CHAPTER Thermodynamics and

6 Chemical Energetics

Chapter Outline
■ Thermodynamics ■ Thermodynamic Process ■ Thermodynamic Equilibrium ■ Heat ■ Work ■ Internal Energy
■ First Law of Thermodynamics or Law of Conservation of Energy ■ Second Law of Thermodynamics ■ Entropy
■ Zeroth Law of Thermodynamics ■ Third Law of Thermodyanmics ■ Gibbs Free Energy (G) ■ Thermochemistry
■ Heat or Enthalpy of Reaction ■ Sources of Energy ■ Conservation of Energy

Thermodynamics Heterogenous It is non-uniform as it consists of two or

more phases. For example, ice and water, solid in contact
Thermodynamics is a branch of science which deals with with a liquid.
the quantitative relationships between different forms of Systems are further divided into three parts:
energy; the study of interconversion of heat and work. Open system In such a system, both matter and energy can
Main Objectives be exchanged with the surroundings. For example, a beaker
containing boiling water, lime kiln, ice in an open beaker.
• To decide the feasibility of a given transfromation.
• To derive various energy changes and their inter relations. Closed system Such a system exchanges energy with its
surroundings. For example, heating of liquid in a sealed tube
• To derive laws like Phase rule, Law of mass action.
or ice in a closed beaker.
• Presentations of experimental data in a correct manner.
Isolated system In such a system, there is no exchange of
Limitations matter or energy with the surroundings. For example, liquid
• It is not applicable when a substance is present in a small in a sealed thermos flask or ice in a thermos flask.
amount. Properties of a System or State Variables
• It gives no explanation about the rate of reaction.
• It gives no explanation of system far from equation. State variables or functions
• It does not deal with internal structure of atoms and mol- • The state of a system is fixed by its macroscopic proper-
ecules. ties. If any of its macroscopic property is changed the
state of a system also changes. These properties are there-
Terms Related to Thermodynamics fore referred to as state variables.
Surrounding It consists of the region excluding the • The state variables determine the state of a system. These
system. are fundamental properties or thermodynamic parameters.
These depend only upon the initial and final states.
System It is the region or space to be investigated or the Pressure, temperature, volume, mass and composition
Region at which study of pressure, temperature etc. are to be are important state variables. Some otherstate variables
made. Systems are of two types: being enthalpy, free energy, internal energy and entropy.
Homogenous It is uniform all over, that is, made up of one These are of the following two types, viz., intensive and
phase only. For example, pure liquid or pure solid or pure gas. extensive properties.
6.2 ■ Chapter 6

Intensive properties Such properties remain same on • It is achieved by insulating the system or in closed and
any division in system, that is, they do not depend upon insulated containers (thermos).
amount of substance present in the system. For example, Cyclic process Here the system undergoes a series of
temperature, pressure, concentration, density, viscosity, sur- changes but finally comes back to the initial state.
face tension, specific heat, refractive index, pH, EMF of a dry
cell, vapour pressure, dipole moment. • ΔE = 0, ΔH = 0.

Extensive properties These properties depend on the Reversible or Quasi-static Process

amount of substance, that is, their values are different in • It is carried out in such a way that the system remains in
the divided system than in the entire system. For exam- a state of equilibrium.
ple, mass, volume, energy, work, internal energy, entropy,
• All changes occurring at any particular stage of the pro-
en­thalpy, heat capacity, length.
cess will be exactly reversed when change is carried out
• An extensive property can be made intensive by spec­ in the opposite direction.
ifying it in unit amount of matter. (By dividing two
• It involves slow changes during operation.
extensive properties only) For example,
• This process may occur in any direction.
Mass
Density = • It gives rise to maximum work.
Volume
• Here driving force and opposing force differ from each
Thermodynamic Process other by a small value.

Thermodynamic process is the path along which a change Irreversible Process

of state occurs. • Here direction of change can not be reversed by small
changes in variables. All processes occurring naturally
Types of Processes are irreversible.
Isobaric • It involves fast changes during operation.
• It is a unidirectional process.
Pressure
Isothermal • It gives rise to network.
Adiabatic Wrev > Wirr
Isochoric
Volume
• Here, driving and opposing forces differ by a large amount.

Figure 6.1 Different types of Processes Thermodynamic Equilibrium

Isothermal process Here temperature is kept constant, Thermodynamic equilibrium is of three types, namely, me-
that is, ΔT = 0, ΔE = 0. chanical, thermal and chemical equilibriums.
• It is achieved by using a thermostatic control.
Mechanical equilibrium There is no flow of matter
• Heat can be absorbed or evolved here, that is, it can be
from one part to another, which means that pressure is con-
exchanged with the surroundings. For example, freezing,
stant.
melting, evaporation, condensation.
Isobaric process Here pressure is kept constant, that is, Thermal equilibrium There is no flow of heat from
ΔP = 0. one part to another, that is, temperature is constant.
Example: Expansion of a gas in an open system. Chemical equilibrium There is no change in composi­
• Vaporization and heating of water up to its boiling point tion of any part of the system with time.
occurs at the same atmospheric pressure.
Isochoric process Here volume is kept constant, that is, Heat
ΔV = 0. • Heat is the energy transfer due to difference in tem-
For example, heating of a substance in a closed vessel (sys- perature.
tem) or in a non-expanding chamber. • Heat is a form of energy which the system can ex-change
Adiabatic process Here no exchange of heat takes place with the surroundings, if they are at different temperatures;
between the system and the surroundings. Q = 0. heat flows from higher temperature to lower temperature.
 Thermodynamics and Chemical Energetics ■ 6.3

• Heat is expressed as Q. • It is the total energy of a substance depending upon its

