + H2 (g).

Temperature Temperature
100
(a) Most reactions (b) Explosive reactions
80 2 M HCl, 293 K
H2 Produced (mL)

Reaction rate

60
30 mL

40 1 M HCl, 293 K
20 s

15 mL
20
20 s
Temperature
20 40 60 80 100 120 (c) Enzyme catalysed reactions
Time Elapsed(s)

Fig. 1.3 : Data plot demonstrating concentration Fig. 1.4 : Showing effect of temperature on the rate
effects at 1 M and 2 M HCl, at constant temperature. of reaction.
 Science and Technology
Can you explain the curves shown in
Fig. 1.4? The rate of an enzyme catalysed reaction
increases at first, and then decreases as the
temperature increases. How far enzymes are
susceptible to temperature, you will study in
your higher classes.
Activity 1.3
Repeat the activity 1.2 by taking 3 g of zinc
and 5 mL of 1M HCl at two different
temperatures, 293 K and 308 K. Plot the
graph as done above. Here, you will find that
raising the temperature of the HCl solution
taken in the test tube, volume of the
hydrogen formed during the same time will
be more at 308 K than at 293 K (Fig.1.5).
Further, perform the experiment taking 3 g
of zinc dust, instead of taking zinc granules,
and 1M HCl. Compare the volume of the
hydrogen formed in these two cases. Record
your observations and plot a graph between
time and volume of the hydrogen gas.
Fig. 1.5 : Data plot demonstrating temperature effects
at 293 K and 308 K for 1M HCl.
1.4.3 Effect of Catalysts
In the manufacture of ammonia, iron is used as
a catalyst, and it enhances the rate of this
reaction
Fe (catalyst)
N 2 (g) + 3 H 2 (g) 2 NH3 (g)
Similarly, reaction of SO2 and O2 gives SO3
in presence of nitrogen monoxide (NO), which
acts as a catalyst.
6
NO (g)
2 SO 2 (g) + O 2 (g) 2 SO3 (g)
Initially, NO takes part in the chemical
reaction, but finally, it is regenerated. As such,
there is no change in its concentration.
Thus, catalysts are substances which alter
the rate of chemical reactions without
undergoing any overall chemical change
themselves.
In most of the cases, catalysts are used to
accelerate the reactions. Certain catalysts
however, slow down reactions. For example,
glycerine is sometimes added to hydrogen
peroxide (H2O2) as negative catalyst in order to
slow down its rate of decomposition. Reactions
of biological and industrial importance take place
in presence of catalysts, which would never
occur in their absence. Many industrial
processes, including the manufacture of
NH3, H2SO4, HNO3, ethene (C2H4), polythene and
polystyrene, rely heavily on catalysts. Every
chemical reaction in animals, plants and micro-
organisms requires its own enzyme (catalyst).
1.4.4 Effect of light
Photosynthesis and photography (as mentioned
in Section 1.3), both involve light sensitive
reactions. In our daily life, a coloured cloth
gradually fades when dried in sunlight. Dyes of
the clothes undergo chemical change and fade
gradually. As mentioned earlier, plants prepare
their food in presence of light. The process is
called photosynthesis.
Questions
1. Name the factors which affect the rate of
reaction.
2. In the following reaction,
2 Mg + 2HCl Mg Cl2 + H2
what will be the effect on the rate of evolution
of hydrogen gas if the concentration of HCl is
doubled?
1.5 REVERSIBLE AND IRREVERSIBLE
REACTIONS
Normally, we write most of the reactions with
the assumption that they go to completion, and
indicate them by using single arrow ( ). For
example, we write, the reaction between N2 and
H2 as
N2 (g) + 3H2 (g) 2 NH3 (g)
 Rate of Chemical Reaction and Chemical Equilibrium
Experimentally, it has been found that when
nitrogen and hydrogen gases are taken in
stoichiometric ratio* in reaction container, they
do not fully react to form ammonia. If we take
28 g of nitrogen and 6 g of hydrogen, and allow
them to react in a close container, we expect to
get 34 g of ammonia according to the equation
stoichiometry given above. However, it is not
found in practice. As soon as NH3 is formed, it
starts breaking into nitrogen and hydrogen in
the reverse direction. Here, since reaction is
possible in both the directions, we say reaction
between hydrogen and nitrogen is reversible
and we denote it by,
N2 (g) + 3H2 (g) 2NH3 (g)
A double half-headed arrow ( ) is a sign of
reversibility and indicates that the reaction
can take place in either direction. There are
thousands of such reactions which are
reversible in nature. Some common reversible
reactions are,
H2 (g) + I2 (g) 2 HI (g)
N2 (g) + O2 (g) 2 NO (g)
CaCO3 (s) CaO (s) + CO2(g)
3 Fe (s) + 4 H2O (g) Fe3O4 (s) + 4 H2 (g)
