Chp 6
Chp 6
Chp 6
Equilibrium
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this dynamic equilibrium stage that there is characteristic features. We observe that the
no change in the concentrations of various mass of ice and water do not change with
species in the reaction mixture. Based on the time and the temperature remains constant.
extent to which the reactions proceed to reach However, the equilibrium is not static.
the state of chemical equilibrium, these may The intense activity can be noticed at the
be classified in three groups. boundary between ice and water. Molecules
(i) The reactions that proceed nearly from the liquid water collide against ice and
to completion and only negligible adhere to it and some molecules of ice escape
concentrations of the reactants are into liquid phase. There is no change of mass
left. In some cases, it may not be even of ice and water, as the rates of transfer of
possible to detect these experimentally. molecules from ice into water and of reverse
transfer from water into ice are equal at
(ii) The reactions in which only small
atmospheric pressure and 273 K.
amounts of products are formed and
most of the reactants remain unchanged It is obvious that ice and water are in
at equilibrium stage. equilibrium only at particular temperature
and pressure. For any pure substance at
(iii) The reactions in which the concentrations
atmospheric pressure, the temperature at
of the reactants and products are
which the solid and liquid phases are at
comparable, when the system is in
equilibrium is called the normal melting point
equilibrium.
or normal freezing point of the substance. The
The extent of a reaction in equilibrium system here is in dynamic equilibrium and we
varies with the experimental conditions such can infer the following:
as concentrations of reactants, temperature, (i) Both the opposing processes occur
etc. Optimisation of the operational conditions simultaneously.
is very important in industry and laboratory (ii) Both the processes occur at the same
so that equilibrium is favorable in the rate so that the amount of ice and water
direction of the desired product. Some remains constant.
important aspects of equilibrium involving
physical and chemical processes are dealt in 6.1.2 Liquid-Vapour Equilibrium
this unit along with the equilibrium involving This equilibrium can be better understood if
ions in aqueous solutions which is called as we consider the example of a transparent box
ionic equilibrium. carrying a U-tube with mercury (manometer).
Drying agent like anhydrous calcium chloride
6.1 E Q U IL IBRI U M IN P H Y S I C A L
(or phosphorus penta-oxide) is placed for
PROCESSES
a few hours in the box. After removing the
The characteristics of system at equilibrium drying agent by tilting the box on one side, a
are better understood if we examine some watch glass (or petri dish) containing water
physical processes. The most familiar examples is quickly placed inside the box. It will be
are phase transformation processes, e.g., observed that the mercury level in the right
solid liquid limb of the manometer slowly increases and
liquid gas finally attains a constant value, that is, the
solid gas pressure inside the box increases and reaches
a constant value. Also the volume of water in
6.1.1 Solid-Liquid Equilibrium
the watch glass decreases (Fig. 6.1). Initially
Ice and water kept in a perfectly insulated there was no water vapour (or very less) inside
thermos flask (no exchange of heat between its the box. As water evaporated the pressure in
contents and the surroundings) at 273K and the box increased due to addition of water
the atmospheric pressure are in equilibrium molecules into the gaseous phase inside
state and the system shows interesting the box. The rate of evaporation is constant.
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However, the rate of increase in pressure vapour to liquid state is much less than the
decreases with time due to condensation rate of evaporation. These are open systems
of vapour into water. Finally it leads to an and it is not possible to reach equilibrium in
equilibrium condition when there is no net an open system.
evaporation. This implies that the number
Water and water vapour are in equilibrium
of water molecules from the gaseous state
into the liquid state also increases till the position at atmospheric pressure (1.013 bar)
equilibrium is attained i.e., and at 100°C in a closed vessel. The boiling
point of water is 100°C at 1.013 bar pressure.
rate of evaporation= rate of condensation
For any pure liquid at one atmospheric
H2O(l) H2O (vap)
pressure (1.013 bar), the temperature
At equilibrium the pressure exerted by at which the liquid and vapours are at
the water molecules at a given temperature equilibrium is called normal boiling point of
remains constant and is called the equilibrium the liquid. Boiling point of the liquid depends
vapour pressure of water (or just vapour on the atmospheric pressure. It depends on
pressure of water); vapour pressure of water the altitude of the place; at high altitude the
increases with temperature. If the above boiling point decreases.
experiment is repeated with methyl alcohol,
acetone and ether, it is observed that different 6.1.3 Solid – Vapour Equilibrium
liquids have different equilibrium vapour
Let us now consider the systems where solids
pressures at the same temperature, and the
sublime to vapour phase. If we place solid
liquid which has a higher vapour pressure is
iodine in a closed vessel, after sometime
more volatile and has a lower boiling point.
the vessel gets filled up with violet vapour
If we expose three watch glasses containing and the intensity of colour increases with
separately 1mL each of acetone, ethyl alcohol, time. After certain time the intensity of
and water to atmosphere and repeat the colour becomes constant and at this stage
experiment with different volumes of the
equilibrium is attained. Hence solid iodine
liquids in a warmer room, it is observed
sublimes to give iodine vapour and the iodine
that in all such cases the liquid eventually
vapour condenses to give solid iodine. The
disappears and the time taken for complete
equilibrium can be represented as,
evaporation depends on (i) the nature of the
liquid, (ii) the amount of the liquid and (iii) the I2(solid) I2 (vapour)
temperature. When the watch glass is open Other examples showing this kind of
to the atmosphere, the rate of evaporation equilibrium are,
remains constant but the molecules are
dispersed into large volume of the room. As Camphor (solid) Camphor (vapour)
a consequence the rate of condensation from NH4Cl (solid) NH4Cl (vapour)
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6.1.4 Equilibrium Involving Dissolution pressure of the gas above the solvent.
of Solid or Gases in Liquids This amount decreases with increase of
Solids in liquids temperature. The soda water bottle is sealed
under pressure of gas when its solubility in
We know from our experience that we can
water is high. As soon as the bottle is opened,
dissolve only a limited amount of salt or
some of the dissolved carbon dioxide gas
sugar in a given amount of water at room
escapes to reach a new equilibrium condition
temperature. If we make a thick sugar syrup
required for the lower pressure, namely its
solution by dissolving sugar at a higher
partial pressure in the atmosphere. This is
temperature, sugar crystals separate out if we
how the soda water in bottle when left open
cool the syrup to the room temperature. We call
to the air for some time, turns ‘flat’. It can be
it a saturated solution when no more of solute
generalised that:
can be dissolved in it at a given temperature.
