Thermochemistry PDF

Vidyamandir Classes Thermochemistry
Thermochemistry
BASICS Section - 1
In this chapter, we will study the heat changes that take place when a chemical process occurs. Heat
(a form of energy) is either evolved or absorbed in the course of chemical reaction. The study of energetics
considers the relationship between thermodynamical functions : heat (q), work (W) and internal energy
(U or E).
1. Definitions :
System :
A small portion of the universe with-in which we confine our study of energy changes is called as a system.
Surroundings :
The remainder of the universe (i.e., apart from the system), which can interact with the system is called as
surroundings.
Open System :
This type of system can exchange matter as well as energy
with surroundings. The boundary is not sealed and not
insulated. Sodium reacting with water in an open bea-
ker is an example of open system.
Closed System :
This type of system can exchange energy in the form of
heat, work or radiations but not matter with its sur-
roundings. The boundary between system and surround-
ings is sealed but not insulated. For example, liquid in con-
tact with vapour in a sealed forms a closed system. Heat
can be transferred through the walls of the tube to the sur-
roundings but total amount of matter remains the same as
vapours cannot escape.
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Thermochemistry Vidyamandir Classes
Isolated System :
This type of system has no interaction with its sur-

roundings. Neither matter nor energy can be exchanged
with surroundings. A substance contained in an ideal ther-
mos-flask is an example of an isolated system.
2. Thermodynamics Properties :
(i) Intensive Properties :
The properties which do not depend upon the quantity of matter present in the system are called
Intensive properties. Pressure, temperature, specific heat, surface tension, refractive index, viscos-
ity, melting point, boiling point, volume per mole (molar volume), concentration, colour potential
electrical field electrical resistivity, specific energy, etc. are examples of intensive properties of the
system.
(ii) Extensive Properties :
The properties whose magnitude depends upon the quantity of matter present in the system are
called Extensive Properties. Internal energy, total moles, volume, enthalpy, entropy, Gibbs en-
ergy, length, mass, electrical resistance etc. are examples of extensive properties.
3. Internal Energy (U) :
All the possible forms of energy that are associated with a system are referred to as Internal Energy. It
includes kinetic energy due to all kind of motion of the particles of the system, and their potential energy due
to intermolecular forces (interaction). It is impossible to measure the exact value of the internal energy of a
system. It can be measured when the system changes its state i.e. as change in internal energy (U).
The internal energy change of a system depends upon the state of the system and not on how the system
achieved the particular state. Such a thermodynamic function is called as state function. Other examples
are: temperature, pressure volume, enthalpy, entropy, Gibbs energy etc.
If U1 is the internal energy of a system in state 1, and U2 in the state 2, then the change in the internal energy
of the system (U) is given by : U = U2 – U1
As stated above, U is independent of the process which takes the system from state 1 to state 2.
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4. First law of Thermodynamics :

Energy can neither be created nor destroyed, although it can be transformed from one form
to another.
If we supply an amount of heat (= q) to the system in state 1, the system does a work w and goes to achieve
the state 2. The heat supplied to the system gets converted into two parts :
(a) Work done by the system
(b) Change in internal energy of the system.
From law of conservation of Energy, we have :
q = U + (– w) . . . . (i)
This equation is known as First Law of Thermodynamics.
5. Sign Convention :
 w is positive, when the work is done on the system.
 w is negative, when the work is done by the system.
 q is positive, when the heat is supplied to the system.
 q is negative, when the heat is lost by the system.
6. Enthalpy :
It is a thermodynamic function (H) defined to study heat changes in chemical reactions. It is also known as
heat content of the stem defined as :
H = U + PV where P : Pressure V : Volume
If the change of state takes place at constant pressure, q is denoted as qp (heat transfer at constant pres-
sure). It is also known as change in enthalpy of the system, represented as
H = qp (H : Enthalpy of the system).
In such a process, volume of the system will change and work done is given as :
w = – P V V : change in volume
 qp = U + P V [Using first law of thermodynamics]
or qp = U2 – U1 + P (V2 – V1)
or qp = (U2 + PV2) – (U1 + PV1)
or qp = H2 – H1 = H where H1 = U1 + PV1 = enthalpy of the system in state 1
and H2 = U2 + PV2 = enthalpy of the system in state 2
Enthalpy change like internal energy change in a state function.

Heat change in all chemical reactions is studied as enthalpy change of the reaction (rH). System in state 1
is taken as system of reactants and in state 2 taken as system of products. Enthalpy change (Heat change)
accompanying the reaction is given as :
rH = Enthalpy of products – Enthalpy of reactants =  (Hproduct) –  (Hreactants)
If the change of state takes place at constant volume, q is denoted as qv (heat transfer at constant volume).
U = qv
7. Exothermic and Endothermic reactions :

(a) Exothermic reactions :
Chemical reactions in which heat is evolved are known as exothermic reactions.
For example : 2Mg(s) + O2(g) 
 2MgO(g)
N2(g) + 3H2(g) 
 2NH3(g)
Both of the above reactions are exothermic reactions because heat is evolved in them.
In general, an exothermic reaction is represented as : Reactants 
 Products + heat
Here enthalpy (or heat content) of reactions is partially transferred to the enthalpy of the products
and partially evolved as heat.
If HR : enthalpy of reactants and HP : enthalpy of products
Clearly, HP < HR  rH < 0 [rH = HP – HR]
i.e. for exothermic reaction, rH (reaction enthalpy) will bear a – ve sign (evolution of heat)
Note : In exothermic reaction, for some time (i.e. during the change) temperature of the products will rise above
room temperature. But, very soon the heat is lost to surroundings and the same temperature is maintained.
(b) Endothermic Reactions :