Heat absorbed by the system = Q positive chemical nature, temperature, pressure, and volume,
amount of substrate. It does not depend upon path by
Heat evolved by the system = Q negative
which the final state is achieved.
Work E = Et+Er+Ev+Ee+En+EPE + EB
Et = Transitional energy
Amount of energy transferred by a force. It is the energy Er = Rotational energy
transfer due to difference in pressure, that is, mode of
Ev = Vibrational energy
energy transfer.
W = Intensity factor × Capacity factor Ee = Electrical energy
It is of following types: En = Nuclear energy
EPE = Potential energy
1. Mechanical Work = Force × Displacement
EB = Bond energy
2. Electrical Work = Potential difference × Charge flow
• The exact measurement of interal energy is not possi-
V × Q = EnF ble so it is determined as ΔE, that is, change in internal
energy is measured as:
3. Expansion Work = P × ΔV = –Pex.(V2–V1)
ΔE = ∑Ep – ∑ER
P = External pressure
ΔV = Increase or decrease in volume • It is an extensive property.
• Internal energy is a state property.
4. Gravitational Work = mgh
• The change in the internal energy does not depend on the
Here m = Mass of body path by which the final state is reached.
g = Acceleration due to gravity • For a cyclic process, ΔE is zero (E = state function)
h = Height moved EαT
Unit of work is dyne cm or erg (CGS) or newton metre or
• At constant volume (Isochoric) Qv = ΔE
joule (SI).
• In adiabatic expansion, the gas cools as ΔE decreases.
Facts to Remember • For exothermic process, ΔE is negative as ER > Ep
• If the gas expands, [V2 > V1] then work is done by • For endothermic process, ΔE is positive as ER < Ep
the system and W is negative. • Internal energy for an ideal gas is a function of tempera-
ture only it means when temperature is kept constant, ∆E
• If the gas contracts, [ V2 < V1] then work is done on
is zero.
the system and W is positive.
• For an ideal gas, it is totally kinetic energy as there is no
molecular interaction.
Different Types of Work and Their Formulas • It is determined by using Bomb Calorimeter
Z × ∆T × m
1. Work done in a reversible isothermal process ∆E =
w
V Z = Heat capacity of Bomb Calorimeter
w = –2.303 nRT log10 2
V1
ΔT = Rise in temperature
P w = Weight of substrate (amount)
w = –2.303 nRT log10 1
P2
m = Molar mass of substrate
2. Work done in an irreversible isothermal process
W = –Pext (V2 – V1) or,  irst Law of Thermodynamics or
F
W = –P ΔV Law of Conservation of Energy
• First law of thermodynamics was introduced by Helmholtz.
Internal Energy • This law states that energy can neither be created nor
• The energy stored within a substance is called its internal destroyed but can be converted from one form to another.
energy. The absolute value of internal energy cannot be • The total energy of universe is constant
determined. ΔE = Q – W (work done by the system)
6.4 ■ Chapter 6

ΔE = Q + W (work done on the system) Q = ΔE – W drop in pressure under constant enthalpy conditions when
δE = δQ – δW (work done by the system or in expan­sion) the gas is allowed to expand through a porous plug.
δE = δQ + δW or δE = δQ + PδV dT
–
(Work done on the system or in compression). dP
Q = + ve: Heat is absorbed by the system. mJT = dT = T
dP n CP
Q = – ve: Heat is evolved by the system. • µJT = 0 for an ideal gas as van der Waals forces of attrac-
• For a reversible cyclic process ΔE = 0, tion are negligible.
V2 P1
Q = –Wmax = PΔV = 2.303nRT log10 or
V1 P2 Second Law of Thermodynamics
• For an isochoric process ΔE = Q (ΔV = 0)
• It is not possible to convert heat into work without com-
• For an adiabatic process ΔE = W (as q = 0) pensation.
• During adiabatic compression
• Work can always be converted into heat but the conver-
(P V – P2V2) sion of heat into work does not take place under all con-
W= 1 1
(g – 1) ditions.
• It fails to explain the expansion of gases invaccum when
• It is impossible to construct a machine that is able to
ΔE = O, ΔH = O, W = O.
transfer heat by a cyclic process, from a colder to a hot-
ter body, unless work is done on the machine by some
Enthalpy Change outside agency.
• Enthalpy change is the amount of heat absorbed • Whenever a spontaneous process takes place it is
or evolved by a system at constant pressure or constant accompanied by an increase in the total entropy of the
volume. universe.
• It is not a state function.
• It is denoted by H at constant pressure. Carnot Cycle
• It is denoted by E at constant volume.
• Carnot cycle demonstrates the maximum convertibility
• It is the sum of internal energy and pressure volume of heat into work without any compensation.
work.
• It is a theoretical and an imaginary cycle
• H = E + PV or, ΔH = ΔE + PΔV
W T2 – T1 Q2 – Q1
• Enthalpy of the elements in gaseous, liquid or solid or η= = =
Q2 T2 Q2
cobined state is taken as zero.
η = Hermodynamic efficiency
Relation between Δ H and Δ E Q2 = Heat absorbed from the source at T2
ΔH = ΔE + ΔngRT = ΔE + P ⋅ ΔV Q1 = Heat lost to sink at T1
= ΔE + Δ(PV)
When T2 is much greater than T1 η is more but less than
Here ΔH = change in enthalpy in constant pressure one.
ΔE = change in enthalpy in constant volume
Δng = difference in the moles of gaseous reactants
and product Entropy
• The disorder or randomness in a system is measured in
Joule–Thomson Effect terms of entropy (S). It is a state function and an exten-
The phenomenon of change of temperature when a gas sive property.
is made to expand adiabatically, from a region of high
pressure into a region of low pressure, is known as Joule– • The absolute value of S is not determined, so mostly
Thomson effect. change in entropy ΔS is measured.

Joule–Thomson coefficient (µ) It is the number of Qrev V

∆S = = –2.303nR log 2
T V1
degrees of temperature change produced per atmospheric
 Thermodynamics and Chemical Energetics ■ 6.5

V2 • When a rubber band is stretched, entropy decreases

As, Qrev = –Wrev = –2.303 nR log
V1 because the macro molecules get uncoiled and hence
Unit of entropy is J K–1 mol–1 arranged in a more ordered manner, which means that
randomness decreases.
Randomness α Entropy
• When an egg is boiled, the entropy increases because
Facts About Entropy denaturation occurs resulting into a change of proteins
from helical form into random coiled form.
• In nature, all processes are irreversible followed by
• Molecules kept in a large volume container have a high
an increase in entropy. Entropy of the universe tends
value of entropy.
towards a maximum.
• Cases of increase in entropy
T2 1. Dissolution of a solute in water
∆S = 2.303 × CP log
T1 2. Decomposition of a compound
Cp = Molar heat capacity at constant pressure. 3. Vaporization and fusion
• For a spontaneous process, entropy increases. 4. Expansion of ideal gas from one container to an evac-
ΔS = Positive uated chamber.
• Decrease in entropy occure during crystallization and
At 298K and 1 atm ΔS° = Σ S°p – Σ S°R combination.
Spontaneous Process • Entropy is directly proportional to atomic weight. For
example, I2 > Br2 > Cl2
The chemical or physical process which occurs in a par­
• Entropy is directly proportional to number of bonds For
ticular set of conditions, either on its own or after proper
example, ethane > ethene > ethyne
initiation is known as spontaneous process. All natural
pro­cesses are spontaneous.
Zeroth Law of Thermodynamics
• ΔSsys + ΔSsurr = 0 for reversible processes
• ΔSsys + ΔSsurr > 0 for irreversible processes According to the zeroth law, “Two systems in thermal equi­
librium with a third system are also in thermal equilibrium
with each other.”
Entropy Changes in Different Processes
1. Isothermal reversible expansion of an ideal gas Third Law of Thermodyanmics
V2 P At the absolute zero of temperature, the entropy of any sub-
∆S = nR loge ​ or 1
V1 P2 stance may become zero but does become zero in case of
2. Adiabatic reversible expansion perfectly crystalline structure.
Q = 0, ΔS = 0 ∫ S=0
lim T → 0
3. Isobaric process • In case of CO and NO molecules in solid state, entropy
T or randomness is not zero even at absolute zero tem­
∆S = CP log 2
T1 perature (0 K).
4. Isochoric process
T
Gibbs Free Energy (G)
∆S = CV log 2
T1 • Free energy of a system is defined as the maximum
5. Entropy changes during phase transition amount of energy available to a system during a process
Q DH that can be converted into useful work. It is a state func-
∆S = S2 – S1 = rev = tion and an extensive property.
T T
DHfusion • It is denoted by G or ΔG°
∆Sfusion =
Tfusion or MP G = H – TS
DHvap ΔG = ΔH–TΔS
∆Svap =
Tvap or BP ΔG° = ΔH° – TΔS°
Unavailable energy = Entropy × Temperature This is called Gibbs–Helmholtz equation.
6.6 ■ Chapter 6