The concentration of the solute in a saturated (i) For solid liquid equilibrium, there is
solution depends upon the temperature. In only one temperature (melting point) at
a saturated solution, a dynamic equilibrium 1 atm (1.013 bar) at which the two
exits between the solute molecules in the solid phases can coexist. If there is no
state and in the solution: exchange of heat with the surroundings,
the mass of the two phases remains
Sugar (solution) Sugar (solid), and
constant.
the rate of dissolution of sugar = rate of
crystallisation of sugar. (ii) For liquid vapour equilibrium, the
vapour pressure is constant at a given
Equality of the two rates and dynamic
temperature.
nature of equilibrium has been confirmed with
the help of radioactive sugar. If we drop some (iii) For dissolution of solids in liquids,
radioactive sugar into saturated solution of the solubility is constant at a given
non-radioactive sugar, then after some time temperature.
radioactivity is observed both in the solution (iv) For dissolution of gases in liquids,
and in the solid sugar. Initially there were no the concentration of a gas in liquid
radioactive sugar molecules in the solution is proportional to the pressure
but due to dynamic nature of equilibrium, (concentration) of the gas over the liquid.
there is exchange between the radioactive These observations are summarised in
and non-radioactive sugar molecules between Table 6.1
the two phases. The ratio of the radioactive Table 6.1 Some Features of Physical Equilibria
to non-radioactive molecules in the solution
increases till it attains a constant value. Process Conclusion
Liquid Vapour p H 2O constant at given
Gases in liquids temperature
H2O (l) H2O (g)
When a soda water bottle is opened, some of
Solid Liquid Melting point is fixed at
the carbon dioxide gas dissolved in it fizzes constant pressure
out rapidly. The phenomenon arises due H2O (s) H2O (l)
to difference in solubility of carbon dioxide Solute(s) Solute Concentration of solute
at different pressures. There is equilibrium (solution) in solution is constant
between the molecules in the gaseous state Sugar(s) Sugar at a given temperature
and the molecules dissolved in the liquid (solution)
under pressure i.e.,
Gas(g) Gas (aq) [gas(aq)]/[gas(g)] is
CO2 (gas) CO2 (in solution) constant at a given
This equilibrium is governed by Henry’s temperature
CO2(g) CO2(aq)
law, which states that the mass of a gas [CO2(aq)]/[CO2(g)] is
dissolved in a given mass of a solvent at constant at a given
any temperature is proportional to the temperature
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1 2 1 2
(a) (b)
Fig.6.3 Demonstrating dynamic nature of equilibrium. (a) initial stage (b) final stage after the
equilibrium is attained.
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composition of an equilibrium mixture? The Six sets of experiments with varying initial
last question in particular is important when conditions were performed, starting with only
choosing conditions for synthesis of industrial gaseous H2 and I2 in a sealed reaction vessel
chemicals such as H2, NH3, CaO etc. in first four experiments (1, 2, 3 and 4) and
To answer these questions, let us consider only HI in other two experiments (5 and 6).
a general reversible reaction: Experiment 1, 2, 3 and 4 were performed
A+B C+D taking different concentrations of H2 and / or
where A and B are the reactants, C and D I2, and with time it was observed that intensity
are the products in the balanced chemical of the purple colour remained constant and
equation. On the basis of experimental studies equilibrium was attained. Similarly, for
of many reversible reactions, the Norwegian experiments 5 and 6, the equilibrium was
chemists Cato Maximillian Guldberg and attained from the opposite direction.
Peter Waage proposed in 1864 that the Data obtained from all six sets of
concentrations in an equilibrium mixture experiments are given in Table 6.2.
are related by the following equilibrium
equation, It is evident from the experiments 1, 2,
3 and 4 that number of moles of dihydrogen
Kc
CD (6.1) reacted = number of moles of iodine reacted
A B = ½ (number of moles of HI formed). Also,
(6.1) where Kc is the equilibrium constant and experiments 5 and 6 indicate that,
the expression on the right side is called the [H2(g)]eq = [I2(g)]eq
equilibrium constant expression.
The equilibrium equation is also known as Knowing the above facts, in order
the law of mass action because in the early to establish a relationship between
days of chemistry, concentration was called concentrations of the reactants and products,
“active mass”. In order to appreciate their several combinations can be tried. Let us
work better, let us consider reaction between consider the simple expression,
gaseous H2 and I2 carried out in a sealed vessel [HI(g)]eq / [H2(g)]eq [I2(g)]eq
at 731K.
H2(g) + I2(g) 2HI(g) It can be seen from Table 6.3 that if we
1 mol 1 mol 2 mol put the equilibrium concentrations of the
reactants and products, the above expression
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Table 6.3 Expression Involving the The equilibrium constant for a general
Equilibrium Concentration of reaction,
Reactants
aA + bB cC + dD
H2(g) + I2(g) 2HI(g)
is expressed as,
Kc = [C]c[D]d / [A]a[B]b (6.4)
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178 chemistry
Therefore,
n/V is concentration expressed in mol/m3 NH3 ( g ) [RT ]
2 −2
= = K c ( RT )
−2
If concentration c, is in mol/L or mol/dm3,
N 2 ( g ) H 2 ( g )
3
and p is in bar then
p = cRT,
or K p = K c ( RT ) (6.14)
−2
We can also write p = [gas]RT.
Here, R= 0.0831 bar litre/mol K Similarly, for a general reaction
At constant temperature, the pressure of aA + bB cC + dD
the gas is proportional to its concentration i.e.,
p ∝ [gas]
Kp =
( p )( p ) [C] [D] ( RT )(
C
c
=
d
D
c d c +d )
RT )
(c + d ) −(a +b )
b (
=
HI ( g )
2
[ A ] [B ]
a
Kc =
H2 ( g ) I2 ( g )
[ C ] [D]
c d
RT )
∆n
= K c ( RT )
∆n
b (
= (6.15)
or K c =
( p HI ) 2
(6.12)
[ A ] [B ]
a
( p )( p )
H2 I2
where ∆n = (number of moles of gaseous
products) – (number of moles of gaseous
Further, since p HI = HI ( g ) RT reactants) in the balanced chemical equation.
It is necessary that while calculating the value
pI2 = I2 ( g ) RT of Kp, pressure should be expressed in bar
p H2 = H2 ( g ) RT because standard state for pressure is 1 bar.
We know from Unit 1 that :
Therefore, 1pascal, Pa=1Nm–2, and 1bar = 105 Pa
HI ( g ) [RT ] Kp values for a few selected reactions at
( pHI )2
2 2
(p )
2
NH 3
Kp =
( p )( p )
3
N2 H2
Problem 6.3
NH3 ( g ) [RT ]
2 2
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Calculate Kc for the reaction, the value 0.194 should be neglected because
PCl5 PCl3 + Cl2 it will give concentration of the reactant
Solution which is more than initial concentration.
The equilibrium constant Kc for the above Hence the equilibrium concentrations are,
reaction can be written as, [CO2] = [H2-] = x = 0.067 M
Kc
PCl Cl 1.59
3 2
2
1.79
[CO] = [H2O] = 0.1 – 0.067 = 0.033 M
PCl 5 1.41 Problem 6.5
Problem 6.4 For the equilibrium,
The value of K c = 4.24 at 800K for the 2NOCl(g) 2NO(g) + Cl2(g)
reaction, the value of the equilibrium constant, Kc is
CO (g) + H2O (g) CO2 (g) + H2 (g) 3.75 × 10 –6 at 1069 K. Calculate the Kp for
Calculate equilibrium concentrations of CO2, the reaction at this temperature?
H2, CO and H2O at 800 K, if only CO and
H2O are present initially at concentrations Solution
of 0.10M each.