Chemical reactions in which the heat is absorbed from the surroundings are known as
endothermic reactions.
For example : N2 (g) + O2 (g) 
 2 NO (g)
H2 (g) + I2 (g) 
 2 HI (g)
Both of the above reactions are endothermic reactions because in them heat is absorbed from the
surroundings.
In general, an endothermic reaction can be expressed as :
Reactants + heat 
 Products

Here, enthalpy of products is derived from enthalpy of reactants plus the absorbed heat.
Clearly HP > HR
 rH > 0 [rH = HP – HR]
i.e. for endothermic reactions, rH (reaction enthalpy) will bear a +ve sign (absorption of heat)
Note : In endothermic reactions, (unlike exothermic reactions), temperature of the reacting mixture falls during the
change. But very soon, heat is absorbed from the surrounding and same temperature is restored.
8. Enthalpy Change at Standard Conditions :

rH depends upon the conditions under which a reaction is performed. So to compare enthalpy changes of
various reactions, they are performed at standard conditions.
Standard conditions for temperature and pressure are 298 K (or 25°C) and 1.0 atm pressure. Any enthalpy
change measured under these conditions is known as Standard Enthalpy change or Standard Heat of
reaction and it is denoted as  r H  .
It is also important to specify the states of all reactants and products in a reaction. [‘s’ for solids, ‘l’ for
liquids, ‘g’ for gases (or free atoms), ‘aq’ for solution in water].
A chemical reaction which clearly informs about the heat change accompanying it (i.e. exothermic or endot-
hermic) and the physical state of all reactants and products is known as Thermochemical Equation.
1
For example :  CO( g ) ;
C(s)  O2 ( g )  rH1 = – 385.2 kJ (Exothermic)
2
1 1
N2 ( g )  O2 ( g ) 
 NO( g ) ; rH = + 90.25 kJ (Endothermic)
2 2
Note : rH is the reaction enthalpy for a reaction in any form (i.e. stoichiometric coefficients) e.g. refer to the
reaction below :
2C(s) + O2 (g) 
 2 CO(g) ; rH2 = – 770.4 kJ (Exothermic)
Here, rH2 =2 rH1
9. Enthalpy of a Compound :
To define the enthalpy of a compound, it is taken that the enthalpy of an element in its most stable state at
standard conditions is zero.

Standard states of some elements :

C : Graphite ; S : Rhombic ; Br as Br2 () ; I as I2 (s); H as H2 (g) ;
Cl as Cl2 (g); N as N2 (g) ; O as O2 (g);
P : White (Exception : Red Phosphorus is more stable than White Phosphorus)
e.g. H
Cl 2 (g)
 0 ; H
H 2 (g)
0; H
O 2 (g)
 0; H
Br2 ( )
 0 ; H
I2 (s)
0;
Consider the following thermochemical equations at 25°C and 1 atm.
1 1
H2 (g) + Cl2 (g) 
 HCl (g)
2 2
It represents formation of HCl at standard conditions i.e.  f H   H of given reaction
From definition : rH =  (Hproducts) –  (Hreactants) =  ai (H)m, products –  bi (H)m, reactants
[Hm is the molar enthalpy of the compound and ai & bi the stoichiometric coefficients of products and
reactants respectively]
1  1  
  r H   f H   H 
HCl   H H 2  H Cl2  [see definition of  f H  in Section – 2]
2 2 
  f H   H HCl  0 [Enthalpy of elements in standard state = 0]
 H 
(HCl)   f H(HCl)
Hence the enthalpy of a compound is the standard heat of formation of the compound OR enthalpy
of a compound is often taken as standard enthalpy of formation of that compound.
Enthalpy of a compound A at standard conditions =  f H  of A
 
Note : By convention,  f H  H   aq   0
Illustration - 1 How much heat is evolved by the preparation of 100 gm of iron by the following
reaction ?
 2 Fe(s) + Al2O3 (s) ; rH = – 202.6 kcal/mol
2 Al (s) + Fe2O3 (s) 
SOLUTION :
From thermochemical reaction, it is clear that 202.6 kcal of heat is involved when two moles of Fe (iron) is
formed.
 2 moles of Fe  202.6 kcal
 1 mole of Fe  101.3 kcal
 100/56 mole of Fe  101.3 × 100/56 = 180.9 kcal

Heat of Reaction Section - 2
The heat of a reaction can be assigned special names in the following manner :
(a) Standard Heat of Formation (  f H  ) :

The heat evolved or absorbed when one mol of any compound is formed from its elements in their
standard states. It is usually denoted by  f H    f H  can be given –ve or +ve sign, depending
upon whether formation is exothermic or endothermic.
C(s, graphite) + 2 H2 (g) 

 CH4 (g) ;  f H  = – 74.3 kJ/mol
1 1
H2 (g) + I2 (s) 
 HI (g) ;  f H  = 25.92 kJ/mol
2 2
Note : To write chemical equations for formation, balance the reaction for one mole of compound whose formation
is to be studied.
(b) Standard Heat of Combustion (  c H  ) :

