Chemical energetics

The branch of chemistry which deals with absorption of

energy or evolution of energy in chemical reaction is
called chemical energetic.
System: The part of universe which is under study is called
system. For example: a glass full of water,
 surrounding
• The part of universe which is rest of system is
called surrounding.
• Universe = system + surrounding
• Boundary: The wall which separates system
from surrounding is called boundary.
 Types of system
• . Open system: The system in which both mass
and energy are transferred is called open system.
In open system one side has no boundary. For
example, a cup of tea, earth, human body etc.
• Closed system: The system in which only energy
is transferred but not matter or mass is called
closed system. For example: hot water in glass
which is covered, pressure cooker in cold
condition etc.
 Isolated system
• The system in which neither energy nor mass
is transferred is called isolated system.
For example hot water in thermos ,ice in thermo
flask etc.
Homogeneous and heterogeneous system

• The system in which all the substances are in

same state of matter is called homogeneous
system. For example: manufacture of ammonia by
Haber’s process, formation of sulphurtrioxide in
contact process for manufacture of sulphuric acid.
• The system in which all the substances are not in
same state is called heterogeneous system.
• For example: decomposition of calcium carbonate
into calcium oxide and carbon dioxide.
 State function or state variable
• The property which depends on the initial and
final state of the system but not on path
change is called state function. For example
temperature, pressure , volume , enthalpy,
internal energy , entropy, Gibb’s free energy
etc.
• Path function: The property which depends on
the path but not on state is called path
function. For example work.
 Types of variables or thermodynamic

• Dependent variables: The variable which

depends on the other variable is called
dependent variable. For example, volume is
dependent variable.
• Independent variable : The variable which
does not depend on the other variable is
called independent variable. For example:
temperature, pressure etc.
Extensive and intensive properties
• The property which depends on the amount of
the substance but not on the nature of substance
is called extensive property. For example: mass,
area, work, volume, amount of heat, number of
moles, enthalpy, entropy etc.
• The property which depends on the nature of the
substance but not on the amount of substance is
called intensive property. For example: pressure,
temperature, density, refractive index etc.
 Thermodynamic process
• The mode of change i.e. change in temperature,
pressure, volume etc is called thermodynamic
process.
• There are different types of thermodynamic
process.
• 1. Isothermal process: The process in which
temperature is constant is called isothermal
process. It can be carried out in thermo flask.
The temperature change in this process is zero.
• 2. Adiabatic process: The process in which
heat is neither absorbed nor evolved is called
adiabatic process. In adiabatic process, there
is perfect heat insulation.
• 3. Isochoric process: The process in which
volume remains constant is called isochoric
process. It is carried out in closed system.
4.Isobaric process: The process in which pressure
remains constant is called isobaric process . In this
process change in pressure is zero.
5. Cyclic process: The process in which initial and final
position remains same is called cyclic process.
• Reversible process: The process which occurs
infinitely slowly is called reversible process. In this
Process work done is maximum. This process can be
reversed back. It is hypothetical process. In this process
driving force is slightly greater than opposing force.
• Irreversible process: The process which
occurs rapidly is called irreversible process. It
is unidirectional process. Work done in this
process is minimum. It is practical process.
 Internal energy(E)
• The associated with substance is called internal
energy. It is denoted by E. It is difficult to calculate
the absolute internal energy of the system. But
change in internal energy can be experimentally
measured by Bomb calorimeter. In case of
chemical reaction
• Energy change of reaction∆E = Ep – Er
• Ep = energy of product , Er = energy of reactant.
• It is thermodynamic state function.
 SIGN CONVENTION
When heat is absorbed, q=+ve
When heat is evolved from the system, q=-ve
When work is done by the system, w=-ve
When work is done on the system, w=+ve
 First law of thermodynamics:
• This law is also known as the law of conservation
of energy.
• Statements of this law are as follows:
i) Energy can neither be created nor be
destroyed, only it can be changed from one
form to other form.
ii) When a particular energy of one form is
disappear then equal amount of other form of
energy is appeared.
Iii) Total energy of universe remains constant.
Mathematical statement of first law of
thermodynamics:
If a system of internal energy E1 absorbs heat q,
it’s certain amount is used to do some external
work(w) by the system and certain heat is used
to increase internal energy of the system from E1
to E2.
• From the sign convention:
E2 = E1 + q – w
E2 – E1 = q – w