We know that,
Solution Kp = Kc(RT)∆n
For the reaction, For the above reaction,
CO (g) + H2O (g) CO2 (g) + H2 (g) ∆n = (2+1) – 2 = 1
Kp = 3.75 ×10–6 (0.0831 × 1069)
Initial concentration:
Kp = 0.033
0.1M 0.1M 0 0
Let x mole per litre of each of the product
be formed. 6.5 HETEROGENEOUS EQUILIBRIA
At equilibrium: Equilibrium in a system having more than one
(0.1-x) M (0.1-x) M xM xM phase is called heterogeneous equilibrium.
The equilibrium between water vapour and
where x is the amount of CO2 and H2 at
equilibrium. liquid water in a closed container is an
example of heterogeneous equilibrium.
Hence, equilibrium constant can be written
as, H2O(l) H2O(g)
Kc = x2/(0.1-x)2 = 4.24 In this example, there is a gas phase and
x2 = 4.24(0.01 + x2-0.2x) a liquid phase. In the same way, equilibrium
x2 = 0.0424 + 4.24x2-0.848x between a solid and its saturated solution,
3.24x2 – 0.848x + 0.0424 = 0 Ca(OH)2 (s) + (aq) Ca2+ (aq) + 2OH–(aq)
a = 3.24, b = – 0.848, c = 0.0424 is a heterogeneous equilibrium.
(for quadratic equation ax2 + bx + c = 0, Heterogeneous equilibria often involve
x
b b2 4ac pure solids or liquids. We can simplify
equilibrium expressions for the heterogeneous
2a equilibria involving a pure liquid or a pure
x = 0.848±√(0.848)2– 4(3.24)(0.0424)/ solid, as the molar concentration of a pure
solid or liquid is constant (i.e., independent
(3.24×2)
of the amount present). In other words if a
x = (0.848 ± 0.4118)/ 6.48
substance ‘X’ is involved, then [X(s)] and [X(l)]
x1 = (0.848 – 0.4118)/6.48 = 0.067 are constant, whatever the amount of ‘X’ is
x2 = (0.848 + 0.4118)/6.48 = 0.194 taken. Contrary to this, [X(g)] and [X(aq)] will
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(a) The decomposition of H2O into H2 and If Qc = Kc, the reaction mixture is already
O2 at 500 K has a very small equilibrium at equilibrium.
constant, Kc = 4.1 × 10 –48 Consider the gaseous reaction of H 2
(b) N2(g) + O2(g) 2NO(g), with I2,
at 298 K has Kc = 4.8 ×10 – 31. H2(g) + I2(g) 2HI(g); Kc = 57.0 at 700 K.
• If K c is in the range of 10 – 3 to 10 3 , Suppose we have molar concentrations
appreciable concentrations of both [H2]t=0.10M, [I2]t = 0.20 M and [HI]t = 0.40 M.
reactants and products are present. (the subscript t on the concentration symbols
Consider the following examples: means that the concentrations were measured
(a) For reaction of H2 with I2 to give HI, at some arbitrary time t, not necessarily at
equilibrium).
Kc = 57.0 at 700K.
Thus, the reaction quotient, Qc at this
(b) Also, gas phase decomposition of N2O4
stage of the reaction is given by,
to NO2 is another reaction with a value
Qc = [HI]t2 / [H2]t [I2]t = (0.40)2/ (0.10)×(0.20)
of K c = 4.64 × 10 –3 at 25°C which is
neither too small nor too large. Hence, = 8.0
equilibrium mixtures contain appreciable Now, in this case, Qc (8.0) does not equal
concentrations of both N2O4 and NO2. Kc (57.0), so the mixture of H2(g), I2(g) and HI(g)
These generarlisations are illustrated in is not at equilibrium; that is, more H2(g) and
Fig. 6.6 I2(g) will react to form more HI(g) and their
concentrations will decrease till Qc = Kc.
The reaction quotient, Q c is useful in
predicting the direction of reaction by
comparing the values of Qc and Kc.
Thus, we can make the following
generalisations concerning the direction of
Fig.6.6 Dependence of extent of reaction on Kc the reaction (Fig. 6.7) :
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2
concentrations into the equilibrium equation K p = p NO2 / p N 2O4
for the reaction and solve for x. If you are
= (8.34)2/0.81 = 85.87
to solve a quadratic equation choose the
mathematical solution that makes chemical Kp = Kc(RT)∆n
sense. 85.87 = Kc(0.083 × 400)1
Step 4. Calculate the equilibrium Kc = 2.586 = 2.6
concentrations from the calculated value of x.
Step 5. Check your results by substituting Problem 6.9
them into the equilibrium equation. 3.00 mol of PCl5 kept in 1L closed reaction
vessel was allowed to attain equilibrium
at 380K. Calculate composition of the
Problem 6.8 mixture at equilibrium. Kc= 1.80
13.8g of N2O4 was placed in a 1L reaction Solution
vessel at 400K and allowed to attain PCl5 PCl3 + Cl2
equilibrium Initial
N 2O4 (g) 2NO2 (g) concentration: 3.0 0 0
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reactants to products while minimising the “When the concentration of any of the
expenditure of energy. This implies maximum reactants or products in a reaction at
yield of products at mild temperature and equilibrium is changed, the composition
pressure conditions. If it does not happen, of the equilibrium mixture changes so as
then the experimental conditions need to be to minimize the effect of concentration
adjusted. For example, in the Haber process changes”.
for the synthesis of ammonia from N2 and Let us take the reaction,
H2, the choice of experimental conditions is
of real economic importance. Annual world H2(g) + I2(g) 2HI(g)
production of ammonia is about hundred If H2 is added to the reaction mixture
million tones, primarily for use as fertilisers. at equilibrium, then the equilibrium of the
Equilibrium constant, Kc is independent reaction is disturbed. In order to restore it,
of initial concentrations. But if a system at the reaction proceeds in a direction wherein
equilibrium is subjected to a change in the H2 is consumed, i.e., more of H2 and I2 react
concentration of one or more of the reacting to form HI and finally the equilibrium shifts
substances, then the system is no longer at in right (forward) direction (Fig.6.8). This is in
equilibrium; and net reaction takes place in accordance with the Le Chatelier’s principle
some direction until the system returns to which implies that in case of addition of a
equilibrium once again. Similarly, a change reactant/product, a new equilibrium will
in temperature or pressure of the system may be set up in which the concentration of the
also alter the equilibrium. In order to decide reactant/product should be less than what it
what course the reaction adopts and make was after the addition but more than what it
a qualitative prediction about the effect of a was in the original mixture.
change in conditions on equilibrium we use
Le Chatelier’s principle. It states that a
change in any of the factors that determine
the equilibrium conditions of a system
will cause the system to change in such a
manner so as to reduce or to counteract
the effect of the change. This is applicable
to all physical and chemical equilibria.
We shall now be discussing factors which
can influence the equilibrium.
6.8.1 Effect of Concentration Change
In general, when equilibrium is disturbed
by the addition/removal of any reactant/
products, Le Chatelier’s principle predicts
that:
• The concentration stress of an added
reactant/product is relieved by net
reaction in the direction that consumes Fig. 6.8 Effect of addition of H 2 on change
of concentration for the reactants
the added substance. and products in the reaction,
• The concentration stress of a removed H2(g) + I2 (g) 2HI(g)
reactant/product is relieved by net
reaction in the direction that replenishes The same point can be explained in terms
the removed substance. of the reaction quotient, Qc,
or in other words, Qc = [HI]2/ [H2][I2]
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partial pressure and the concentration are Production of ammonia according to the
doubled. We obtain the reaction quotient by reaction,
replacing each equilibrium concentration by N2(g) + 3H2(g) 2NH3(g);
double its value.