However, when a major portion of the
reactant(s) is converted into product(s), and it is
not easily possible to detect the presence of the
reactant(s) after the reaction has taken place,
we say reaction has gone to completion and it is
of irreversible nature.
You will come across many more such
reactions during your studies in this class and
later.
1.6 REVERSIBLE PROCESSES AND
CHEMICAL EQUILIBRIUM
We have just seen that formation of ammonia is
a reversible process. Let us reproduce the
reaction for discussion,
N2 (g) + 3H2 (g) 2 NH3 (g)
If we say that nitrogen and hydrogen react
under appropriate conditions and give ammonia,
then this statement is expressed in the form of
an equation as
N2 (g) + 3 H2 (g) 2 NH3 (g)
* ratio of masses of constituents in the balanced chemical equation.
7
The reaction is taking place in forward
direction and we, therefore, say it is a forward
reaction. We can also write decomposition of
NH3 as,
2NH3 (g) N2 (g) + 3H2 (g)
which is, in fact, a reverse of the forward reaction
and takes place in opposite direction, and
therefore, we call this reaction as reverse
reaction. We represent forward and reverse
reactions together as
N2 (g) + 3H2 (g) 2 NH3 (g)
Such reactions never go to completion if
performed in a close container. For a reversible
chemical reaction, an equilibrium state is attained
when the rate at which a chemical reaction is
proceeding in forward direction equals the rate
at which the reverse reaction is proceeding
(Fig. 1.6). At equilibrium,
Rate of forward = Rate of of reverse
reverse
reaction = reaction
In case of ammonia, when reaction is
performed at high pressure and temperature in
a close container, at equilibrium,
Rate of formation = Rate of decomposition
=
of ammonia of ammonia
Now, what happens to molecules of ammonia
(NH 3 ), hydrogen (H 2 ) , and nitrogen (N 2 ) at
N2(g)+3H2(g) 2NH3(g)
(Rate decreasing with time)
Equilibrium
Rate
(Rate increasing with time)
2NH3(g) N2(g) + 3H2(g)
(1.1) 0
Time
Fig. 1.6 : A graph showing how the reaction rates for
the synthesis (formation) and decomposition of ammonia
change with time. Initially, at time zero, only hydrogen
and nitrogen are present in a closed container.
 Science and Technology
8
equilibrium? Do all the ammonia molecules
remain intact and do not decompose, and all the
molecules of nitrogen and hydrogen become
inactive and do not combine, and a static
equilibrium is attained? Or, some ammonia
molecules decompose into nitrogen and hydrogen
molecules and some hydrogen and nitrogen
molecules combine according to law of constant
proportion (Chapter 2 of Class IX) to form
ammonia and a dynamism is there.
In case of ammonia, using deuterium, D (an
isotope of hydrogen) it has been proved that even
at equilibrium, decomposition of ammonia into
hydrogen and nitrogen and combination of
hydrogen and nitrogen into ammonia continues.
This supports dynamic nature of equilibrium.
Fig. 1.7 : (a) Static equilibrium : Children on a
see-saw. At the balance point (i.e the equilibrium
position), no movement of the children on the
see-saw occurs.
Rate of evaporation
rate of condensation
(a)
Fig. 1.8 : Equilibrium vapour pressure.
Since the rate of decomposition and rate of
formation is the same at equilibrium, the
concentrations of ammonia, hydrogen and
nitrogen remain constant. This equilibrium is
dynamic in nature and is therefore, called
dynamic equilibrium. An analogy between
static and dynamic equilibrium is shown in
Fig.1.7 (a) and 1.7 (b).
Equilibrium is also attained in physical
processes like vapourisation, condensation,
fusion and freezing, if performed in close
containers. At a particular temperature, a closed
vessel containing water or a volatile liquid will
show equilibrium vapour pressure, which can
be measured using a manometer (Fig.1.8). All
such physical processes reach to the state of
Boy running
up an escalator
Escalator
moving down
Fig. 1.7 : (b) Dynamic equilibrium : Boy ascending an
escalator at the same rate as the escalator descends.
At the balance point, (i.e the equilibrium position) the
boy and the escalator are moving at the same rate in
opposite direction maintaining the equilibrium position.
Rate of evaporation =
rate of condensation
(b)
 Rate of Chemical Reaction and Chemical Equilibrium
9
equilibrium, which is dynamic in nature. In a
close container containing water, rate of
evaporation and rate of condensation of water
molecules become equal at equilibrium.
1.6.1 Characteristic Features of Dynamic
Equilibrium