∆ E = q-w………….(1)
q = ∆E + w……….(2)
q= ∆ E + P∆V ……..(3)
Equations (1) ,(2) and (3) are mathematical statements
of first law of thermodynamics.
• In isothermal process
q= w because at constant temperature is
constant.
In adiabatic process q=o
i.e. ∆E= -w
In adiabatic process work is done on the system
by increase of internal energy.
Isochoric process: w=o
q= ∆E
In the isochoric process, there is maximum change in
internal energy.
Limitations of first law of thermodynamics:
i) It fails to explain about the direction of flow of heat.
Ii) It does not explain why is efficiency of heat engine
not 100%
Iii) It does not explain about the spontaneous process.
 Enthalpy
• It is heat content of the system, it is denoted by H. It is
thermodynamic state function. It is defined as
• H= E + P V
• Where E is internal energy, P and V are pressure and volume
respectively.
• It is difficult to measure the absolute enthalpy of the system but
the change in enthalpy can be experimentally measured.
For the chemical reaction
 ∆ H = Hp- Hr
Where Hp = enthalpy of product 
Hr = enthalpy of reactant
• Let Er is internal energy of reactant and Vr is
the volume of reactant at given pressure P
• Hr= Er + PVr………………..(1)
• Let Ep is internal energy of product , Vp is the
volume of the product at same pressure P.
• Hp = Ep + PVp………………..(2)
• From equations (1) and (2)
• ∆ H= (Ep- Er) +P(Vp- Vr)
∆ H = ∆ E + P ∆ V………………(3)
• Equation (3) shows relationship between
enthalpy change, internal energy change and
volume change at constant pressure.
• From first law of thermodynamics, at constant
pressure.
q= ∆ E + P ∆ V………………(4)
• From equations(3) and (4)
∆H=q
For endothermic reaction
q=+ve
∆H= +Ve
Hp>Hr
For exothermic reaction
q=-ve

∆H= -ve
Hp<Hr
 Relation between enthalpy change and
internal energy change:
• At constant pressure the relation between
enthalpy change, internal energy change and
volume change is given as
• ∆H = ∆E + P∆V……..(1)
In case of solid and liquid reactions, volume
change is nearly zero.
Hence for solid and liquid reaction
∆H = ∆E
• In case of gaseous reaction ∆H and ∆E are not equal
because volume change is significant.
• For ideal gas
• PV=nRT………..(2)
• At constant temperature and pressure
P ∆ V = ∆nRT………(3)
By putting the value of P ∆ V in equation (1) we get
∆H = ∆E + ∆nRT………..(4)
Equation (4) is the required relationship between ∆H
and ∆E for gaseous reaction at constant temperature
and pressure.∆n= total moles of products – total moles
 Factors affecting on the enthalpy change:

• It depends on
• i) Temperature
• Ii) pressure
• Iii) state of the product formed.
 Standard enthalpy change( ∆H ) o

• The enthalpy change when temperature is 25oC

and pressure is 1atm. is called standard enthalpy
change. It is denoted by ∆Ho

Enthalpy change of reaction or heat of reaction:

The enthalpy change or amount of heat absorbed
or evolved when all the moles of reactants are
combined to give product is called heat of reaction
or enthalpy of reaction.
 Types of heat of reaction
• 1.Heat of formation or enthalpy of formation:
The amount of heat absorbed or evolved or
enthalpy change when one mole of compound is
formed from it’s constituent elements is called
heat of formation or enthalpy of formation.
• Heat of formation = heat of reaction/number
of moles of products
• 2H2 + O2 2H2O ∆H = -136Kcal.
• Heat of formation of water = -136/2
• =-68 Kcal/mole
• Heat of formation of diatomic gas is zero.
Heat of combustion or enthalpy of combustion:
The amount of heat evolved or enthalpy change
when one mole of compound is completely oxidized
by excess of oxygen is called heat of combustion or
enthalpy of combustion.
• For example
C + O2 CO2 ∆H=-94.4KCal.
C + 1/2O2 CO ∆H=-26.8KCal.
The heat of combustion of carbon is -94.4KCal.
Calorific value: The amount of energy evolved
when 1gram of food or 1ml of fuel is completely
oxidized by excess of oxygen is called calorific
value of food or fuel.
 Heat of neutralization or enthalpy of
neutralization:
• The amount of heat evolved when one gram
equivalent of acid or base is completely
neutralized is called heat of neutralization.
• The heat of neutralization of strong acid and
strong base is generally -13.68KCal.
• The heat of neutralization of weak acid and
weak base is less than -13.68KCal. Because part
of heat is lost for the complete ionization weak
acid or weak base.
 Heat of solution
• The amount of heat absorbed or evolved
when one mole of solute is completely
dissolved by the excess of solvent is called
heat of solution. When solution is cooled by
dissolution heat of solution is endothermic in
nature. When solution is hot by dissolution
then heat of solution is exothermic in nature.
 Heat of physical changes or enthalpy of
physical changes:
• Heat of fusion
• Heat of vaporization
• Heat of sublimation
 Heat of fusion
• Heat of fusion:-Heat of fusion is the enthalpy
change or amount of heat absorbed when one
mole of solid is converted into liquid.
• H2O(s) H2O(l) ∆H=6.1KJ
• Thus heat of fusion of ice is 6.1KJ/mol.
 Heat of vaporisation
• The amount of heat absorbed or enthalpy
change when one mole of liquid is completely
converted into vapor is called heat of
vaporisation.
• H2O(l) H2O(g) ∆H=43.9KJ
Hess’s law of constant heat of summation:

• Statement: For a particular chemical process

amount of heat absorbed or evolved is
constant though it occurs in one step or in
series of steps.
• Method-I
• A product ∆H =∆H1
 Method-II

• A B ∆H=∆H2
• B C ∆H =∆H3
• C product ∆H=∆H4
From Hess’s law,
∆H1 = ∆H2 +∆H3 +∆H4
Theoretical proof
• if A gives product by method first it absorbs ∆H1
amount of heat. If A gives product by method
second then it absorb ∆H2+∆H3+∆H4
amount of heat . If total amount of heat absorbed
and evolved in the same process is not equal then
it contradicts the first law of thermodynamics.
Hence, Hess’s law is theoretically proved on the
basis of first law of thermodynamics.
 Experimental verification of first law of
thermodynamics
• Carbon dioxide can be prepared by two ways:
• In method first it can be prepared in only one step by
complete combustion of carbon.
• C(s) + O2(g) CO2(g) ∆H= -94.4Kcal.
• In method second carbon is first partially oxidized to
carbon monoxide then carbon monoxide into carbon
dioxide in two steps.
• C(s) + ½ O2(g) CO(g) ∆H1= -26.8Kcal
• CO(g)+1/2O2(g) CO2(g) ∆H2=-67.6Kcal.
• Total amount of heat evolved in each process is -94.4Kcal.
Hence, it verifies the Hess’s law of constant heat of
summation.
• Application of Hess’s law:
• i) It helps to calculate the heat of formation, heat of
combustion and other type of heat of reactions.
• Ii) By the application of Hess’s law the two
thermochemical equations can be added. A
thermochemical equation is multiplied by certain integer.
One thermochemical equation is subtracted from other .
 Numerical problems
• Calculate the enthalpy of formation of NH3
from the following equation
• N2(g) +3H2(g) 2NH3(g) ∆H=-186kj
• Solution:
• Heat of formation =
• = = -93kj/mol.
• Calculate the enthalpy of formation of benzene, if enthalpy of
combustion of benzene, carbon and hydrogen are
-3280kj/mol., -395kj/mol. and -285kj/mol. respectively.
• C6H6 + O2 6CO2+ 3H2O ∆H=-3280kj…. (1)
• C + O2 CO2 ∆H=-395kj…… (2)
• H2 + O2 H2O ∆H=-285kj ……. (3)
• In equation (1)
• ∆H= ∑ ∆Hproduct - ∑ ∆Hreactant
• -3280kj = 6(-395) + 3(-285) –[∆HC6H6+ 0]
∆HC6H6 = -2370-855+3280
• =55KJ/mol.
• Enthalpy of formation of benzene, water and
carbon dioxide are 55kj/mol.,-285kj/mol. and
--395kj/mol. respectively. Find the enthalpy of
combustion of benzene.
 Bond energy
• The amount of energy required to dissociate
one mole of particular type of bond is called
bond dissociation energy. In the chemical
reaction bond dissociation is endothermic
process and bond formation is exothermic
process. In chemical reaction bond
dissociation of reactants and bond formation
of products occur.
• By the help of bond energy method, enthalpy change is
given as below:
• ∆H =∑bond energies of reactants - ∑bond energies of
products
• Qn-1. The bond dissociation energy of hydrogen and
chlorine are 435kj/mol. and 243 kj/mol. The bond
dissociation energy of HCl is 431kj/mol. Find the
enthalpy of reaction
• H2 + Cl2 2HCl
• Also find the enthalpy of formation of HCl.
• Solution:
• Bond energy of hydrogen = 435kj/mol.
• Bond energy of chlorine = 243kj/mol.
• Bond energy of hydrogen chloride = 431kj/mol.
• Enthalpy change of reaction (∆H) = ∑bond energies of
reactants - ∑bond energies of products
= (435 + 243) -2(431)
= 678 – 862
= -184 kj.
Heat of formation of HCl = heat of reaction/number of moles of
product
=-184/2
• The bond energy of hydrogen and chlorine are
435kj/mol. and 243kj/mol. If heat of formation
of HCl is -92kj/mol. then find the bond energy
of H-Cl bond.
• H2 + Cl2 = 2HCl
 Chemical thermodynamics
• Spontaneous process:
• The process which occurs in it’s own direction
with out adding any external agency is called
spontaneous process. Spontaneous process
may be slow or may be fast. It is irreversible in
nature.
• It occurs up to the completion or up to
equilibrium without absorbing any external
energy.
• For example:
• i) Rolling of ball down the hill.
• Ii) Flow of water from higher level to lower
level.
• Iii) Intermixing of gases.
• Iv) Neutralization of acid by base.
• V) Rusting of iron.etc.
• Generally, in spontaneous process energy or
enthalpy is decreased i.e. spontaneous
process is exothermic in nature.
• In terms of enthalpy change,
• If ∆H = -ve then process is spontaneous.
• If ∆H=+Ve then process is non-spontaneous.
• If ∆H= 0 then process is at equilibrium.
• In some of the process, spontaneity occurs though the
process is endothermic,
• For example melting of ice, evaporation of water occur
spontaneously though they are endothermic in nature.
• It means only decrease in enthalpy is not sole criterion
for spontaneity. In the case of melting of ice and
evaporation of water, there is increase in disorder.
• Hence increase in disorder also describe the spontaneity
of the process.
 Entropy(s)
• Entropy is the measurement of disorder or
randomness of the system. It is denoted by s
• It is difficult to measure absolute entropy but
entropy change can be measured as
• ∆S= ∆H/T =q/T
• Unit of entropy change is joule per kelvin or
calorie per kelvin
• The unit of molar entropy change is joule per
kelvin per mole or calorie per kelvin per mole.
 Physical significance of entropy
• Solid molecules are more ordered than liquid .
It means disorder of liquid is more than solid.
Gas is highly disordered than liquid and solid.
• It is found that
• Entropy of solid<entropy of liquid<<entropy of
gas.
• Hence entropy is the measurement of
disorder or randomness of the system.
 Entropy change and spotaneity
• In case of isolated system,
• When ∆s=+ve then process is spontaneous
• When ∆s=-Ve then process is non-
spontaneous.
• When ∆s = 0 then process is at equilibrium.
• For non isolated system
• ∆Suniverse = ∆Ssystem + ∆Ssurrounding
• When ∆Suniverse = +ve then process is
spontaneous.
• When ∆Suniverse = -ve then process is non-
spontaneous
• When ∆Suniverse = 0 then process is at
equilibrium.
 Standard entropy change(∆s ) o