• It is a state function and an extensive property. • At constant volume, Q = ΔE

• During a spontaneous change, ΔG decreases. So, heat capacity at constant volume,
• ΔG = – ve (spontaneous process) ∂E
Cv =
• ΔG = + ve (non-spontaneous process) ∂T v
• ΔG = 0 (process in equilibrium) • At constant pressure, Q = ΔE + PΔV = ΔH
• In exergonic reaction, ΔG = –ve. So, heat capacity at constant pressure,
• In endergonic reaction, ΔG = +ve. ∂H
Cp = ​
∂T p
Table 6.1 G
 ibbs Free Energy: Spontaneous and
Non-spontaneous Processes • For 1 mole of a gas, heat capacities at constant vol­ume
and constant pressure are denoted by Cv and Cp respec-
ΔH ΔS ΔG = ΔH – T ΔS Remarks tively. These are termed as molar heat capaci­ties. Thus,
– + Always –ve Spontaneous for 1 mole of a gas,
+ – Always +ve Non-spontaneous ∂E
+ + +ve at low temp Non-spontaneous Cv =
∂T v
–ve at high temp Spontaneous
∂H
– – –ve at low temp Spontaneous and Cp =
+ve at high temp Non-spontaneous ∂T p

• CP – CV = PΔV = R
Some Relations Importance of Cp and Cv From the ratio of Cp and Cv
ΔG0 = –n FE° we get an idea about the atomicity of a gas.
Here
• For monoatomic gas, Cp = 5 calories; Cv = 3 calories
n = Number of mole of electron Cp 5
hence γ = = = 1.67
F = Faraday constant Cv 3
E° = Standard emf • For diatomic gas, Cp = 7 calories; Cv = 5 calories
ΔG° = –2.303 RT log K Cp 7
hence γ = = = 1.40
K = Equilibrium constant Cv 5
ΔG° = ΣG°P – ΣG°R • For triatomic gas, Cp = 8 calories; Cv = 6 calories
Cp 8
hence γ = = = 1.33
Heat Capacity Cv 6
• Heat capacity of a system is defined as the quantity of Phase transition The change of matter from one
heat required to raise the temperature of the system by state (solid, liquid or gas) to another state is called Phase
one degree. transition.
• The specific heat capacity is denoted by C and can be • Such changes occur at definite temperatures, such as
calculated with the help of the formula melting point (solid to liquid), boiling point (liquid to
vapours) etc. and are accompanied by absorption or evo-
Q = C × m × ΔT lution of heat.
Here, Heat engine A machine which can do work by using heat
Q =  Heat required to raise the temperature by that flows out spontaneously from a high temperature source
l degree to a low temperature sink is called a heat engine.
C = Specific heat capacity Driving force The overall force responsible for reaction
m = Mass to occur.
ΔT = Temperature change
• Let a very small quantity of heat dQ be given to a system
Thermochemistry
so that the temperature of the system rises by dT. Thermochemistry deals with the heat changes during chemi­cal
dQ reactions. It is called energetics and is based on First Law
Thus, heat capacity =
dT of Thermodynamics.
 Thermodynamics and Chemical Energetics ■ 6.7

Exothermic Reaction
Temperature
• Heat is evolved in this case.
It is given by Kirchoff equation.
• ΔH is –ve as HR > Hp
Effect of temperature on heat of reaction is given by
• ΔH = Hp – HR = –ve (At constant pressure) ΔE = (Ep – Kirchoff s relation.
ER) = –ve (At constant volume) ER > EP DH2 – DH1
∆Cp
T2 – T1
Endothermic Reaction
• Heat is absorbed in this case. DE2 – DE1
= ∆Cv
T2 – T1
• ΔH or ΔE = +ve for endothermic reaction
• ΔH = HP – HR = +ve (At constant pressure) Pressure and volume
As HP > HR ΔH = ΔE + Δn*RT
• ΔE = (EP – ER) = +ve (At constant volume) ΔH = ΔE + PΔV
As EP > ER
ΔH = ΔE + PΔV
Heat or Enthalpy of Reaction ΔH = ΔE + (PfVf –PiVi)
• Heat of reaction is the change in enthalpy (amount of Δn* = number of gaseous product – number of reactant
heat evolved or absorbed) when the number of g moles molecules.
of the substance, indicated by a chemical reaction, have
undergone complete reaction.
• It is determined by water and bomb calorimeters. Heat of Combustion
Mathematically, it is given as: • Heat of combustion is the change in enthalpy, when one
mole of a substance is completely oxidized.
ΔH = ΣHP – ΣHR
• ΔH is –ve as heat in always evolved in this case, that
• It can be express by [ΔH]p or [ΔE]V means, it is an exothermic process.
• Heat of combustion is used to calculate calorific value of
Factors Affecting Heat of Reaction food and fuels.
Nature or physical state of reactant and • It is also useful in confirming structure of organic mol-
products ecules having C, H, O, N etc.
1 • Enthalpy change accompanied by combustion of l g
H2(g) + O (g) H2O(g) ΔH = –57.8kcal
2 2 solid or 1 g liquid or 1 cc gas is called calorific value.
1
H2(g) + O2(g) H2O(l) ΔH = –68.32kcal Heat of combustion
2 C.V. =
Molecular weight
When steam condenses heat is evolved.
C + O2 CO2 ΔH = – 94 kcal
Allotropic forms of the element 94
C + O2 = – = –7.83 kcal
Cdiamond + O2 (g) CO2 (g) ΔH = –94.3 kcal 12

Camorphous + O2 (g) CO2 (g) ΔH = –97.6 kcal

C12H22O11 + 12O2 12CO2 + 11H2O

Cdiamond Camorphous ΔH = 3.3 kcal

ΔH = – 1349 kcal
1349
This heat is called heat of transition. C.V. = – = –3.94
342
Enthalpies of solution ΔH(heat of reaction) = –ΣΔ​H°P​ ​ ​ – ΣΔ​HR​ ° ​ ​
H2S(g) + I2(g) 2HI + S; ΔH = –17.3 kcal Calorimetry
H2S(sol) + I2(sol) 2HI + S; ΔH = –21.93 kcal Heat exchange = Heat capacity × Temperature change
sol. (heat exchange—when no chemical change or state change
occurs)
6.8 ■ Chapter 6