(i) At equilibrium, macroscopic (observable)
properties such as concentration, density,
colour, etc., are constant under the given
condition of temperature, pressure and
initial amount of the substances.
(ii) At equilibrium, microscopic (at molecular
level) processes continue, but they are in
balance. This means that no overall large
scale (macroscopic) changes occur. Rate of
forward process (reaction) is equal to the
rate of reverse process, and as a
consequence of this, no net change results.
(iii) The equilibrium can be attained from either
direction, beginning with only the materials
on one side of the change. Such changes
are described as reversible.
(iv) Equilibrium can be achieved in a closed
system. In a closed system, there is no loss
or gain of matter to or from the
surroundings. An open system may allow
matter to escape or to enter. Therefore, in
an open system, the equilibrium cannot be
attained.
1.6.2 Equilibrium Constant and Extent of
a Chemical Reaction
It has been experimentally found that at a
particular temperature, when equilibrium is
attained, the ratio between concentration of
reactants and products becomes constant.
For reaction
N2 (g) + 3 H2 (g) 2 NH3 (g) + 92 kJ
[ NH3 ]
2
=K
[ N 2 ][ H2 ]
At equilibrium, 3
Here, concentration of product (ammonia)
occurs in numerator, and those of reactants
(hydrogen and nitrogen) occur in denominator.
Each concentration term, [NH3], or [N2], or [H2],
is raised to a power equal to stoichiometric*
* Coefficients used just before the reactants or products in a balanced chemical equation.
coefficient in the balanced equation. K is called
equilibrium constant. For a general reaction,
aA+ bB cC +dD
at equilibrium, equilibrium constant can be
written as,
[C] c [ D ] d
K=
[ A] a [ B ] b (1.2)
In the above expression, square bracket
denotes molar concentration, i.e. concentration
in mol/L as mentioned earlier. The expression
(1.2) is also known as Law of Chemical
Equilibrium. At a particular temperature,
equilibrium constant has a definite value. When
we express concentration in mol L-1, equilibrium
constant is denoted by Kc.
Magnitude of equilibrium constant, K,
indicates how far a chemical reaction can go. In
other words, it is an indicator of the extent of a
chemical reaction. Larger the value of K, higher
will be the equilibrium concentration of products
on the right hand side of the reaction. Smaller
value of K indicates lower concentration of
the products at equilibrium. For the reaction at
298 K,
PCl3 (g) + Cl2 (g) PCl5 (g) ; Kc = 1.9
Low value of equilibrium constant shows that
at equilibrium, the concentration of product
(PCl5) will be low. Similarly, for reaction at
298 K,
N2 (g) + O2 (g) 2 NO (g)
2
[NO ]
Kc = = 4.8 10-31
[N 2 ][O 2 ]
Very small value of Kc implies that reactants
N2 and O2 will be dominant species in the system
at equilibrium.
For reaction (1.1) at 298 K given earlier,
2
[NH 3 ]
Kc = 3
= 3.6 108
[N 2 ][H 2 ]
Large value of K c indicates that at
equilibrium, virtually a major portion of nitrogen
and hydrogen (mixed in molar ratio 1 : 3) will be
converted into ammonia.
 Science and Technology
10
NH3 is manufactured at a very high pressure
(200 to 1000 atmosphere) and at a slightly higher
temperature 723 K, as the reaction is very slow
at room temperature. We have already seen in
this Chapter that rate of a reaction increases by
raising temperature of the reactants. The value
of equilibrium constant also depends on
temperature. You will study other relevant
details in this regard in your higher classes.
Questions
1. Explain what is meant by a reversible
reaction?
2. State the law of chemical equilibrium. Write
an expression of this law for the following
hypothetical reaction :
2X + 4Y 3Z
So far, we have discussed reversible
reactions, in which, mostly molecules take part
and equilibrium is established. Now, we shall
discuss ionic processes, in which equilibrium
exists. Before discussing them, we shall first
consider electrolytes and their dissociation in
aqueous solution.
1.7 DISSOCIATION OF ELECTROLYTES
You have already studied that sodium chloride
is an ionic substance and is made of Na+ and
Cl ions. In solid crystal of sodium chloride, Na+
and Cl ions are tightly bound by coulombic
forces. When solid sodium chloride is dissolved
Fig.1.9 : Dissolution and dissociation of NaCl in water
in water, the ions which are tightly bound,
become free to move in solution (Fig.1.9). The
process can be depicted as
NaCl (s) + H2O (l) Na+ (aq) + Cl (aq)
This process of breaking of NaCl in free Na+