The heat evolved (or enthalpy change) when one mole of any substance is completely burnt in excess
of oxygen.
 c H  will always bear –ve sign for it being enthalpy change of an exothermic reaction.
CH4(g) + 2 O2(g) 
 CO2(g) + 2 H2O() ;  c H  = –212 kcal/mol
C(s, graphite) + O2(g) 

 CO2 (g) ;  c H  = –94 kcal/mol
Note : To write chemical equations for combustion, balance the reaction for one mole of compound whose com
bustion is to be studied.
Illustration - 2 15
Calculate  r H  for the reaction : C6H6 () + O (g) 
 6 CO2 (g) + 3 H2O ()
2 2
Given the standard heat of formations (  f H  ) of H2O (), CO2 (g) and C6H6 () are – 57.80 kcal/mol,
– 94.05 kcal/mol and 19.8 kcal/mol respectively.
SOLUTION :
Whenever, standard heat of formation (  f H  ) of a compound is given it means that enthalpy of
that particular compound at standard state is given. Also, note that in the question, molar enthalpy
changes are given.

Using the definition of enthalpy change as : rH = H(products) – H (reactants)
For the given reaction :  r H   (H  

products )   (H reactants )
or  r H   (f H  
products )  (  f H reactants )
15
C6H6 () + O (g) 
 6 CO2 (g) + 3 H2O ()
2 2
f H 19.8 0 (–94.05) (–57.8)
  r H  = [6 × (–94.05) + 3 × (–57.8)] – [19.8] = – 757.50 kcal/mol.
(c) Heat of Dissociation (  bond H  ) :

It is the amount of energy required to break one mole of bonds in a molecule (in gas phase) into
gaseous atoms.
 2H (g) ;  bond H  = 103 kcal/mol

H – H (g) 
 2C (g) ;  bond H  = 80 kcal/mol

C – C (g) 
Note : (i)  bond H  is always positive i.e. energy is always required to break the bond between two atoms.
(ii) Whenever a bond is formed between two atoms in gaseous state, energy is always released.
(d) Heat of Phase change :

It is the amount of energy required to change the phase of a substance under the particular conditions
for the phase change.
H2O (s) 
 H2O () ;  fus H  = 6 kJ/mol at 273 K and 1 atm
H2O () 
 H2O (g) ;  vap H  = 40.8 kJ/mol at 373 K and 1 atm
CO2 (s) 
 CO2 (g) ; sub H = 108 kcal/mol at 195 K and 1 atm
Note : (i)  fus H  : Amount of heat required to melt one mole of a substance at a constant temperature
and 1atm pressure.
(ii)  vap H  : Amount of heat required to vaporize one mole of a substance at a constant
temperature and 1 atm pressure.
(iii) sub H : Amount of heat required to sublime one mole of a substance at a constant
temperature and 1 atm pressure.

(e) Heat of Atomization (  a H  ) :

It is the amount of energy required to break the bonds in a molecule (in gas phase) into gaseous
atoms.
Na (s) 
 Na (g) ;  a H  = 108 kJ/mol
H – H (g) 
 2H (g) ;  a H  = 435 kJ/mol
CH4 (g) 
 C (g) + 4 H (g) ;  a H  = 1665 kJ/mol
Note : (i) For a monoatomic molecule (i.e. atom) in solid phase,  a H  is also called as sub H  .
(ii) For a diatomic molecule,  a H  is also called as  bond H  .
(iii) For a polyatomic molecule, it is the enery required to break all the bonds to form gaseous atoms.
(f) Average Heat of Dissociation ( mean, bond H  ) :
It is the average amount of energy required to break one mole of bonds in a polyatomic
molecule (in gas phase) into gaseous atoms.
CH4 (g) 
 C (g) + 4 H (g) ;  a H  = 1665 kJ/mol
Note : In general, in a polyatomic molecule, the energy required to break a bond changes in the successive bond
dissociations. For example :
CH4 (g) 
 CH3 (g) + H (g) ;  bond H1
CH3 (g) 
 CH2 (g) + H (g) ;  bond H 
2
CH2 (g) 
 CH (g) + H (g) ;  bond H 3
CH (g) 
 C (g) + H (g) ;  bond H 
4
 1 
Here :  bond H1   bond H 2   bond H3   bond H 4 and  mean, bond H   a H
4

(g) Heat of Lattice(  lattice H  ) and Heat of Hydration(  hyd H  ) :
 lattice H  : It is the energy required to break one mole of an ionic compound into ions in their
gaseous atoms.
 Na+ (g) + Cl– (g)

NaCl (s)  ;  lattice H  = 787 kJ/mol
 hyd H  : It is the energy released when atoms (gaseous) in one mole of an ionic compound gets
hydated.
Na+ (g) + Cl– (g) (  NaCl ) 

 Na+ (aq.) + Cl– (aq.) ;
 hyd H  = –783 kJ/mol

Note :  lattice H  is always positive and  hyd H is always negative.
(h) Heat of Solution ( sol H  ) :
It is the change in enthalpy when one mole of a substance (solute) is completely dissolved in excess of
water.
 Na+(aq) + Cl–(aq)
NaCl(s) + aq  ; sol H  = 5 kJ
HCl(g) + aq 
 HCl(aq) ; sol H  = –x kJ