∆H= – 92.38 kJ mol–1
CH4 ( g ) H2O ( g )
Qc = is an exothermic process. According to
CO ( g ) H2 ( g )
3
Le Chatelier’s principle, raising the
temperature shifts the equilibrium to left
As Qc < Kc , the reaction proceeds in the and decreases the equilibrium concentration
forward direction. of ammonia. In other words, low temperature
In reaction C(s) + CO2(g) 2CO(g), when is favourable for high yield of ammonia, but
practically very low temperatures slow down
pressure is increased, the reaction goes in the
the reaction and thus a catalyst is used.
reverse direction because the number of moles
of gas increases in the forward direction. Effect of Temperature – An experiment
Effect of temperature on equilibrium can
6.8.3 Effect of Inert Gas Addition
be demonstrated by taking NO2 gas (brown
If the volume is kept constant and an inert gas in colour) which dimerises into N 2O 4 gas
such as argon is added which does not take (colourless).
part in the reaction, the equilibrium remains
2NO2(g) N2O4(g); ∆H = –57.2 kJ mol–1
undisturbed. It is because the addition of
an inert gas at constant volume does not NO 2 gas prepared by addition of Cu
change the partial pressures or the molar turnings to conc. HNO3 is collected in two
concentrations of the substance involved in 5 mL test tubes (ensuring same intensity
the reaction. The reaction quotient changes of colour of gas in each tube) and stopper
only if the added gas is a reactant or product sealed with araldite. Three 250 mL beakers
involved in the reaction. 1, 2 and 3 containing freesing mixture, water
at room temperature and hot water (363K),
6.8.4 Effect of Temperature Change respectively, are taken (Fig. 6.9). Both the test
Whenever an equilibrium is disturbed by tubes are placed in beaker 2 for 8-10 minutes.
a change in the concentration, pressure or After this one is placed in beaker 1 and the
volume, the composition of the equilibrium other in beaker 3. The effect of temperature
mixture changes because the reaction on direction of reaction is depicted very well
quotient, Qc no longer equals the equilibrium in this experiment. At low temperatures in
constant, Kc. However, when a change in beaker 1, the forward reaction of formation of
temperature occurs, the value of equilibrium N2O4 is preferred, as reaction is exothermic,
constant, Kc is changed. and thus, intensity of brown colour due
to NO2 decreases. While in beaker 3, high
In general, the temperature dependence temperature favours the reverse reaction of
of the equilibrium constant depends on the
sign of ∆H for the reaction.
• The equilibrium constant for an exothermic
reaction (negative ∆H) decreases as the
temperature increases.
• The equilibrium constant for an
endothermic reaction (positive ∆H)
increases as the temperature increases.
Temperature changes affect the Fig. 6.9 Effect of temperature on equilibrium for
equilibrium constant and rates of reactions. the reaction, 2NO2 (g) N2O4 (g)
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formation of NO2 and thus, the brown colour Similarly, in manufacture of sulphuric
intensifies. acid by contact process,
Effect of temperature can also be seen in 2SO2(g) + O2(g) 2SO3(g); Kc = 1.7 × 1026
an endothermic reaction, though the value of K is suggestive of reaction
[Co(H2O) 6]3+ (aq) + 4Cl –(aq) [CoCl4]2–(aq) + going to completion, but practically the
6H2O(l) oxidation of SO2 to SO3 is very slow. Thus,
pink colourless blue platinum or divanadium penta-oxide (V2O5)
is used as catalyst to increase the rate of the
At room temperature, the equilibrium
mixture is blue due to [CoCl4]2–. When cooled reaction.
in a freesing mixture, the colour of the mixture Note: If a reaction has an exceedingly small
turns pink due to [Co(H2O)6]3+. K, a catalyst would be of little help.
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Faraday was born near London into a family of very limited means. At the age of
14 he was an apprentice to a kind bookbinder who allowed Faraday to read the
books he was binding. Through a fortunate chance he became laboratory assistant
to Davy, and during 1813-4, Faraday accompanied him to the Continent. During
this trip he gained much from the experience of coming into contact with many of the
leading scientists of the time. In 1825, he succeeded Davy as Director of the Royal
Institution laboratories, and in 1833 he also became the first Fullerian Professor of
Chemistry. Faraday’s first important work was on analytical chemistry. After 1821
Michael Faraday
much of his work was on electricity and magnetism and different electromagnetic
(1791–1867)
phenomena. His ideas have led to the establishment of modern field theory.
He discovered his two laws of electrolysis in 1834. Faraday was a very modest and kind hearted
person. He declined all honours and avoided scientific controversies. He preferred to work alone and
never had any assistant. He disseminated science in a variety of ways including his Friday evening
discourses, which he founded at the Royal Institution. He has been very famous for his Christmas
lecture on the ‘Chemical History of a Candle’. He published nearly 450 scientific papers.
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Arrhenius was born near Uppsala, Sweden. He presented his thesis, on the
conductivities of electrolyte solutions, to the University of Uppsala in 1884. For the
next five years he travelled extensively and visited a number of research centers
in Europe. In 1895 he was appointed professor of physics at the newly formed
University of Stockholm, serving its rector from 1897 to 1902. From 1905 until his
death he was Director of physical chemistry at the Nobel Institute in Stockholm. He
continued to work for many years on electrolytic solutions. In 1899 he discussed
the temperature dependence of reaction rates on the basis of an equation, now
usually known as Arrhenius equation.
He worked in a variety of fields, and made important contributions to
Svante Arrhenius
immunochemistry, cosmology, the origin of life, and the causes of ice age. He was
(1859-1927)
the first to discuss the ‘green house effect’ calling by that name. He received Nobel
Prize in Chemistry in 1903 for his theory of electrolytic dissociation and its use in
the development of chemistry.
6.10.3 Lewis Acids and Bases (HClO4), hydrochloric acid (HCl), hydrobromic
G.N. Lewis in 1923 defined an acid as a acid (HBr), hyrdoiodic acid (HI), nitric acid
species which accepts electron pair and base (HNO3) and sulphuric acid (H2SO4) are termed
which donates an electron pair. As far as bases strong because they are almost completely
are concerned, there is not much difference dissociated into their constituent ions in an
between Brönsted-Lowry and Lewis concepts, aqueous medium, thereby acting as proton
as the base provides a lone pair in both the (H +) donors. Similarly, strong bases like
cases. However, in Lewis concept many lithium hydroxide (LiOH), sodium hydroxide
acids do not have proton. A typical example (NaOH), potassium hydroxide (KOH), caesium
is reaction of electron deficient species BF3 hydroxide (CsOH) and barium hydroxide
with NH3. Ba(OH)2 are almost completely dissociated
into ions in an aqueous medium giving
BF3 does not have a proton but still acts
hydroxyl ions, OH–. According to Arrhenius
as an acid and reacts with NH3 by accepting
concept they are strong acids and bases as
its lone pair of electrons. The reaction can be
they are able to completely dissociate and
represented by,
produce H3O+ and OH– ions respectively in
BF3 + :NH3 → BF3:NH3 the medium. Alternatively, the strength of an
Electron deficient species like AlCl3, Co3+, acid or base may also be gauged in terms of
Mg , etc. can act as Lewis acids while species
2+
Brönsted-Lowry concept of acids and bases,
like H2O, NH3, OH– etc. which can donate a wherein a strong acid means a good proton
pair of electrons, can act as Lewis bases. donor and a strong base implies a good proton
acceptor. Consider, the acid-base dissociation
Problem 6.15 equilibrium of a weak acid HA,
Classify the following species into Lewis HA(aq) + H2O(l) H3O+(aq) + A–(aq)
acids and Lewis bases and show how these conjugate conjugate
act as such: acid base acid base
(a) HO – (b) F – (c) H+ (d) BCl3 In section 6.10.2 we saw that acid (or
Solution base) dissociation equilibrium is dynamic
involving a transfer of proton in forward and
(a) Hydroxyl ion is a Lewis base as it can reverse directions. Now, the question arises
donate an electron lone pair (:OH– ). that if the equilibrium is dynamic then with
(b) Flouride ion acts as a Lewis base passage of time which direction is favoured?