Heat of Formation ΔH= –12.3 kcal, that is heat of ionization of CH3COOH

The amount of heat evolved or absorbed, or change in en­ is 0.3 kcal or 1.9 kJ/mole
thalpy when 1 mole of a substance is obtained from its con­ • If both the electrolytes are weak then
stituents or free elements as in following example,
CH3COOH + NH3 CH3COONH4 + H2O
N2 + 3H2 2NH3; ∆H = –22 kcal
+ 50.4 kJ/mole
N2 + O2 2NO; ∆H = +42 kcal
CH3COOH + NH4OH CH3COONH4 + H2O
• Heat of formation of NH3 is –11 kcal ΔH = –11.9 kcal
Heat of formation of NO is +21 kcal • In case of HF, ΔH is more due to increased hydration of
• Heat of formation at 25°C and 1 atm pressure is called F– ions.
standard heat of formation (∆H°).
• Standard heat of formation of a free element is taken Heat of Hydration
as zero. (Ggraphite, Smonoclinic) The enthalpy change that occurs during hydration of one g
• Heat of formation may be +ve or –ve. mole substance is called heat of hydration.
• If ∆H is –ve, compound formation is exothermic.
CuSO4 + 5H2O CuSO4.5H2O + 78.21 kJ/mole
• If ∆H is +ve, compound formation is endothermic.
or 18.7 kcal/mole
• Stability of a compound formed by exothermic reac­tion
is more than that of a compound formed by endo­thermic ΔH = –18.7 kcal/mole
reaction.
• Greater the liberated energy, greater is the stability of the • It is mostly exothermic
compound. ΔHsol = ΔHhy – Lattice energy
Following compounds are placed in the observed order • If ΔHH > L.E. then solute dissolve in water
of stability. HF > HCl > HBr > HI. • ΔHH < L.E. then solute does not dissolve in water
Heat of Neutralization • ΔH ≈ L.E. then solute is in equilibrium with solvent
• Heat of neutralization is the enthalpy change accom­- in water
panied during neutralization of 1 g mole of an acid and
base. It is also known as heat of formation of water. Bond Energy
+ –
H Cl + Na OH + –
NaCl + H2O + 13.7 kcal/mole Bond energy may be defined as, “The quantity of heat
evolved when a bond is formed between two free atoms
or 57.3 kJ/mole
in a gaseous state to form a molecular product in a gas­
H+ + OH– H2O + 13.7 kcal or 57.3 kJ/mole eous state.” It is also known as enthalpy of formation of the
ΔH = –13.7 kcal or –57.3 kJ/mole bond.
• It is always exothermic. ΔH = –ve It can also be defined as, “The average quantity of heat
• In laboratory, it is measured by using polythene on poly- required to break (dissociate) bonds of that type present in
styrene bottles. one mole of the compound.”
• Heat of neutralization of strong acid and strong base is Making use of the above defined defination in the case of
always –13.7 kcal/mole or –57.3 kJ/mole. C (g) + 4H (g) CH4 (g); ΔH = –398 kcal
the average bond energy per mole of C–H bond in this
• It is independent of the nature of strong acid or strong
398
base. example = – = –99.5 kcal
4
• If one electrolyte is weak then ΔH will be less than –13.7 When a reaction is carried out in the gas phase at
kcal as some amount of heat will be absorbed in ioniza- constant pressure then enthalpy of the reaction is given as:
tion of weak electrolyte, as shown here.
ΔH = ΣBER – ΣBEP
CH3COOH + NaOH CH3COONa + H2O + or
55.2 kJ/mole or
ΔH = (Energy needed to break the bonds in the molecules
13.4 kcal/mole
of the reactants) – (Energy released when bonds in the mol­
HCl + NH4OH NH4Cl + H2O ecules of the products are formed).
 Thermodynamics and Chemical Energetics ■ 6.9

For example, in the case of formation of HCl (g) from KCl KCl
H2 (g) and Cl2 (g), ΔH = –185 kJ/mol (X H2O) (Y H2O)
EH_H= 437 kJ HCl + 10H2O HCl.10H2O
EC–Cl = 244 kJ
∆H = –69 kJ/m

EH–Cl = 433kJ
It’s value depands upon the concentration of solution
So, ΔH = EH_H +EC_Cl – (2EH–Cl) and amount of solvent used.
= 437+ 244 – (2 × 433)
= –185 kJ Heat of Solution
It is help ful in finding heat of reaction and resonance Heat of solution is change in enthalpy, that occurs when one
energy. mole of a solute is dissolved in excess of solvent.
Heat of Atomization • ΔH = +ve for (hydrated salts)
It is the enthalpy change (heat required) when bonds of one • ΔH = –ve for (anhydrous salts)
mole of a substance are broken down completely to obtain KC1 + H2O KC1 (aq)
atoms in the gaseous phase (isolated) or, it is the enthalpy
ΔH = –18.6 kJ/moIe
change when one mole of atoms in the gas phase are formed
from the corresponding element in its standard state. H2SO4 + H2O H2SO4 (aq)
In case of diatomic molecules it is also called bond dis­ ΔH = –20.2 kcal
sociation enthalpy.
It is denoted by ΔHa or ΔH. Heat of Fusion
For example, H2 (g) 2H (g) – 435 kJ Heat of fusion is the change in enthalpy, that occurs in con-
ΔH = +435 kJ/mol verting one mole of solid into the liquid state at its melting
point. It is equal tolatent heat of fusion per gram multiplied
CH4 (g) C (g) + 4H (g) + 1665 kJ
by the molar mass.
ΔH = +1665 kJ/mol
• It is always +ve as heat is needed to overcome the
Enthalpy of Dissociation or Ionization intermolecular forces between constituents particles
It is defined as, “The quantity of heat absorbed when of solid.
one mole of a substance is completely dissociated into H2O(s) H2O(l); ΔH = 0.6 kJ/mole
its ions.”
For example, in case of H2O (l) H+ + OH–, the Heat of Vaporization
value of ΔH = 13.7 kcal
Heat of vaporization is the change in enthalpy, that occurs
Phase Transition and Transition Energy in converting one mole of liquid into the gaseous state at its
• The change of matter from one state (solid, liquid or boiling point. For example,
gas) to another state is called phase transition. H2O(l) H2O(g); ΔH = 42 kJ/mole
• Such changes occur at definite temperatures such as
melting point (solid to liquid), or boiling point (liquid to Heat of Sublimation
vapours), and are accompanied by absorption or evolu- Heat of sublimation is the change in enthalpy that occurs in
tion of heat. The enthalpy change during such phase tran- converting one mole of a solid directly into its vapour state
sitions is called heat of transition or transition energy. at a temperature below its melting point.
For example,
C (diamond) C (amorphous) I2(s) I2(g); ΔH = 62.4 kJ/mole
ΔH = 3.3 kcal • ΔHsub =ΔHvap + ΔHfus
Heat of Dilution Hess’s law This rule is a consequence of Ist Law of Ther-
Heat of dilution is the change in enthalpy that occurs when modynamics and according to the Hess’s law, the enthalpy
a solution containing one mole of solute is diluted from one change for a process is independent of the path it follows.
concentration to another concentration.
6.10 ■ Chapter 6