and Cl ions is dissociation. Further, sometimes
solute is a polar covalent compound, like
hydrochloric acid gas (HCl), and when added in
water, it interacts with water and forms ions.
This is depicted as
HCl (g) + H2O (l) H3O+ (aq) + Cl (aq)
Here, H3O+ ion and Cl ions were not present
earlier, but resulted due to interaction with water.
In the above two cases, compound is nearly
broken into ions and we call such compounds
strong electrolytes. Here, NaCl is almost fully
dissociated into Na+ and Cl. Similarly, HCl is
also dissociated into H+ and Cl. However, there
are substances like CH3COOH, which when
added to water, dissociate partially.
CH3COOH (aq) + H2O (l) H3O+ (aq) +
CH3COO (aq)
In this case, all the molecules of CH3COOH
do not dissociate into H3O+ and CH3COO ions.
There is an equilibrium between ions formed and
undissociated molecules. Such substances are
called weak electrolytes. There are many
electrolytes in this category, such as NH4OH,
oxalic acid, etc. Dissociation of acetic acid is
Sodium ion
Chloride ion
Water dipole
 Rate of Chemical Reaction and Chemical Equilibrium
11
represented by double arrow ( ) as we have
used in the case of reversible chemical reactions
earlier. We write,
CH3COOH (aq) + H2O (l) H3O+ (aq) +
CH3COO (aq)
1.8 ACIDS AND BASES
According to earlier views of scientists, acids
were substances that tasted sour, changed the
colour of the litmus paper from blue to red,
reacted with certain metals to give off hydrogen
gas, and formed carbondioxide with carbonates.
Above all, acids were able to neutralize bases.
Bases were considered substances that tasted
bitter, felt slippery, changed the colour of litmus
paper from red to blue. Above all, bases were
able to neutralize acids.
In 1884, Svante Arrhenius proposed a new
theory of acids and bases. According to him,
acids are substances that produce hydrogen ions
(H+) when mixed with water, and bases are
substances that produce hydroxyl ions (OH-)
when mixed with water. For example, HCl when
dissolved in water, gives out H+ ion and Cl- ion.
HCl (aq) H+ (aq) + Cl (aq)
Therefore, HCl is an acid. Similarly, NaOH,
when dissolved in water, gives out OH- ions and
therefore, is a base.
NaOH (aq) Na+ (aq) + OH (aq)
Arrhenius theory was applicable for quite a
good number of compounds such as KOH, NaOH,
H2SO4, HNO3, etc. Thus, the concept of acids and
bases was applicable for those substances which
gave H+ and OH- ions, respectively. Acids and
bases both come in the category of electrolytes
and therefore, are also classified as weak and
strong acids and bases, similar to electrolytes.
For example, HCl, HNO3 and H2SO4 are strong
acids and CH3COOH, H2CO3 are weak acids.
Similarly, NaOH, KOH are strong bases and
NH4OH, Ca(OH)2 are weak bases.
Neutral
Increasingly
acidic
7
+ _
H OH
0
Fig. 1.10 : pH Scale. A neutral solution has pH of 7, which means H+ ion concentration is equal to the OH ion
concentration.
Please remember, log1010x = x or log1010x = x
Arrhenius concept of acids and bases lasted
till early twentieth century. Soon after this,
chemists realised that acids and bases could be
discussed by focussing on the ability of ions and
molecules to donate or accept protons (hydrogen
ion H+). This definition is much broader and you
will learn it in your higher classes.
1.8.1 pH SCALE
The hydrogen ion concentration is a significant
quantity in every biological process and in a large
number of industrial processes. We describe
quantitatively acidic and basic character of
aqueous solutions in terms of hydrogen ion and
hydroxyl ion concentration. For the purpose of
convenience, Sorensen, in 1909, defined a new
scale called pH Scale. pH is defined as the
negative logarithm (base 10) of the hydrogen
ion concentration in moles per litre.
pH = log10 [H+]
Since H + ion is associated with H 2 O
molecules, therefore, we normally write H+ as
H3O+ and pH is written as
pH = log10 [H3O+]
It is very easy to convert hydrogen ion
concentration [H + ] to pH, and vice versa.
At 298 K (25C) in a neutral solution,
Hydrogen ion concentration [H+] = hydroxyl
ion concentration [OH] = 1.010-7 mol L-1.
Therefore, pH of a neutral solution can be written
as
pH = log10 [H+] = log10 [110-7] = 7
when pH is above 7, the solution is basic, and
when it is below 7, the solution is acidic
(Fig 1.10). For example, if H+ concentration of
the solution is 110-2 mol L-1,
pH = log10 [H+] = log10 [110-2] = [2] = 2.
The solution is acidic.
Increas
ingly
basic
14
 Science and Technology
12