as it can donate any one of its four What is the driving force behind it? In order
electron lone pairs. to answer these questions we shall deal
(c) A proton is a Lewis acid as it can into the issue of comparing the strengths
accept a lone pair of electrons from of the two acids (or bases) involved in the
bases like hydroxyl ion and fluoride dissociation equilibrium. Consider the two
ion. acids HA and H 3O + present in the above
(d) BCl3 acts as a Lewis acid as it can mentioned acid-dissociation equilibrium.
accept a lone pair of electrons from We have to see which amongst them is a
species like ammonia or amine stronger proton donor. Whichever exceeds
molecules. in its tendency of donating a proton over the
other shall be termed as the stronger acid
6.11 IONIZATION OF ACIDS AND BASES and the equilibrium will shift in the direction
of weaker acid. Say, if HA is a stronger acid
Arrhenius concept of acids and bases
than H3O+, then HA will donate protons and
becomes useful in case of ionization of acids
not H3O+, and the solution will mainly contain
and bases as mostly ionizations in chemical
A– and H3O+ ions. The equilibrium moves in
and biological systems occur in aqueous
the direction of formation of weaker acid
medium. Strong acids like perchloric acid
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and weaker base because the stronger acid H2O(l) + H2O(l) H3O+(aq) + OH–(aq)
donates a proton to the stronger base. acid base conjugate conjugate
It follows that as a strong acid dissociates acid base
completely in water, the resulting base formed The dissociation constant is represented by,
would be very weak i.e., strong acids have K = [H3O+] [OH–] / [H2O] (6.26)
very weak conjugate bases. Strong acids
like perchloric acid (HClO4), hydrochloric acid The concentration of water is omitted from
(HCl), hydrobromic acid (HBr), hydroiodic acid the denominator as water is a pure liquid and
(HI), nitric acid (HNO3) and sulphuric acid its concentration remains constant. [H2O] is
(H2SO4) will give conjugate base ions ClO4–, Cl, incorporated within the equilibrium constant
Br–, I–, NO3– and HSO4– , which are much weaker to give a new constant, Kw, which is called the
bases than H2O. Similarly a very strong base ionic product of water.
would give a very weak conjugate acid. On the Kw = [H+][OH–] (6.27)
other hand, a weak acid say HA is only partially
The concentration of H has been found
+
dissociated in aqueous medium and thus, the
out experimentally as 1.0 × 10–7 M at 298 K.
solution mainly contains undissociated HA
And, as dissociation of water produces equal
molecules. Typical weak acids are nitrous
number of H+ and OH– ions, the concentration
acid (HNO2), hydrofluoric acid (HF) and acetic
of hydroxyl ions, [OH–] = [H+] = 1.0 × 10–7 M.
acid (CH3COOH). It should be noted that the
weak acids have very strong conjugate bases. Thus, the value of Kw at 298K,
For example, NH2–, O 2– and H – are very good Kw = [H3O+][OH–] = (1 × 10–7)2 = 1 × 10–14 M2
proton acceptors and thus, much stronger (6.28)
bases than H2O.
The value of Kw is temperature dependent
Certain water soluble organic compounds as it is an equilibrium constant.
like phenolphthalein and bromothymol blue
The density of pure water is 1000 g / L
behave as weak acids and exhibit different
and its molar mass is 18.0 g /mol. From this
colours in their acid (HIn) and conjugate base
the molarity of pure water can be given as,
(In– ) forms.
[H2O] = (1000 g /L)(1 mol/18.0 g) = 55.55 M.
HIn(aq) + H2O(l) H3O+(aq) + In–(aq)
Therefore, the ratio of dissociated water to
acid conjugate conjugate
that of undissociated water can be given as:
indicator acid base
10 –7 / (55.55) = 1.8 × 10–9 or ~ 2 in 10–9 (thus,
colour A colour B equilibrium lies mainly towards undissociated
Such compounds are useful as indicators water)
in acid-base titrations, and finding out H+ ion
concentration. We can distinguish acidic, neutral and
basic aqueous solutions by the relative values
6.11.1 The Ionization Constant of Water of the H3O+ and OH– concentrations:
and its Ionic Product
Acidic: [H3O+] > [OH– ]
Some substances like water are unique in
their ability of acting both as an acid and a Neutral: [H3O+] = [OH– ]
base. We have seen this in case of water in Basic : [H3O+] < [OH–]
section 6.10.2. In presence of an acid, HA it
accepts a proton and acts as the base while 6.11.2 The pH Scale
in the presence of a base, B– it acts as an Hydronium ion concentration in molarity is
acid by donating a proton. In pure water, one more conveniently expressed on a logarithmic
H2O molecule donates proton and acts as an scale known as the pH scale. The pH of a
acid and another water molecules accepts a solution is defined as the negative logarithm
proton and acts as a base at the same time.
The following equilibrium exists:
to base 10 of the activity a H of hydrogen
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ion. In dilute solutions (< 0.01 M), activity when the hydrogen ion concentration, [H+]
of hydrogen ion (H+) is equal in magnitude changes by a factor of 100, the value of pH
to molarity represented by [H+]. It should changes by 2 units. Now you can realise why
be noted that activity has no units and is the change in pH with temperature is often
defined as: ignored.