Q
A Z Some Major Chemical Fuels

q q Natural gas: It is mainly composed of methane and

1 4
some other gaseous hydrocarbons like ethane, propane and
B C D
q q butane.
2 3

Figure 6.2 Hess’s Law Petroleum: It contains hundred of hydrocarbons and

Examples: many other organic compounds having S, O, N. For
C + O2 CO2; ΔH = –94.3 kcal example, kerosene oil, petrol, diesel, LPG (it is liquefied pe-
1 troleum gas having mainly butane and isobutane).
C + O2 CO; ΔH = –68.3 kcal
2 Coal: It is a solid and a crude form of carbon having higher
1 hydrocarbons and some other organic compounds having S,
CO + O2 CO2; ΔH = –26 kcal
2 O and N.
Q = Q1 + Q2 = –94.3
• ΔH or ΔE is not proportional to the path of a reaction.
• ΔH or ΔE is a state function which depends only on Wood and dung The major constituent in these is meth­
initial and final states (first law of thermodynamics). ane.
• ΔH or ΔE is an extensive property.
Falling water Flowing or falling water has mechanical
Sources of Energy energy which can be used to run the turbine which in turn
Energy is needed in every field of life and its importance is generaes electricity (hydroelectric power).
increasing day by day. Major sources of energy are given Nuclear energy It is the latest major source of energy.
below: Here energy is obtained by the fission of fissile material like
Fossil fuels Some major fuels are natural gas, coal and U-238 and Pu-241.
petroleum products, that is, carbon containing species
Geothermal sources, wind energy, ocean currents may
(major sources).
also be good sources of energy.
These undergo combustion to release heat in the form
of energy, and this energy is further used according to need.
For example, during electricity manufacture this released The Sun as the Primary Source of Energy
heat converts water into steam, which in turn runs the Sun is the ultimate source of energy. Its energy is called
turbine, and thus generates electricity. solar energy. (Fig. 6.3)

Causes winds, tides Causes rain Rivers, Waterfalls

ocean waves
Heat

He
at Hydorelectric power
Wind energy,
geothermal power Solar energy Production of
Sun electricity

Light

Plants produce food by

Organic waste and photosynthesis Fossilized to
excreta used for perroleum, coal,
gobar gas (Food or) Animals natural gas

Fuel Fossil fuels

Figure 6.3 Sun: The Ultimate Source of Energy
 Thermodynamics and Chemical Energetics ■ 6.11

Conservation of Energy
Important Formula
Eighty per cent of the energy requirements are fulfilled by
fossil fuel. Their stock, however, is limited and these are Work
depletable or non-renewable sources of energy. Hence, their Electrical Work = Potential difference × Charge flow
conservation is a must. = V × Q = EnF
Conservation of energy is possible in the following ways: Expansion Work = P × ΔV
P = External pressure
• We must use most efficient type of fuel, preferably from ΔV = Increase or decrease in volume.
a renewable source.
• We must use high efficiency devices for the combustion Different types of works and the formulas
of such fuel. We must use solar home appliances instead 1. Work done in a reversible isothermal process
of electrical and fuel appliances. V2
W= –2.303 nRT log
• Deforestation must be avoided. V1
• Electrical appliances and vehicles must be regularly W= –2.303 nRT log
P1
serviced. P2
• We must shut off the engine of the vehicles when 2. Work done in an irreversible isothermal process
stopping for a long period. W = –Pext(V2 – V1)
• Excessive use of electric appliances and vehicles should that is, W = –P ΔV
be avoided.
• ΔE = ΣEp – ΣER

Points to Remember Bomb calorimeter

Lavosier and laplace law The amount of heat Z×T×m
required to break a compound into its element is equal ∆E =
w
to the heat evolved during its formation.
First law of thermodynamic or
ΔHD = – ΔHf
Law of conservation of energy
A calorimeter It is used to find enthalpy of reaction ΔE = Q – W (that is, work done by the system)
Z × DT × m ΔE= Q + W (that is, work done on the system)
∆H =
w or
1. It is not applicable when (i) reaction is slow (ii) ΔH Q = ΔE – W
is low (iii) reaction does not complete. δE = δQ – δW
(Work done by the system or in expansion) or
2. ΔH does not change with temperature appreciably.
δE = δQ + δW or δE = δQ + PδV

Resonance Energy
For a reversible cycle
Resonance energy = Expected heat of hydrogenation –
ΔE = 0,
Calculated heat of hydrogenation
V2 P1
For example, resonance energy of CO2 is 32 calorie Q = –Wmax = PΔV = 2.303 nRT log or
V1 P2
per mole.
For adults 2500–3000 kcal energy per day is needed. For an isochoric process
ΔE = Q(ΔV = 0)
Trouton’s rule law During adiabatic compression
(P1V1 – P2V2)
DHvap W=
= Joule/K mol (γ – 1)
Tb
6.12 ■ Chapter 6

Enthalpy change • ΔG° = –2.303 RT log K

Here K = Equilibrium constant
ΔH = ΔE + PΔV
• ΔG° = ∑G°P – ∑G°R
Relation between ΔH and ΔE • At constant pressure, Q = ΔE + PΔV = ΔH
ΔH = ΔE + Δng RT • CP – CV = PΔV = R

Entropy Heat or enthalpy of reaction

Qrev V Mathematically, ΔH = ∑HP – ∑HR
∆S = = –2.303 nR log 2
T V1 • It can be expressed by [ΔH]P or [ΔE]V
T2
∆S = 2.303 × CP log
T1
Kirchoff equation
∆S° = ∑S°P – ∑S°R
DH2 – DH1
= ΔCP
T2 – T1
Entropy changes in processes
DE2 – DE1
Isothermal reversible expansion of an ideal gas = ΔCV
T2 – T1
V2 P1
∆S = R loge or
V1 P2 Pressure and volume
Adiabatic reversible expansion ΔH = ΔE + ΔnRT
Q = 0, ΔS = 0 ΔH = ΔE + PΔV
Isobaric process ΔH = ΔE + Δ(PV)
T
∆S = CP log 2 Δn = Number of gaseous product – N
 umber of reactant
T1
molecules
Isochoric process
T2 Calorimetry
∆S = CV log
T1
Heat exchange = Heat capacity × temperature change
Phase Transition (heat exchange—when no chemical change or state change
Qrev DH occur)
∆S = S2 – S1 = =
T T
DHfusion Heat of hydration
∆Sfusion =
Tfusion or Mp ΔHsol = ΔHhy – Lattice energy
DHvap
∆Svap =
Tvap or BP Bond energy
• ΔH = ∑BER – ∑BEp
Gibbs free energy
• G = H – TS • ΔHsub = ΔHvap + ΔHfus
• ΔG° = ΔH° – TΔS° Hess’s law Q = Q1 + Q2 + Q3 + Q4.......