Note : (i) sol H  =  lattice H  +  hyd H (can be positive or negative)
(ii) Generally, when gases are dissolved, heat is evolved. In case of salts (solids), heat is absorbed
except when anhydrous salts are dissolved.
(i) Heat of Ionisation ( ionisation H  ) :
It is the amount of heat absorbed when one mole of a compound completely dissociates into ions in a
solution.
 H+(aq) + CN–(aq)
HCN(aq)  ; ionisation H  = + p
 NH4+(aq) + OH–(aq)
NH4OH(aq)  ; ionisation H  = + q

(j) Heat of Neutralisation (  neutralisation H  ) :
It is the amount of heat liberated when one gm-equivalent of acid completely neutralises by one gm-
equivalent of base. In water, all strong acids (HCl, H2SO4, HNO3) and strong bases [NaOH, Ca(OH)2,
etc] ionise completely.  neutralisation H  is constant for strong acid and base neutralization and is
equal to –13.7 kcal/mol = –57.27 kJ/mol.
Neutralisation can be treated as :
H +(aq) + OH–(aq)  H2O ()

 ;  neutralisation H  = –13.7 kcal/mol
Note : (i)  neutralisation H  for weak acids (HCN, CH3COOH, benzoic acid) and weak bases (NH4OH,
amines) is lower than that for strong acids and bases. The reason is that heat is absorbed in complete
ionisation of weak acids and bases (unlike in case of strong acids and bases where no heat is required
for ionisation).
(ii)  neutralisation H  for the reaction between HCl and NaOH in aprotic solvents (solvents which doesn’t
ionizes) e.g. benzene etc. is less than –13.7 kcal/mol because HCl is a polar covalent substance and
doesnt get ionizes in aprotic solvent so requires non-zero ionisation H  for neutralization.
(iii)  neutralisation H  for the reaction between HF and NaOH is –16.27 kcal/mol which is greater than
the expected value of –13.7 kcal/mol (obviously to be compared in terms of magnitude). The differ-
ence is due to a very high heat of hydration of flouride ion due to its small size.

Hess’s Law of Constant Heat Summation Section - 3
It states that change in enthalpy for any chemical reaction is constant, whether the reaction occurs
in one step (directly) or in several steps (indirectly).
OR
The enthalpy change in a reaction depends upon initial and final states and is independent of the
route followed to complete the reaction.
It is the direct consequence of law of conservation of energy. rH of overall reaction will be obtained by
“appropriate summation” of the changes in enthalpies of various intermediate steps.
Illustrating the concept :
Find the enthalpy change for formation of NO2(g).
1
N (g) + O2 (g) 
 NO2(g) ; f H = ?
2 2
Using given thermochemical equations, and applying Hess’s Law :
1 1
(i) N2 (g) + O2 (g) 
 NO (g) ; rH1  (f H) NO
2 2
1
(ii) NO (g) + O (g) 
 NO2 (g) ; rH2  (c H) NO  ( f H) NO2
2 2
Adding two equations, we get :
1
N (g) + O2 (g) 
 NO2 (g)  rH = rH1 + rH2
2 2
Illustrating the concept :
1
Find rH of reaction : H2 (g) + O (g) 
 H2O (g)
2 2
1
(i) H2(g) + O (g) 
 H2O () ; rH1= –68.3 kcal/mol  (f H)H 2O  (c H)H 2
2 2
(ii) H2O () 

 H2O (g) ; rH2 = 10.52 kcal/mol  ( vap H)H 2 O
From Hess’s Law : rH = rH1 + rH2 = (–68.3) + (10.52) = –57.78 kcal/mol

Illustration - 3Enthalpy of neutralisation of acetic acid by NaOH is 50.6 kJ/mol. Calculate H for ionisation
of CH3COOH. Given, the heat of neutralisation of a strong acid with a strong base is –57.3 kJ/mol.
SOLUTION :
The neutralisation of a strong acid by a strong base is represented as :
H+ (aq) + OH– (aq) 

 H2O () ;  Neutralisation H   57.3 kJ / mol
Now acetic acid is a weak acid, so its neutralisation is represented in two stages: First complete ionisation
of weak acid and then complete neutralisation of the fully ionised acid by the base.
1.  CH3COO– (aq) + H+ (aq) ;  Io n isatio n H   ?

CH3COOH (aq) 
2. H+ (aq) + OH– (aq) 

 H2O () ;  Neutralisation H   57.3 kJ / mol
Now adding the two equations to get the equation of neutralisation ;
 CH3COO– (aq) + H2O () ;  Neutralisation H   50.6 kJ / mol

CH3COOH (aq) + OH– (aq) 
From Hess’s Law :  Ionisation H   ( 57.3)  50.6   Ionisation H   6.7 kJ / mol
Illustration - 4 Find the heat of formation of ethyl alcohol from following data :
C (s) + O2 (g) 
 CO2 (g) ; rH = –94 kcal/mol
1
H2 (g) + O (g) 
 H2O () ; rH = –68 kcal/mol
2 2
C2H5OH () + 3O2 (g) 
 2 CO2 (g) + 3 H2O () ; rH = –327 kcal/mol
SOLUTION :
Always write the balanced thermodynamic equation for which rH is to be calculated.
1
2 C (s) + 3 H2 (g) +  C2H5OH () ; fH = ?
O (g) 
2 2
Given :
I. C (s) + O2 (g) 
 CO2 (g) ; rH1 = –94 kcal/mol  (f H)CO 2  (c H)C
1
II. H2 (g) + O (g) 
 H2O () ; rH2 = –68 kcal/mol  (f H)H 2O  (c H)H 2
2 2
 2 CO2 (g) + 3 H2O () ; rH3 = –327 kcal  (c H)C2 H5OH
III. C2H5OH () + 3O2 (g) 