= [H+] / mol L–1 Measurement of pH of a solution is very
From the definition of pH, the following essential as its value should be known
when dealing with biological and cosmetic
can be written,
applications. The pH of a solution can be
pH = – log aH+ = – log {[H+] / mol L–1} found roughly with the help of pH paper that
Thus, an acidic solution of HCl (10–2 M) has different colour in solutions of different
will have a pH = 2. Similarly, a basic solution pH. Now-a-days pH paper is available with
of NaOH having [OH–] =10–4 M and [H3O+] = four strips on it. The different strips have
10–10 M will have a pH = 10. At 25 °C, pure different colours (Fig. 6.11) at the same pH.
water has a concentration of hydrogen ions, The pH in the range of 1-14 can be determined
[H + ] = 10–7 M. Hence, the pH of pure water is with an accuracy of ~0.5 using pH paper.
given as:
pH = –log(10–7) = 7
Acidic solutions possess a concentration
of hydrogen ions, [H + ] > 10–7 M, while basic
solutions possess a concentration of hydrogen
ions, [H+] < 10–7 M. thus, we can summarise
that
Fig.6.11 pH-paper with four strips that may have
Acidic solution has pH < 7 different colours at the same pH
Basic solution has pH > 7
Neutral solution has pH = 7 For greater accuracy pH meters are used.
pH meter is a device that measures the
Now again, consider the equation (6.28)
pH-dependent electrical potential of the test
at 298 K
solution within 0.001 precision. pH meters
Kw = [H3O+] [OH–] = 10–14
of the size of a writing pen are now available
Taking negative logarithm on both sides in the market. The pH of some very common
of equation, we obtain substances are given in Table 6.5 (page 195).
–log Kw = – log {[H3O+] [OH–]}
Problem 6.16
= – log [H3O+] – log [OH–]
The concentration of hydrogen ion in a
= – log 10 –14
sample of soft drink is 3.8 × 10–3M. what
pKw = pH + pOH = 14 (6.29) is its pH ?
Note that although K w may change
with temperature the variations in pH with Solution
temperature are so small that we often pH = – log[3.8 × 10–3]
ignore it. = – {log[3.8] + log[10–3]}
pK w is a very important quantity for = – {(0.58) + (– 3.0)} = – { – 2.42} = 2.42
aqueous solutions and controls the relative Therefore, the pH of the soft drink is 2.42
concentrations of hydrogen and hydroxyl and it can be inferred that it is acidic.
ions as their product is a constant. It should
Problem 6.17
be noted that as the pH scale is logarithmic,
a change in pH by just one unit also means Calculate pH of a 1.0 × 10 –8 M solution of
change in [H+] by a factor of 10. Similarly, HCl.
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Kb = [NH2NH3+][OH–] / [NH2NH2]
Net: 2 H2O(l) H3O+(aq) + OH –(aq)
= (5.98 × 10–5)2 / 0.004 = 8.96 × 10–7
Kw = [H3O+][ OH– ] = 1.0 × 10–14 M
pKb = –logKb = –log(8.96 × 10–7) = 6.04.
Where, Ka represents the strength of NH4+
Problem 6.22 as an acid and Kb represents the strength of
Calculate the pH of the solution in which NH3 as a base.
0.2M NH4Cl and 0.1M NH3 are present. The It can be seen from the net reaction that
pKb of ammonia solution is 4.75. the equilibrium constant is equal to the
product of equilibrium constants Ka and Kb
Solution
for the reactions added. Thus,
NH3 + H2O NH4+ + OH– Ka × K b = {[H3O+][ NH3] / [NH4+ ]} × {[NH4+]
The ionization constant of NH3, [OH–] / [NH3]}
Kb = antilog (–pKb) i.e. = [H3O+][OH–] = Kw
= (5.6 ×10–10) × (1.8 × 10–5) = 1.0 × 10–14 M
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chloride solution of same molar concentration. We shall now consider the equilibrium
For a buffer solution formed by ammonium between the sparingly soluble ionic salt and
chloride and ammonium hydroxide, equation its saturated aqueous solution.
(6.42) becomes:
6.13.1 Solubility Product Constant
[Conjugate acid,BH+ ]
pH = 9.25 + log Let us now have a solid like barium sulphate
[Base,B] in contact with its saturated aqueous solution.
pH of the buffer solution is not affected by The equilibrium between the undisolved solid
dilution because ratio under the logarithmic and the ions in a saturated solution can be
term remains unchanged. represented by the equation:
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p q
A solid salt of the general formula M x X y Table 6.9 The Solubility Product Constants,
with molar solubility S in equilibrium with Ksp of Some Common Ionic Salts at
its saturated solution may be represented by 298K.
the equation:
MxXy(s) xMp+(aq) + yXq– (aq)
(where x × p = y × q–)
+
Problem 6.26
Calculate the solubility of A2 X3 in pure
water, assuming that neither kind of ion
reacts with water. The solubility product of
A2X3, Ksp = 1.1 × 10–23.
Solution
A2X3 → 2A3+ + 3X2–
Ksp = [A3+]2 [X2–]3 = 1.1 × 10–23
If S = solubility of A2X3, then
[A3+] = 2S; [X2–] = 3S
therefore, Ksp = (2S)2(3S)3 = 108S5
= 1.1 × 10–23
thus, S5 = 1 × 10–25
S = 1.0 × 10–5 mol/L.
Problem 6.27
The values of Ksp of two sparingly soluble
salts Ni(OH)2 and AgCN are 2.0 × 10–15 and
6 × 0–17 respectively. Which salt is more
soluble? Explain.
Solution
AgCN Ag+ + CN–
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SUMMARY
When the number of molecules leaving the liquid to vapour equals the number of molecules
returning to the liquid from vapour, equilibrium is said to be attained and is dynamic in
nature. Equilibrium can be established for both physical and chemical processes and at
this stage rate of forward and reverse reactions are equal. Equilibrium constant, Kc is
expressed as the concentration of products divided by reactants, each term raised to the
stoichiometric coefficient.
For reaction, a A + b B c C +d D
Kc = [C]c[D]d/[A]a[B]b
Equilibrium constant has constant value at a fixed temperature and at this stage all the
macroscopic properties such as concentration, pressure, etc. become constant. For a gaseous
reaction equilibrium constant is expressed as Kp and is written by replacing concentration
terms by partial pressures in Kc expression. The direction of reaction can be predicted by
reaction quotient Qc which is equal to Kc at equilibrium. Le Chatelier’s principle states that
the change in any factor such as temperature, pressure, concentration, etc. will cause the
equilibrium to shift in such a direction so as to reduce or counteract the effect of the change.
It can be used to study the effect of various factors such as temperature, concentration,
pressure, catalyst and inert gases on the direction of equilibrium and to control the yield of
products by controlling these factors. Catalyst does not effect the equilibrium composition
of a reaction mixture but increases the rate of chemical reaction by making available a new
lower energy pathway for conversion of reactants to products and vice-versa.
All substances that conduct electricity in aqueous solutions are called electrolytes. Acids,
bases and salts are electrolytes and the conduction of electricity by their aqueous solutions
is due to anions and cations produced by the dissociation or ionization of electrolytes
in aqueous solution. The strong electrolytes are completely dissociated. In weak electrolytes
there is equilibrium between the ions and the unionized electrolyte molecules. According to
Arrhenius, acids give hydrogen ions while bases produce hydroxyl ions in their aqueous
solutions. Brönsted-Lowry on the other hand, defined an acid as a proton donor and a base as
a proton acceptor. When a Brönsted-Lowry acid reacts with a base, it produces its conjugate
base and a conjugate acid corresponding to the base with which it reacts. Thus a conjugate
pair of acid-base differs only by one proton. Lewis further generalised the definition of an
acid as an electron pair acceptor and a base as an electron pair donor. The expressions
for ionization (equilibrium) constants of weak acids (Ka) and weak bases (Kb) are developed
using Arrhenius definition. The degree of ionization and its dependence on concentration and
common ion are discussed. The pH scale (pH = –log[H+]) for the hydrogen ion concentration
(activity) has been introduced and extended to other quantities (pOH = – log[OH–]); pKa = –log[Ka];
pKb = –log[Kb]; and pKw = –log[Kw] etc.). The ionization of water has been considered and we
note that the equation: pH + pOH = pKw is always satisfied. The salts of strong acid and
weak base, weak acid and strong base, and weak acid and weak base undergo hydrolysis in
aqueous solution. The definition of buffer solutions, and their importance are discussed
briefly. The solubility equilibrium of sparingly soluble salts is discussed and the equilibrium
constant is introduced as solubility product constant (Ksp). Its relationship with solubility
of the salt is established. The conditions of precipitation of the salt from their solutions
or their dissolution in water are worked out. The role of common ion and the solubility of
sparingly soluble salts is also discussed.