If H+ concentration is 110-9 mol L-1, Solution

pH = log10 [110-9] = 9. We know that pH = log [H+]
The solution is basic. If pH is 5, the hydrogen ion concentration will be
In some cases, it is easy to take logarithm of 110-5 mol L-1.
hydrogen ion concentration. For example, if
If pH is 4, the hydrogen ion concentration will be
hydrogen ion concentration is 110 -9 ,
110-4 mol L-1.
110-2, or 110-7 mol L-1, pH will be 9, 2 and 7
Increase in concentration of H+ ions
respectively. It is slightly difficult to determine
pH when concentration term is like 5 10-5 or 4 1
9 10-4 mol L-1. Here, 5 and 9 create problem in 1 10 mol L
= 5 1 =10 times
taking logarithm and therefore, we take help of 1 10 mol L
logarithm table. You will learn about logarithm
and pH in detail in higher classes. pH of some H+ molarity is increased 10 times from
common solutions are given in Table 1.2. 110-5 mol L-1 to 110-4 mol L-1.

Table 1.2 : Approximate Values of pH for Question

Some Familiar Solutions
Solution pH The pH values of three acids A, B and C having
equal molar concentration are 5.0, 2.8 and
1M NaOH 14 3.5 at 298 K. Arrange these acids in order of
1M NH3 (household ammonia) 11.6 their increasing acidity.
Saturated Mg(OH)2 10.5
(milk of magnesia)
Blood 7.3 7.5 WHAT YOU HAVE LEARNT
Saliva 6.5 7.5
Urine 5.5 7.5 l Some reactions are slow, some are
Coffee 4.5 5.5 moderate and some are very fast. Rate
Beer 4.0 5.0 of reaction ranges from microseconds
Tomato juice 4.0 4.4 to millions of years.
Wine 2.8 3.8 l Rate of a reaction is defined as rate of
Vinegar 2.4 3.4 change of concentration of a particular
Lemon juice 2.2 2.4 reactant or product. It is expressed as:
Gastric juice 1.0 3.0 Reaction rate = Change in concen-
Battery acid 0.5 tration of a substance (reactant or
product) per unit time.
1M HCl 0 l Rate of a reaction depends on
concentration, temperature and
Example 1.1 catalyst.
l Chemical reactions are accompanied
Determine the pH of the acidic solution formed
with energy changes. Energy is released
when 0.02 mol of HCl is added to enough water
or absorbed in the form of heat or light.
to make the final volume 2.0 L.
On this basis, there are two types of
Solution reactions: exothermic and endothermic.
0.02 mol HCl is present in 2 L. l Reactions can also be classified broadly
Therefore, 0.01 mol HCl will be present in 1 L. in categories of reversible and
Hydrogen ion concentration = 0.01 mol/ 1 L irreversible. Theoretically, all reactions
= 0.01 mol L-1 are reversible.
pH = log [0.01] = log [1 10-2] = 2 l Reversible reactions attain a state of
Example 1.2 equilibrium, at which rate of forward
reaction is equal to rate of reverse
pH of a solution changes from 5 to 4. How many
reaction. This equilibrium is dynamic
times do you expect a change in hydrogen ion
in nature.
concentration?
 Rate of Chemical Reaction and Chemical Equilibrium
13