Now adding appropriately to get the required equation (Using Hess’s Law) :
Operate : 2 (I) + 3(II) – (III) to get :
1
2 C (s) + 3 H2 (g) + O (g) 
 C2H5OH ()
2 2
From Hess’s Law : fH = 2(rH1) + 3(rH2) - rH3 = 2 (–94) + 3(–68) – (–327) = –65 kcal/mol
Illustration - 5 From the following data, calculate the standard enthalpy change for the combustion of
cyclopropane at 298 K :
The enthalpy of formation of CO 2 (g), H 2 O() and propene(g) are –393.5, –285.8 and 20.42 kJ mol–1
respectively.
The enthalpy of isomerisation of cyclopropane to propene is –33.0 kJ mol–1.
SOLUTION :
9
CH3CH = CH2(g) + O (g) 
 3CO2(g) + 3H2O() . . . . (i)
2 2
       9  
c H (Propene) = 3 f H(CO2 )  3 f H (H 2O)     f H(Propene)   f H O2 
 2 
= 3 (– 393.5) + 3 (– 285.8) – (20.42) = – 2058.32 kJ mol–1
To the above reaction, if we add the reaction :
isomerization H   33.0 kJ mol1
we get :

Hence, c H(cyclopropane)  (2058.32  33.0) kJ mol 1  2091.32 kJ mol 1

Heat of Reaction and Bond Energy Section - 4
Let us consider that the bond energy of AB molecule is x kcal/mol.

Bond Formation :  A – B ; rH = – x
A + B  (Bond formation is exothermic)
Bond Dissociation :  A + B ; rH = + x
A – B  (Bond dissociation is endothermic)
During a chemical reaction, atoms and molecules are rearranged to form new molecules. During
the course of chemical reaction, old bonds are broken (of reactants) and new ones are formed (of
products).
A given chemical reaction can be analysed energetically into two parts :
(i) Bond Breaking (endothermic, rH > 0)
(ii) Bond Formation (exothermic, rH < 0)
If rH1 is the enthalpy change during bond breaking (i) and rH2 is the enthalpy change during bond
formation (ii), then overall enthalpy change of the reaction (rH) is given by Hess’s Law:
rH = rH1 + rH2
As discussed, rH can be calculated using Hess’s law of constant heat summation or using :
rH = H Product  H Reactants .
rH can also be theoretically calculated using bond energies in the following manner :
(i) On the reactants side, calculate the energy required to break all the bonds. If there is an element in
Solid / Liquid state, also consider the energy required to convert it into gaseous state.
(ii) On the products side, calculate the energy released when products are formed. If there is an ele-
ments/compound in Solid/Liquid state, also consider the energy released when it is converted from
gaseous state to the required state.
(iii) Add total energy released and absorbed to get rH.
Illustration - 6 Find rH of the reaction : OF2 (g) + H2O (g) 

 O2 (g) + 2 HF (g) ;
Average bond energies of O–F, O–H, O = O, H–F are 44, 111, 118 and 135 kcal/mol respectively.
SOLUTION :
OF2 (g) + H2O (g) 
 O2 (g) + 2 HF (g) ; rH = ?
(i) Bond Breaking: (endothermic) : rH1
 O (g) + 2 F (g) ; rH = + 2 × 44
F – O – F (g)  [bond energy of O – F = 44]
 O (g) + 2 H (g) ; rH = + 2 × 111
H – O – H(g)  1 [bond energy of O – H = 111]
 rH1 = 2 × 44 + 2 × 111 = + 310 kcal.

(ii) Bond Formation: (exothermic) : rH2

O (g) + O (g) 
 O = O(g) ; rH = –118 [bond energy of O = O = 118]
2[H (g) + F (g) 
 H – F (g)] ; rH = – 2 × 135 [bond energy of H – F = 135]
 rH2 = –118 + (–2 × 135) = –388 kcal
Now using Hess’s Law ; rH = rH 1 + rH2 = 310 + (–388) = –78 kcal
Illustration - 7 Find f H of HCl (g) if bond energies of H2, Cl2 and HCl are 104, 58, 103 kcal/mol respec-
tively.
SOLUTION :
1 1
H2 (g) + Cl2(g) 
 HCl (g) ; f H = ?
2 2
Now analyse the given thermochemical equation in two parts :
(i) Bond Breaking [rH1] : Endothermic Reaction
H2(g) 
 2 H(g) ; rH = 104 kcal/mol
Cl2(g) 
 2 Cl(g) ; rH = 58 kcal/mol
1
[H (g) 
 2 H(g) ; 104] [as we need mole of each reactant]
2 2
1
[ Cl2(g) 
 2 Cl(g) ; 58]
2
1 1
 rH1 = × 104 + × 58 = 81 kcal
2 2
(ii) Bond Formation : (rH2) : Exothermic reaction
 HCl (g) ; r H = –103 kcal

H(g)+ Cl (g)  (Bond energy of HCl = 103 kJ/mol)
r H2 = –103 kcal
Now r H = f H = r H1 + r H2 (using Hess’s Law)
 f H = 81 + (–103) = –22 kcal/mol

Illustration - 8 Calculate rH for the following homogeous gaseous reaction :