Some relations Resonance energy

• ΔG° = –n F E° Resonance energy = Expected heat of hydrogenation –
• n = Number of mole of electron Calculated heat of hydrogenation
• E°= Standard emf
 CHAPTER
Chemical Equilibrium
7A
Chapter Outline
■ Types of Reactions ■ Equilibrium

Types of Reactions For example,

N2 + O2 2NO
A chemical reaction is a process in which the reactants un­
dergo changes and produce substances, called products, 3Fe + 4H2O Fe3O4 + 4H2
which are different from them. In an open flask, vaporization of water as well as decom­
Chemical reactions are classified as irreversible and position of calcium carbonate are irreversible reactions and
reversible reactions. in closed flasks both, the reactions become reversible.

Irreversible Reactions
Active Mass or Molar Concentration
Irreversible reactions occur in one direction only and go on
w
to completion. For example, CAor [A] = __________
​ m × V (liters) = γ. molarity

1. When unreactive products are formed Here γ is activity coeficient (for dilute solution it is
Δ taken as unity).
NH4NO2 N2 + 2H2O
1. Unit is mol L–1
2. All precipitate reactions are irreversible 2. At constant temperature
BaCl2(aq) + H2SO4(aq) BaSO4(ppt.) + Partial pressure ∝ Active mass
2HCl(aq) 3. Active mass of pure solid or pure liquid is assumed to be
3. Neutralization reaction one.
H2SO4 + 2KOH K2SO4 + 2H2O 4. Active mass of any gas at NTP is 1/22.4

4. Redox reactions
2FeCl3 + SnCl2 SnCl4 + 2FeCl2 Equilibrium
5. Combustion reactions
The word “Equilibrium” in physical sense is explained as
2Mg + O2 2MgO
the “No change of state of the body”.
Reversible Reactions When the two opposing processes (reactions) occur
Reversible reactions occur in both forward and backward simultaneously with equal rates, the system will be in the
di­rections and therefore never go on to completion. state of equilibrium.
7.2 ■ Chapter 7

Equilibrium is classified as shown below: • If a chemical equilibrium has only one phase, it is called
Equilibrium
homogeneous and if it has more than one phase it is
called heterogeneous.
H2 (g) + I2 (g) 2HI (g)
Chemical Equilibrium Physical Equilibrium
Number of phases = 1 (Homogeneous chemical
equilibrium)
2HgO (s) 2Hg (l) + O2 (g)
Heterogeneous Chemical Homogeneous Chemical
Equilibrium Equilibrium Number of phases = 3 (Heterogeneous chemical
equilibrium)
Figure 7.1 Classification of Equilibrium
Product
Physical Equilibrium

Concn
Equilibrium
When an equilibrium exists between same chemical spe­
cies, it is called physical equilibrium. In it, the opposing Reactant
process involves only physical changes. Time
H2O (s) H2O (l)
Ice Water Rate of forward reaction

Facts to Remember Rate

Equilibrium
• Physical equilibrium may be of these types:
Rate of backward reaction
(i) Solid liquid
e.g., Ice water
Time Time at which
(ii) Liquid Gas equilibrium is achieved
e.g., Water Steam Figure 7.2 Chemical Equilibrium
‘l’ ‘g’

(iii) Solid Gas • Chemical equilibrium is the stage of a reversible reac­

e.g., I2 I2 By Sublimation tion at which the active masses of the reactants and the
‘s’ ‘g’ products become constant in mixture and do not change
Here rate of evaporation and condensation are with time.
same. • It is the state of a reversible reaction at which measur­
able properties like colour, density, pressure and con­
(iv) Solid Solution centration are nearly unchangeable.
In water
e.g., Sugar Sugar Solution
Solid Features
Here rate of dissolution and precipitation are same • Rate of forward reaction is equal to rate of backward
reaction.
(v) Gas Solution
• It is obtained only when reversible reaction is carried out
e.g., O2 O2
g aq. soln.
in a closed space.
• At constant temperature it is characterized by proper­ties
like colour, density, pressure.
Chemical Equilibrium • It is possible from both the directions.
• When an equilibrium exists between different chemi­cal • It is dynamic in nature. It means the reaction is not going
species, it is called chemical equilibrium. to be ceased as reaction occurs in both the directions
with equal rates.
N2(g) + 3H2(g) 2NH3(g)
• A positive catalyst can set up equilibrium in less time but
CaCO3 (s) CaO (s) + CO2 (g) cannot change it.
 Chemical Equilibrium ■ 7.3

• At equilibrium, ΔG is equal to zero. For a reaction

As ΔG = ΔΗ – TΔS V1
And ΔΗ = TΔS A+B C+D
V2
So ΔG = O
V2 ∝ [A] [B] or V1=K1[A][B]
Types of chemical equilibrium Chemical equilibrium V2 ∝ [C] [D] or V2=K2[C][D]
can be classified into following two types, viz., homoge­
We know that at equilibrium V1 = V2
neous and heterogenous.
So, K1 [A] [B] = K2 [C] [D]
Homogeneous Here reactants and products are present in K1 [C] [D]
______
the same phase or physical states. = ​  [A] [B]​
K2
Example: N2(g) + O2(g) 2NO(g) [C]nl [D]n 2 [product]
Kc = or ​ ________
[reactant] ​at constant temperature
[A]m1 [B]m2
R–COOH + R’–OH R–COOR’ + H2O or
‘l’ ‘l’ ‘l’ ‘l’
For m1A + m2B n1C + n2D
Heterogeneous Here reactants and products are present in nl
[C] [D] n2