l Physical processes also show dynamic l Electrolytes are substances which

equilibrium. Equilibrium is always
attained in a closed system.
l Equilibrium concentration(s) of
product(s) and reactant(s) depict a
constant ratio, which is called
equilibrium constant. Equilibrium
constant is indicator of the extent of a
chemical reaction. For a general
reaction a A + b B W c C + d D,
equilibrium constant is,
provide cations and anions when
dissolved in water. On the basis of
dissociation, electrolytes are called
weak or strong electrolytes.
l Acids and bases are also electrolytes.
Acids provide hydrogen ions (H+) and
bases provide hydroxyl ions (OH) in the
solution on dissociation. There is also
equilibrium between dissociated and
undissociated molecules of acids and
bases.
l Negative logarithm of hydrogen ion
concentration is defined as pH of a
solution. It is expressed as pH = log[H+]
and a pH scale is used to denote acidity
or alkalinity of a solution.

EXERCISES

1. Which of the following reactions are slow and which are fast?
(i) Setting of cement.
(ii) Formation of coal in the earth crust.
(iii) Reaction between aqueous solution of BaCl2 and H2SO4.
2. Give one example of a reaction which takes place
(i) instantaneously
(ii) at moderate rate
3. How will you define the rate of a chemical reaction? What is the meaning of average rate
of a chemical reaction?
4. What are various factors which effect the rate of a chemical reaction? Explain with
suitable examples.
5. What is the role of a catalyst in a chemical reaction? Does a catalyst undergo any
change at the end of a chemical reaction?
6. What is the effect of temperature on the following:
(i) Dissociation of an electrolyte (dissolution is taken as an endothermic process).
(ii) Rate of a reaction in gaseous state.
(iii) Concentration of product(s) of an exothermic reversible reaction carried out in
a closed container.
7. What do you mean by dynamic equilibrium? In what way is it different from static
equilibrium? Explain with suitable examples.
8. Can we achieve equilibrium between water and its vapour in an open container? Explain
your answer and say what will happen eventually?
9. Which of the following processes will be at equilibrium:
(i) Water maintained at 233 K in a closed container.
(ii) Sulphur dioxide being released in atmosphere at 298K.
(iii) Heating of calcium carbonate at 773 K in a closed kiln.
10. Which of the following reactions will favour the formation of product(s) when the
temperature is raised by 10 C and reaction is carried out in a closed container:
(i) N2 (g) + 3H2(g) W 2 NH3(g) + 92 kJ
(ii) 2Cl2(g) + 2H2O(g) W 4HCl (g) + O2(g) 113 kJ
 Science and Technology
14

11. Write an expression for equilibrium constant for the following reactions:
(i) 2NO2(g) N2O4(g)
(ii) 2SO2(g) + O2(g) 2SO3(g)
(iii) CO(g) + 3H2(g) CH4(g) + H2O(g)
(iv) Fe3+(aq) + SCN-(aq) FeSCN2+ (aq)
12. Classify the following acids and bases in the categories of weak and strong:
(i) HCl (iv) HCN (vii) NaOH
(ii) H2SO 4 (v) HClO 4 (viii) Ca(OH) 2
(iii) CH 3COOH (vi) H3PO4 (ix) NH4OH
13. Find the pH of the solutions if the acids are fully dissociated.
(i) 0.01 M HCl
(ii) 0.05 M H2SO4
14. Classify the following into strong and weak electrolytes on the basis of their behaviour
in aqueous solution:
(i) NaCl
(ii) NH 4 Cl
(iii) CH 3COOH
(iv) HCN
(v) NaOH
15. Calculate the pH of the solution when hydrogen ion concentration is:
(i) 1.0 10-7 M
(ii) 1.0 10-9 M
16. At 298 K, equilibrium concentrations of the reactants and products for the reaction,
H2(g) + I2(g) 2HI(g) are as follows: [HI] = 0.490 M, [H2] = 0.080 M and [I2] = 0.060 M.
Calculate the equilibrium constant at this temperature.
17. Equilibrium constants for the reactions given below are provided in the right hand side
at 298 K:
N2O4(g) 2NO2(g); K = 4.66 10-3
2NH3 N2(g) + 3H2(g); K = 3.0 10-9
In which case, formation of the products will be more favoured?