• The entropy change at 25oC temperature and

1atm pressure is called standard entropy
change ∆so. For chemical reaction standard
entropy change is given by
• ∆so =∑∆soproduct - ∑∆soreactant
 Second law of thermodynamics
• Statements:
• 1.In a cyclic process heat can not flow from low
temperature to high temperature
spontaneously with out doing external work on
it.
• 2. Total heat absorbed from the source of heat
engine can not be converted into work with out
any changes on it. It means efficiency of heat
engine is never 100% or unity.
• 3. Spontaneous process is irreversible in
nature.
• 4. Natural process occurs spontaneously i.e.
entropy of universe increases day by day.
• 5. Total heat can not be converted into work
but total work can be converted into heat.
 Explanation of second law of
thermodynamics
• system

Ssu
sT
• T1
y
surrounding
T2
T1>T2
• Let Q amount of heat is followed from low temperature
surrounding to high temperature system.
• ∆Ssystem = Q/T1
• ∆Ssurrounding =- Q/T2
• T1>T2
• Q/T1<Q/T2
• ∆Suniverse = ∆Ssystem + ∆Ssurrounding
• ∆Suniverse = Q/T1 –Q/T2
• ∆Suniverse = -ve
• Since ∆Suniverse is found in negative so heat can
not follow spontaneously from low
temperature surrounding to high temperature
system.
 Types of entropy change
• Entropy of fusion: Entropy change when one mole of
solid is completely converted into liquid is called
entropy of fusion.
• ∆Sfusion =
1.The latent heat of fusion of ice is 336j/g. Find the
molar entropy of fusion of ice.
Hint:
∆ Hfusion = 336j/1g = 336X18 j/mole.
T = 273K
 Entropy of vaporization
• The entropy change when one mole of liquid
is completely converted into vapor is called
entropy of vaporization.
• ∆Svap. = =
 Gibb’s free energy
• The thermodynamic function which indicates the
maximum use full work can be done by the
system is called Gibb’s free energy. It is denoted
by G and defined as
• G = H-TS……………..(1)
• Where H is enthalpy, T is absolute temperature
and S is entropy of the system.
• It is state function because it’s change does not
depend on path but depends on state.
• It is difficult to measure absolute Gibb’s free energy but
decrease in Gibb’s free energy is equal to the useful work done
by the system.
• ∆G = G2 –G1
• G2 is final Gibb’s free energy and G1 is initial Gibb’s free energy.
• At same constant temperature and pressure
• G1 = H1 – TS1
• G2 = H2 – TS2
• ∆G = (H2-H1) – T(S2-S1)
• ∆G = ∆H -T ∆S…………….(2)
• This equation is known as Gibb’s Helmholtz’s
equation.