different phases or physical states. Kc =

[A]m1 [B]m2
Example: 3Fe(s) + 4H2O(l) Fe3O4(s) + 4H2(g) • Completion of reaction ∝ Kc
Stability of reactant ∝ 1/Kc
Law of Mass Action Stability of product ∝ Kc
• Law of mass action was introduced by Guldberg and Kc does not depend upon
Waage. • Initial concentration or pressure of reactants and products
• It states that the rate at which a substance reacts is involved.
directly proportional to its active mass and the rate at • The presence of a catalyst.
which different substances react together is directly pro­ • Presence of an inert gas.
portional to the product of their active masses. • The direction from which equilibrium has been set up.
V1 Kc depends upon
• A+B C+D
V2 (1) Temperature
If active masses of and D are [A], [B], [C], [D] respec­ • The variation of equilibrium constant with temperature
tively, then is given by van’t Hoff equation as follows:
K= Ae–ΔΗ°/RT
Rate of reaction of A ∝ [A]
K (T2–T1)
Rate of reaction of Β ∝ [Β] ​  ΔΗ°R ​ ​  ______
log10 2 = ______
2.303 T1.T2​
K1
V1 ∝ [A] [Β] = K1 [A] [B] K∝T (ΔΗ = +ve)
V2 ∝ [C][D] = K2 [C] [D] K ∝ 1/T (ΔΗ = –νe)
• Law of mass action is not applicable for solids and for • When a graph is plotted between log10K and 1/T, a
them, active mass is always one. For example, straight line will be formed, the slope of which is equal
to ​ –∆H
°
KClO3(s) 2KCl + 3O2
2.303 R
Equilibrium Constant
• Equilibrium constant is the ratio of the rate of forward and
backward reactions at a particular temperature, or in other
words it is the ratio of active masses of the reactants to that
of active masses of products at a par­ticular temperature.
• It is denoted by Kc when the concentration is taken into
consideration and by Kp when the partial pressure is Figure 7.3 Graphs for Endothermic and Exothermic
taken into consideration. Reactions
7.4 ■ Chapter 7

(2) Mode of representation of reaction • If Δn is positive, then Kp > Kc, as in

Let us consider a reaction PCl5 PCl3 +Cl2
A +B C+D 2NH3 N2 + 3H2
​ ______
[C] [D] ​ • If Δn is negative, then Kc > Kp, as in
Kc = [A] [B]
2SO2 + O2 2SO3
Now if we write the above reaction as follows:
C+D A+B Units of equilibrium constant (K)
[A] [B] Kc = (mol/L)Δn
K’c = ______
​  [C] [D] ​
Kp = (atm)Δn
Hence, Kc = 1/K’c
Equilibrium constant for a multi-step reaction
(3) Stoichiometric representation of chemical equation
K = K1 . K2 . K3
Let us consider a reaction
For example, for a multistep reaction like
A+ B C+D
H2O2 + 2H+ 2I– I2 + 2H2O
[C] [D]
Kc= ______
​  [A] [B] ​ We follow the steps as given below:
If we write the above reaction as follows: H2O2 + I– OH– + HOI (K1)
m1A + m2B n1C + n2D, then H+ + OH– H2O (K2)
+ –
[C]n1 [D]n2 HOI + H + I H2O + I2 (K3)
Kc = Here K =K1 . K2. K3
[A]m1 [B]m2
Examples:
Reaction or concentration quotient: (Q)
1. N2 + 2O2 2NO2 It may be defined in a same manner to equilibrium constant
[NO2]2 (Keq.) however the molar concentrations in case of Q are not
Here K’c = ​ _______
[N2][O2]2
​ necessarily equilibrium values.
_1 m1A + m2B n1C + n2D
2 N2 + O2 NO2
[NO2]2 [C]n1 [D]n 2
Here K’c = ​ _______ ​= √Kc Q=
[N2]1/2 [O2] [A]m1 [B]m2
2. N2 + 3H2 2NH3 and It helps in predicting the direction of reaction as follows:
NH3 1
_ N + 3/2 H2 then (1) If Q = keq, The reaction is at equilibrium.
2 2
K’c= 1/√kc (2) If Q > keq, Backward reaction is favourable.
(3) If Q < keq forward reaction is favourable.
Equilibrium constant in terms of partial pressure Keq Q Keq Q
If partial pressures of A, B, C, D are given as PA, PB, Pc, PD Q Movement Movement Keq
respectively, then for the reaction, Kp is given as Toward Toward

m1A + m2B n1C + n2D Equilibrim Equilibrim

[PC ]n1 [PD ]n 2

Kp =
[PA ]m1 [PB ]m2 Figure 7.4 Reaction Quotient

Relation between Kp and Kc Relation between standard gibbs free energy

Kp = Kc.(RT)(m1 + m2) – (n1 + n2) and equilibrium constant
Δn = Sum of gaseous products – Sum of gaseous reactants The relation between the two is given by the equation
Δn = (m1 + m2) – (n1 + n2) mentioned below:
Kp = Kc.(RT)Δn ΔG = ΔG° + 2.303 RT log10 Q
• If Δn is zero Kp = Kc, as in As ΔG = 0, Q = K. So,
ΔG° = –2.303 RT log10 K
N2 + O2 2ΝΟ
 Chemical Equilibrium ■ 7.5

Here if ΔG° > 0 (+ve), then < 1, making the backward • If the system at equilibrium is subjected to a change
reaction feasible. of concentration or temperature or pressure, the
If ΔG° < 0 (–ve), then > 1, making the forward reaction system adjusts itself in such a way that the effect of these
feasible. changes can be neglected or minimized.

Expressions of Kc and Kp for Some Reactions Effect of concentration

• An increase in concentration of any substance favours the
1. In case of HI or NO formation reaction in which it is used up, that is, in opposite direction.
4x 2 • An increase in concentration of reactant favours forma­
Kc =
(a − x) (b − x) tion of more product, that is, forward reaction.
4x 2 • Increase in concentration of product favours backward
Kp =
(a − x) (b − x) reaction, that is, its continuous removal is essential for
its greater formation.
2. In case of NH3 formation
4x 2 V 2 Effect of pressure
Kc =
(a − x)(b − 3x)3 • High pressure is favourable for the reaction in which
1
3. In case of PCl5 dissociation there is a decrease in volume or nr > np. [As P ∝ ]
V
x2 • Low pressure is favourable for the reaction, in which
Kc =
(a − x)V there is an increase in volume or nr < np.
Px 2 • Pressure is kept constant when volume is constant or
Kp = nr = np.
(1 − x 2 )
Here nr = Moles of gaseous reactant
4. Dissociation of N2O4
np = Moles of gaseous product
4α 2 p
Kp =
(1 − α 2 ) Effect of temperature
Here a and b represent the initial concentration of the • Increase in temperature favours the forward reaction in
reactants. endothermic reaction (ΔΗ = +ve).
• Decrease in temperature favours the forward reaction in
exothermic reaction (ΔΗ = –ve).
Degree of Dissociation (α)
Degree of dissociation is the ratio of number of molecules Applications of Le Chatelier’s principle
dissociated at equilibrium, to the initial number of mol­ 1. Ice–water system (melting of ice)
ecules. Ice Water – Heat (ΔΗ = +ve)
It is given as: Since this is an endothermic process and there is a
D–d 1  D−d 
α = _____
​ d(n–1)or​ =   de­crease in volume, the favourable conditions for melt­
(n − 1)  d 
ing of ice are high temperature and high pressure.
Molecular weight 2. Water-steam system (evaporation of water)
Here D = _____________
​ 
   2 ​
Water Steam – Heat (ΔΗ = +ve)
= density before dissociation
Since this is an endothermic process and there is an incr­
d = vapour density ease in volume, so the favourable conditions for evap­
= density after dissociation oration of water are high temperature and low pres­sure.
n = number of species formed after dissociation 3. Solubility of gases in liquids When a gas dis­
solves in a liquid, there is a decrease in its volume,
Le Chatelier’s Principle so an increase in pressure will favour the dissolu­
• Le Chatelier’s principle describes the effect of change in tion of a gas in liquid, that is, solubility of a gas is
concentration, pressure and temperature on a re­versible directly propor­tional to partial pressure of the gas
system. (Henry’s law).
7.6 ■ Chapter 7