CH3COCH3(g) + 2O2(g) 
 CH3COOH(g) + CO2(g) + H2O(g)
Use the data in kcal mol–1. bond C – H = 99 ; bond C – C = 83 ; bond C = O = 173 ;
bond O = O = 118 ; bond C – O = 84 ; bond O – H = 110
SOLUTION :
First calculate the energy required to break all the bonds in reactants side and to convert them into gaseous
atoms.
H O
| ||
(i) 4H(g) + 2C(g) + 2O(g) 
 H  C  C  O – H (g)
|
H
Energy released = 3Bond C – H + Bond C – C + Bond C = O + Bond C–O + Bond O–H
= 3 × 99 + 83 + 173 + 84 + 110 = 747 kcal

(ii) C (g) + 2O (g) 
 O = C = O (g)
Energy released = 2Bond C = O = 2 × 173 = 346 kcal
 Total energy released = 1313 kcal
 rH = 1169 + (–1313) = –144 kcal mol–1
(iii) 2H(g) + O(g) 
 H – O – H(g)
Energy released = 2Bond O – H = 2 × 110 = 220 kcal
Note : (i) While calculating rH using the bond energy concept, it is important to know the structure of the
molecules/compounds taking part in the reaction.
(ii) If the reaction would have been :
CH3COCH3(g) + 2O2(g) 
 CH3COOH(g) + CO2(g) + H2O()
then we also need to consider the energy released for the conversion of H2O(g) 
 H2O()
rH = –144 – 9.72 = – 153.72 kcal

Illustration - 9 Compute the heat of formation of liquid methyl alcohol, using the following data (in
kJ/mol) : Heat of vaporization of liquid methyl alcohol = 38.
Heat of formation of gaseous atoms from the elements in their standard states: H = 218; C = 715; O = 249.
Average bond energies : C – H = 415; C – O = 356; O – H = 463.
SOLUTION :
The given data is as follows :
(i) CH3OH() 
 CH3OH(g)  r H1Θ  38 kJ mol1
1
(ii) H 2 ( g ) 
 H( g )  r HΘ
2  218 kJ mol
1
2
(iii) C(graphite) 
 C(g)  r H3Θ  715 kJ mol1
1
(iv) O 2 ( g ) 
 O( g ) r HΘ
4  249 kJ mol
1
2
(v) CH(g) 
 C(g) + H(g)  r H5Θ  415 kJ mol1
(vi) CO(g) 
 C(g) + O(g) r HΘ
6  356 kJ mol
1
(vii) OH(g) 
 O(g) + H(g) r HΘ
7  463kJ mol
1
We have to calculate the enthalpy of formation of liquid methyl alcohol, i.e.,
1
(viii) C(graphite) + 2H2(g) + O (g) 
 CH3OH()  r H 8Θ  ?
2 2
First of all, we calculate the enthalpy of reaction :
(ix) CH3OH(g) 
 C(g) + 4H(g) + O(g) ;  r H 9Θ  ?
 H 
 | 
 CH3OH  H  C  O  H 
 | 
 r H 9Θ  3  r H 5Θ   r H Θ Θ
6  r H7  
H
 contains one C  O, one O  H 
 
 and three C  H bonds 
 r H 9Θ = (3415 + 356 + 463) kJ mol = 2064 kJ mol

–1 –1

The equation (viii) can be generated as follows :

Eq. (iii) + 4  Eq. (ii) + Eq. (iv) – Eq. (ix) – Eq. (i)
Hence, the enthalpy of reaction of equation (viii) is given as :
 r H8Θ   r H3Θ  4  r HΘ Θ Θ Θ
2   r H 4   r H9   r H1
= (715 + 4 218 + 249 – 2064 – 38) kJ mol–1 = – 266 kJ mol–1
Illustration - 10 The heat of formation of ethane is –19.5 kcal. Bond energies of H – H, C – H and C – C
bonds are 104.2, 99.0 and 80.0 kcal/mol respectively. Calculate the heat of atomisation of graphite.
SOLUTION :
f H of ethane (C2H6) = –19.5 kcal/mol
2 C (s) + 3 H2 (g) 
 C2H6 (g) ; f H = –19.5 kcal/mol
Let the heat of atomisation is x kcal/mol
Bond Breaking : (rH1) Bond Formation : (rH2)
2[C (s) 
 C(g); +x] 1[C (g) + C (g) 
 C – C (g) ; – 80]
3[H2 (g) 
 2 H (g) ; +104.2] 6[C (g) + H (g) 
 C – H (g) ; – 99]
rH1 = 2x + 312.6 rH2 = (80) + (6 × 99) = 674
From Hess’s Law : f H = r H1 + r H2
–19.5 = (2x + 312.6) – 674  x = 171 kcal.
Illustration - 11 Using the data given below (all values are in kcal/mol at 25°C), calculate the bond ener-
gies of C–C and C–H bonds.
c H Θ ethane   372.0 ; c H Θ propane   530.0 ; a H Θ  172.0 ;

C  Graphite 
 bond H Θ H  H  104.0 ;  f H Θ H O   68.0 ;  f H Θ CO   94.0

2 2
SOLUTION :
From the data given for heats of combustion for ethane and propane, we can calculate the heats of formation
of two compounds (C2H6 and C3H8) as follows :
(a) Writing the equation for combustion of ethane:
7
C2H6 (g) + O (g) 
 2 CO2 (g) + 3 H2O () ;  c H Θ   372.0
2 2