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EXERCISES
6.1 A liquid is in equilibrium with its vapour in a sealed container at a fixed temperature.
The volume of the container is suddenly increased.
c) What happens when equilibrium is restored finally and what will be the final vapour
pressure?
6.2 What is Kc for the following equilibrium when the equilibrium concentration of each
substance is: [SO2]= 0.60M, [O2] = 0.82M and [SO3] = 1.90M ?
I2 (g) 2I (g)
Calculate Kp for the equilibrium.
6.4 Write the expression for the equilibrium constant, Kc for each of the following reactions:
(i) 2NOCl (g) 2NO (g) + Cl2 (g); Kp= 1.8 × 10–2 at 500 K
(ii) CaCO3 (s) CaO(s) + CO2(g); Kp= 167 at 1073 K
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6.9 Nitric oxide reacts with Br2 and gives nitrosyl bromide as per reaction given below:
2NO (g) + Br2 (g) 2NOBr (g)
When 0.087 mol of NO and 0.0437 mol of Br2 are mixed in a closed container at
constant temperature, 0.0518 mol of NOBr is obtained at equilibrium. Calculate
equilibrium amount of NO and Br2 .
6.10 At 450K, Kp= 2.0 × 1010/bar for the given reaction at equilibrium.
2SO2(g) + O2(g) 2SO3 (g)
What is Kc at this temperature ?
6.11 A sample of HI(g) is placed in flask at a pressure of 0.2 atm. At equilibrium the partial
pressure of HI(g) is 0.04 atm. What is Kp for the given equilibrium ?
2HI (g) H2 (g) + I2 (g)
6.12 A mixture of 1.57 mol of N2, 1.92 mol of H2 and 8.13 mol of NH3 is introduced into
a 20 L reaction vessel at 500 K. At this temperature, the equilibrium constant, Kc
for the reaction N2 (g) + 3H2 (g) 2NH3 (g) is 1.7 × 102. Is the reaction mixture at
equilibrium? If not, what is the direction of the net reaction?
NH3 O2 5
4
Kc
NO4 H2O
6
6.14 One mole of H2O and one mole of CO are taken in 10 L vessel and heated to
725 K. At equilibrium 40% of water (by mass) reacts with CO according to the equation,
H2O (g) + CO (g) H2 (g) + CO2 (g)
Calculate the equilibrium constant for the reaction.
concentration of H2(g) and I2(g) assuming that we initially started with HI(g) and
allowed it to reach equilibrium at 700K?
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6.16 What is the equilibrium concentration of each of the substances in the equilibrium
when the initial concentration of ICl was 0.78 M ?
2ICl (g) I2 (g) + Cl2 (g); Kc = 0.14
6.17 Kp = 0.04 atm at 899 K for the equilibrium shown below. What is the equilibrium
concentration of C2H6 when it is placed in a flask at 4.0 atm pressure and allowed
to come to equilibrium?
C2H6 (g) C2H4 (g) + H2 (g)
6.18 Ethyl acetate is formed by the reaction between ethanol and acetic acid and the
equilibrium is represented as:
CH3COOH (l) + C2H5OH (l) CH3COOC2H5 (l) + H2O (l)
(i) Write the concentration ratio (reaction quotient), Qc, for this reaction (note: water
is not in excess and is not a solvent in this reaction)
(ii) At 293 K, if one starts with 1.00 mol of acetic acid and 0.18 mol of ethanol, there
is 0.171 mol of ethyl acetate in the final equilibrium mixture. Calculate the
equilibrium constant.
(iii) Starting with 0.5 mol of ethanol and 1.0 mol of acetic acid and maintaining it at
293 K, 0.214 mol of ethyl acetate is found after sometime. Has equilibrium been
reached?
6.19 A sample of pure PCl 5 was introduced into an evacuated vessel at 473
K. After equilibrium was attained, concentration of PCl 5 was found to be
0.5 × 10–1 mol L–1. If value of Kc is 8.3 × 10–3, what are the concentrations of PCl3 and
Cl2 at equilibrium?
PCl5 (g) PCl3 (g) + Cl2(g)
6.20 One of the reaction that takes place in producing steel from iron ore is the reduction
of iron(II) oxide by carbon monoxide to give iron metal and CO2.
FeO (s) + CO (g) Fe (s) + CO2 (g); Kp = 0.265 atm at 1050K
What are the equilibrium partial pressures of CO and CO2 at 1050 K if the initial
partial pressures are: pCO= 1.4 atm and = 0.80 atm?
At a particular time, the analysis shows that composition of the reaction mixture is
3.0 mol L–1 N2, 2.0 mol L–1 H2 and 0.5 mol L–1 NH3. Is the reaction at equilibrium? If
not in which direction does the reaction tend to proceed to reach equilibrium?
6.22 Bromine monochloride, BrCl decomposes into bromine and chlorine and reaches the
equilibrium:
2BrCl (g) Br2 (g) + Cl2 (g)
6.23 At 1127 K and 1 atm pressure, a gaseous mixture of CO and CO2 in equilibrium with
soild carbon has 90.55% CO by mass
C (s) + CO2 (g) 2CO (g)
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6.24 Calculate a) ∆G and b) the equilibrium constant for the formation of NO2 from NO
and O2 at 298K
NO (g) + ½ O2 (g) NO2 (g)
where
∆fG (NO2) = 52.0 kJ/mol
∆fG (NO) = 87.0 kJ/mol
∆fG (O2) = 0 kJ/mol
6.25 Does the number of moles of reaction products increase, decrease or remain same
when each of the following equilibria is subjected to a decrease in pressure by
increasing the volume?
(a) PCl5 (g) PCl3 (g) + Cl2 (g)
(b) CaO (s) + CO2 (g) CaCO3 (s)
(c) 3Fe (s) + 4H2O (g) Fe3O4 (s) + 4H2 (g)
6.26 Which of the following reactions will get affected by increasing the pressure?
Also, mention whether change will cause the reaction to go into forward or
backward direction.
(i) COCl2 (g) CO (g) + Cl2 (g)
(ii) CH4 (g) + 2S2 (g) CS2 (g) + 2H2S (g)
(iii) CO2 (g) + C (s) 2CO (g)
(iv) 2H2 (g) + CO (g) CH3OH (g)
(v) CaCO3 (s) CaO (s) + CO2 (g)
(vi) 4 NH3 (g) + 5O2 (g) 4NO (g) + 6H2O(g)
6.27 The equilibrium constant for the following reaction is 1.6 ×105 at 1024K
H2(g) + Br2(g) 2HBr(g)
Find the equilibrium pressure of all gases if 10.0 bar of HBr is introduced into a
sealed container at 1024K.