On opening a carbonated water bottle, CO2 comes out

as its pressure decreases. the side which has more volume, that is, the
dissociation of ammonia will be more at
4. Effect of temperature on solubility. constant pressure by adding inert gas like
• Exothermic substances like CaO, Ca(OH)2, KOH argon (Ar).
are more soluble in cold water than in hot water,
which means that low temperature favours their 2NH3 N2 + 3H2
solubility. nR < np
• Endothermic substances like sugar and urea are
2 4
more soluble in hot water than in cold water,
which implies that high temperature favours their
solubility. Points to Remember
5. Formation of nitric oxide.  an’t Hoff reaction isotherm It shows the free
V
N2 (g) + O2 (g) 2NO (g) – 43200 calories energy change of a reaction at any given temperature,
pressure and composition of the reacting system as
• Here favourable conditions for formation of NO follows:
are: higher concentration of N2, O2, constant pres­ ΔG= ΔG° + RT In J
sure (as np = nr) and high temperature (as the for­
ward reaction is endothermic). Since at equilibrium, ΔG is 0 so ΔG0 = –RT In Jeq
Here J stands for reaction quotient of partial pres­
6. Formation of ammonia.
sures of products and reactants.
N2 (g) + 3H2 (g) 2NH3 (g) + 22400 calories Concentration terms of products
J = ​ _______________________
   Concentration terms of reactants ​
   
•  Favourable conditions for NH3 formation are:
higher concentration of N2, H2, high pressure (as np Jcq means the partial pressure of the products and the
< nr) and low temperature (as it is exothermic). reactants at the equilibrium that is Jeq can be replaced
7. Formation of SO3: by Kp.
2SO2 + O2 2SO3 So, ΔG° = –RT In Kp
∆H = –193.2 kJ • The equilibrium equation can not inform us how
long will it take to attain equilibrium during a reac­
The favourable conditions for SO3 formation are low tion.
temperature, high pressure, more concn of SO2, O2
• Le-Chatelier’s principle is not applicable for solids.
8. Formation of H2 by Bosch method:
∆H = + 42 kJ for e.g., Fe+ S → FeS
s ‘s’ ‘s’

The favourable conditions are high temperature, con­
stant pressure and more concn of H2, CO, steam. Important formula
• Conversion of a solid into liquid and of liquid into

Active mass or molar concentration
gas is favoured by high temperature in most cases.
w
• Melting of solids is accompanied by increase of
CAor [A] = _________
​ m × V (litre) ​
volume so low pressure favours their melting while
high pressure favours solidification. Equilibrium constant
For m1A + m2B n1C + n2D
Effects of Adding an Inert Gas on the Equilibrium [C]n1 [D]n 2
Kc = ​
• When np is equal to nr, adding an inert gas either [A]m1 [B]m2
at constant volume or pressure, does not have any
effect. (In case of HI or NO formation)
Equilibrium constant in terms of partial
• When np ≠ nr, there is no effect of adding an inert pressure
gas at constant volume. [PC ]n1 [PD ]n 2
• When np ≠ nr, at constant pressure, on add­ Kp = ​
[PA ]m1 [PB ]m2
ing inert gas, equilibrium will shift towards
 Chemical Equilibrium ■ 7.7

Relation between Kp and Kc Reaction quotient or concentration

quotient (Q)
Kp = Kc.(RT)(n1 + n2) – (m1 + m2)
Δng = (n1 + n2) – (m1 + m2) For m1A + m2B n1C + n2D, then
Kp = Kc.(RT)Δn [C]n1 [D]n 2
Q=
Degree of dissociation (α) [A]m1 [B]m2
D–d
α = ______
​ d (n – 1) ​ • when [C]n1 [D]n2 = [A]m1 [B]m2
Molecular weight Q = Keq (reaction is at equilibrium).
Here D = _____________
​ 
   2 ​ d = Vapour density

Solved Numericals

Kp and Kc Moles of at equilibrium = 2x

= 2 × 1.2 = 2.4.
1. Kc for the reaction
N 2(g) 3H2(g) 2NH3(g) 3. For the reaction H2 + I2 2HI. The equilibrium
–2 2
is 0.5 mole litre at 400 K. Find Kp. Given R = 0.82 concentration of H2, I2 and HI are 8.0, 3.0 and
litre arm degree–1 mole–1. 28.0 moles per litre respectively. Calculate the
equilibrium constant of the reaction.
Solution:
Solution:
Kp = Kc.(RT)Δn
H2 (g) + I2 (g) 2HI (g)
Δn = 2 – 4 = –2
8.0 3.0 28.0 Molar concentration at
Kc = 0.5 mole–2 litre2
equilibrium
T = 400 K
[H]2 (28.0)2
R = 0.82 litre arm degree–1 mole–1 ​  ] [I ] ​= _______
Kc = ______
[H ​  × 3.0 ​= 32.66
8.0
2 2

Kp = 0.5 × (0.082 × 400)–2 = 4.636 × 10–4 arm–2

4. Find the value of Kp for dissociation of:
2. For the reaction: 2HI H2 + I2,
A+B 2C if the equilibrium concentration of HI, H2 and I2 are
2 moles of A and 3 moles of are allowed to react. If the 3.53, 0.4789 and 0.4789 mole litre–1 respectively.
equilibrium constant is 4 at 673 K. Find out the moles
at that equilibrium. Solution:
2HI H2 + I2
Solution:
A + B 2C 3.53 0.4789 0.4789 Molar concentration at
2 3 0 Initial moles equilibrium
[H ][I ] 0.4789 × 0.4789
(2 – x) (3 – x) 2x Moles at equilibrium Kc = ​ ______
2 2
​ = ____________
​ 
   ​= 1.84 × 10–2
[HI]2 [3.53]2
(2 – x) (3
_____ – x)
_____ 2x
__ Molar conecentration
Kp = Kc (RT)Δn
v v v at equilibrium
2 Here Δn = 0
[C] 4x2
Kc = ​ _____ __________
[A][B] ​ = ​  (2 – x)(3 – x) ​= 4 Kp = Kc = 1.814 × 10–2
x2 = 6 – 5x + x2 5. A gaseous mixture contains 0.30 mol CO, 0.10 mole H2
On solving: and 0.2 mole H2O, plus an unknown amount of CH4 in
x = 1.2 each litre. This mixture is in equilibrium at 1200 K.