From definition of rH of a reaction : rH = HProducts – HReactants
The enthalpy of a compound is the enthalpy of formation of that compound at standard conditions (i.e.  f H Θ ).
 7 
Δ c H Θ =  2 Δ f HΘ CO  + 3 Δ f HΘ  H O    Δ f HΘ  C H   Δ f HΘ  O  
 2 2   2 6 2 2 
Note that f HΘ(O 2 ) = 0 (as enthalpy of formation of an element in standard state is taken as zero).
 –372 = 2 × (–94) + 3 × (–68) – f HΘ(C2 H6 )
 f HΘ(C2 H6 ) = –20 kcal/mol
(b) Writing the equation for combustion of propane :
C3H8 (g) + 5 O2 (g) 

 3 CO2 (g) + 4 H2O () ;  c H Θ   530.0
From definition of rH of a reaction : rH = HProducts – HReactants
 c HΘ  3 Δ f HΘ CO  + 4 Δ f HΘ H O    Δ f HΘ C H  + 5Δ f H Θ O  

 2 2   3 8 2 
  530  3    94   4  (68)  Δ f HΘ C H 

3 8
 Δf HΘ C H    24 kcal / mol

3 8
Calculations of bond energies :

Let the bond energy of C – C bond = x kcal mol–1 and the bond energy of C – H bond = y kcal mol–1
(a) For ethane, heat of formation is given as :
 f H Θ = – 20 kcal mol
–1
2 C(s) + 3 H2 (g) 
 C2H6(g) ;
Bond breaking (rH1) : Bond formation (rH2) :

2[ C(s)  C(g) ; + 172 ]
 1[ C (g) + C (g) 
 C – C (g) ; –x ]
3[ H2(g) 
 2H(g) ; + 104 ] 6[ C (g) + H (g) 
 C – H (g) ; –y ]
 rH1 = 2 × 172 + 3 × 104 = 656  rH2 = – (x + 6y)
  f H Θ = heat absorbed + heat released = rH1 + rH2

 – 20 = 656 – (x + 6y)  x + 6y = 676 . . . . (i)

(b) For propane, heat of formation is given as :
 r H Θ = –24 kcal mol

–1
3 C(s) + 4 H2 (g) 
 C3H8 (g) ;
Bond breaking (rH1) : Bond formation (rH2) :

3[ C(s) 
 C(g) ; +172 ] 2[ C(g) + C(g) 
 C – C(g) ; –x ]
4[ H2(g) 
 2H(g) ; +104 ] 8[ C(g) + H(g) 
 C – H(g) ; –y ]
rH1 = 3 × 172 + 4 × 104 = 932  rH2 = – (2x + 8y)
  f H Θ = rH1 + rH2
 – 24 = 932 – (2x + 8y)  x + 4y = 478 . . . . (ii)

Solving (i) and (ii), we get x = 82 and y = 99.
 Bond energy of C – C bond = 82 kcal mol–1 and C – H bond = 99 kcal mol–1
Born Haber’s Cycle Section - 5
The energy binding ions together in a crystal is called as lattice energy (  Lattice H Θ ). Lattice energy is
defined as the enthalpy change which occurs when one mole of an ionic compound dissociates into its ions
in gaseous state which means  Lattice H Θ is +ve i.e.,
 Na  ( g )  Cl ( g )
NaCl( s)   LatticeHΘ   790 kJ mol1
These crystal lattice energies cannot be measured directly. By applying Hess’s Law to a series of elemen-
tary processes starting with Na (s) and Cl2 (g) and ending with formation of NaCl(s),  Lattice H Θ can be
calculated. Such a sequence of reactions for ionic compounds is called as Born-Haber Cycle. The
concept is illustrated below by taking the formation of NaCl(s).
The heat of formation of sodium chloride can be calculated from bond energies very easily.
1
 f H Θ = – 411 kJ mol
–1
Na(s) + Cl (g) 
 NaCl(s)
2 2
The following sequences can give the above equation :
1. Sublimation of one mole of Na(s) :
Na (s) 
 Na (g) sub HΘ   109 kJ mol1

2. Dissociation of half mole of Cl2 :
1
Cl (g) 
 Cl (g)
2 2
1
 Bond H Θ  122 kJ mol1
2
(Bond energy of Cl2 is Bond HΘ
= 244 kJ/mole)
3. Ionisation of one mole of Na atoms :
 Na+ (g) + 1e–
Na (g) 
IE HΘ   496 kJ mol1

(First ionisation energy of Na atoms is 496 kJ/mole)
4. Addition of one mole of electrons to one mole of chlo
rine atoms:
Cl (g) + 1e– 
 Cl– (g)
 EA HΘ   348 kJ mol1
(Electron affinity of chlorine is 348 kJ/mole)

(Electron affinity is the energy released, so H is negative).
5. Condensation of gaseous ions to form one mole of solid NaCl :
This can not be calculated directly.
Na+ (g) + Cl– (g) 
 NaCl (s) r HΘ    Lattice HΘ
The summation of the above five reactions and their H values allows us to calculate the value of  Lattice H Θ .
1
f H Θ (–411) = sub HΘ (+109kJ) +  Bond HΘ (+122kJ) +  IE HΘ (+496kJ) + EA HΘ
2
(–348kJ) –  Lattice H Θ
  Lattice H Θ = +790 kJ/mol of solid NaCl.