6.28 Dihydrogen gas is obtained from natural gas by partial oxidation with steam as per
following endothermic reaction:
CH4 (g) + H2O (g) CO (g) + 3H2 (g)
(a) Write as expression for Kp for the above reaction.
(b) How will the values of Kp and composition of equilibrium mixture be
affected by
(i) increasing the pressure
(ii) increasing the temperature
(iii) using a catalyst?
6.29 Describe the effect of:
a) addition of H2
b) addition of CH3OH
c) removal of CO
d) removal of CH3OH
on the equilibrium of the reaction:
2H2(g) + CO (g) CH3OH (g)
6.30 At 473 K, equilibrium constant Kc for decomposition of phosphorus pentachloride,
PCl5 is 8.3 ×10-3. If decomposition is depicted as,
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6.44 The ionization constant of phenol is 1.0 × 10–10. What is the concentration of phenolate
ion in 0.05 M solution of phenol? What will be its degree of ionization if the solution
is also 0.01M in sodium phenolate?
6.45 The first ionization constant of H2S is 9.1 × 10–8. Calculate the concentration
of HS– ion in its 0.1M solution. How will this concentration be affected if the
solution is 0.1M in HCl also? If the second dissociation constant of H 2S is
1.2 × 10–13, calculate the concentration of S2– under both conditions.
6.46 The ionization constant of acetic acid is 1.74 × 10–5. Calculate the degree of
dissociation of acetic acid in its 0.05 M solution. Calculate the concentration of
acetate ion in the solution and its pH.
6.47 It has been found that the pH of a 0.01M solution of an organic acid is 4.15. Calculate
the concentration of the anion, the ionization constant of the acid and its pKa.
6.48 Assuming complete dissociation, calculate the pH of the following solutions:
(a) 0.003 M HCl (b) 0.005 M NaOH (c) 0.002 M HBr (d) 0.002 M KOH
6.49 Calculate the pH of the following solutions:
a) 2 g of TlOH dissolved in water to give 2 litre of solution.
b) 0.3 g of Ca(OH)2 dissolved in water to give 500 mL of solution.
c) 0.3 g of NaOH dissolved in water to give 200 mL of solution.
d) 1mL of 13.6 M HCl is diluted with water to give 1 litre of solution.
6.50 The degree of ionization of a 0.1M bromoacetic acid solution is 0.132. Calculate the
pH of the solution and the pKa of bromoacetic acid.
6.51 The pH of 0.005M codeine (C18H21NO3) solution is 9.95. Calculate its ionization
constant and pKb.
6.52 What is the pH of 0.001M aniline solution? The ionization constant of aniline
can be taken from Table 6.7. Calculate the degree of ionization of aniline in the
solution. Also calculate the ionization constant of the conjugate acid of aniline.
6.53 Calculate the degree of ionization of 0.05M acetic acid if its pKa value is 4.74.
How is the degree of dissociation affected when its solution also contains
(a) 0.01M (b) 0.1M in HCl ?
6.54 The ionization constant of dimethylamine is 5.4 × 10–4. Calculate its degree of
ionization in its 0.02M solution. What percentage of dimethylamine is ionized if the
solution is also 0.1M in NaOH?
6.55 Calculate the hydrogen ion concentration in the following biological fluids whose
pH are given below:
(a) Human muscle-fluid, 6.83 (b) Human stomach fluid, 1.2
(c) Human blood, 7.38 (d) Human saliva, 6.4.
6.56 The pH of milk, black coffee, tomato juice, lemon juice and egg white are 6.8, 5.0,
4.2, 2.2 and 7.8 respectively. Calculate corresponding hydrogen ion concentration
in each.
6.57 If 0.561 g of KOH is dissolved in water to give 200 mL of solution at 298 K. Calculate
the concentrations of potassium, hydrogen and hydroxyl ions. What is its pH?
6.58 The solubility of Sr(OH)2 at 298 K is 19.23 g/L of solution. Calculate the concentrations
of strontium and hydroxyl ions and the pH of the solution.
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6.59 The ionization constant of propanoic acid is 1.32 × 10–5. Calculate the degree of
ionization of the acid in its 0.05M solution and also its pH. What will be its degree
of ionization if the solution is 0.01M in HCl also?
6.60 The pH of 0.1M solution of cyanic acid (HCNO) is 2.34. Calculate the ionization
constant of the acid and its degree of ionization in the solution.
6.61 The ionization constant of nitrous acid is 4.5 × 10–4. Calculate the pH of 0.04 M
sodium nitrite solution and also its degree of hydrolysis.
6.62 A 0.02M solution of pyridinium hydrochloride has pH = 3.44. Calculate the ionization
constant of pyridine.
6.63 Predict if the solutions of the following salts are neutral, acidic or basic:
NaCl, KBr, NaCN, NH4NO3, NaNO2 and KF
6.64 The ionization constant of chloroacetic acid is 1.35 × 10–3. What will be the pH of
0.1M acid and its 0.1M sodium salt solution?
6.65 Ionic product of water at 310 K is 2.7 × 10–14. What is the pH of neutral water at
this temperature?
6.66 Calculate the pH of the resultant mixtures:
a) 10 mL of 0.2M Ca(OH)2 + 25 mL of 0.1M HCl
b) 10 mL of 0.01M H2SO4 + 10 mL of 0.01M Ca(OH)2
c) 10 mL of 0.1M H2SO4 + 10 mL of 0.1M KOH
6.67 Determine the solubilities of silver chromate, barium chromate, ferric hydroxide,
lead chloride and mercurous iodide at 298K from their solubility product constants
given in Table 6.9. Determine also the molarities of individual ions.
6.68 The solubility product constant of Ag 2CrO 4 and AgBr are 1.1 × 10 –12 and
5.0 × 10–13 respectively. Calculate the ratio of the molarities of their saturated
solutions.
6.69 Equal volumes of 0.002 M solutions of sodium iodate and cupric chlorate are
mixed together. Will it lead to precipitation of copper iodate? (For cupric iodate
Ksp = 7.4 × 10–8 ).
6.70 The ionization constant of benzoic acid is 6.46 × 10–5 and Ksp for silver benzoate is
2.5 × 10–13. How many times is silver benzoate more soluble in a buffer of pH 3.19
compared to its solubility in pure water?
6.71 What is the maximum concentration of equimolar solutions of ferrous sulphate and
sodium sulphide so that when mixed in equal volumes, there is no precipitation of
iron sulphide? (For iron sulphide, Ksp = 6.3 × 10–18).
6.72 What is the minimum volume of water required to dissolve 1g of calcium sulphate
at 298 K? (For calcium sulphate, Ksp is 9.1 × 10–6).
6.73 The concentration of sulphide ion in 0.1M HCl solution saturated with hydrogen
sulphide is 1.0 × 10–19 M. If 10 mL of this is added to 5 mL of 0.04 M solution of the
following: FeSO4, MnCl2, ZnCl2 and CdCl2. in which of these solutions precipitation
will take place?
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