Note : The crystal lattice is a measure of the stability of an ionic solid. The more negative its value, the more energy
is released in the hypothetical reaction in which a mole of ionic solid is formed from its constituent ions in the
gaseous state.

Illustration - 12 Find the electron affinity of chlorine from the following data (in kcal/mol).
Enthalpy of formation of LiCl is –97.5 ; Lattice energy of LiCl = 197.7 ; Dissociation energy of chlorine
= 57.6 ; Sublimation enthalpy of Lithium = 38.3 ; Ionisation energy of Lithium = 123.8
SOLUTION :
For a ionic compound of type LiCl :
1
 Lattice HΘ Θ Θ
LiCl   EA H Cl   f H LiCl   bond HΘ Θ Θ
Cl2   sub H Li   IE H Li
2
Θ 1
197.7   EA HCl  ( 97.5)   57.6  38.3  123.8
2
  EA H Θ
Cl   90.7 kcal / mol
Relation between rH and rU Section - 6
Enthalpy (H) and Internal Energy (U) are related as :

H = U + PV
 H = U + (PV)
or d H = d U + d (PV)
Now, for a reaction, we can write : rH = rU + PV
[Chemical reactions occur at constant T and P] - 12
Illustration
or rH = rU + ngRT
where n g   (n g ) products –  (n g ) reactants = Change in the number of gaseous moles
Illustration - 13 Find the sign of rH – rU for the following reactions :
(i) H2(g) + Cl2(g) 
 HCl(g) (ii) N2(g) + O2(g) 
 NO2(g)
7
(iii) PH3(g) 
 P4(s) + H2(g) (iv) C2 H 6 ( g )   CO2 ( g )  H 2O()
O2 ( g ) 
2

SOLUTION :
First, balance each reaction :
(i) H2(g) + Cl2(g) 
 2HCl(g)
(ii) N2(g) + 2O2(g) 
 2NO2(g)
(iii) 4PH3(g) 
 P4(s) + 6H2(g)
7
(iv) C2H 6 ( g )   2CO 2 ( g )  3H 2O()
O 2 ( g ) 
2
Now, Use : rH – rU = ngRT and n g   (n g ) products –  (n g ) reactants
 If ng > 0, rH – rU > 0 ;
If ng < 0, rH – rU < 0 ;
If ng = 0, rH – rU = 0
(i) ng = 2 – (1 + 1) = 0 (ii) ng = 2 – (1 + 2) = – 1
(iii) ng = (6 + 0) – 4 = 2
 7 5
(iv) ng = (2 + 0) –  1     [Note : For H2O(), ng = 0]
 2 2
Illustration - 14 The enthalpies of combustion of carbon and carbon monoxide in excess of oxygen at
298 K and constant pressure are –393.5 kJ/mol and –283.0 kJ/mol respectively. Calculate the heat of
formation of carbon monoxide at constant volume.
SOLUTION :
Heat change at constant pressure means enthalpy change (rH = qp)
1
Heat of formation of CO is written as : C (s) +  CO (g) ;  f H Θ  ?
O (g) 
2 2
Now we have :
I. C (g) + O2 (g) 
 CO2 (g) ;  c H1Θ  393.5 kJ / mol
1
II. CO (g) + O (g) 
 CO2 (g) ; c HΘ
2  283 kJ / mol
2 2

1
Adding appropriately (i.e., I – II), we get ; C (s) +  CO(g) ;  f H Θ
O (g) 
2 2
From Hess’s Law :  f H Θ   c H1Θ   c H Θ

2
 f HΘ = – 393.5 – (– 283) = – 110.5 kJ/mol
Now, calculation of the heat of formation at constant volume means that we have to calculate change in
internal energy (i.e. rU).
Using : rH = rU + PV [For a chemical reaction]
= rU + ngRT [ng = gaseous moles of products – gaseous moles of reactant]
 rU = rH – ngRT
Now putting the values :
1 1
n g  1   T = 298 K R = 8.314 J/K/mol.  f H Θ = –110.5 kJ/mol
2 2
1
  f U Θ = –110.5 – × 8.314 × 298 × 10–3 = –111.7 kJ/mol
2
Illustration - 15 Standard enthalpy of formation of C3H7NO2(s), CO2(g) and H2O() are –133.6, – 94.0
and – 68.3 kcal/mol respectively. Standard enthalpy of combustion of CH4(g) at 25°C is – 212.8 kcal/mol.
1 1
Calculate r H Θ for the reaction: 2CH4(g) + CO2(g) + N2(g)   C3H7NO2(s) + H2(g)
2 2
Also calculate heat of reaction at constant volume for combustion of C3H7NO2(s).
SOLUTION :
1 1
2CH4(g) + CO2(g) + N2(g) 
 C3H7NO2(s) + H (g) :  r H Θ  ?
2 2 2
To calculate  r H Θ of the above reaction, we need to find out the  f H Θ for CH4 as :
Given : CH4(g) + 2O2(g) 

 CO2(g) + 2H2O() :  c H Θ = – 212.8 kcal/mol
Using the definition of rH, we have :

 r HΘ  [f H Θ(CO2 )  2  f HΘ(H 2O) ]  [f H Θ(CH 4 )  2  f HΘO2 ] [Note : f H Θ(O2 )  0 ]
 – 212.8 = [– 94.0 + 2(– 68.3)] – f HΘ (CH 4 )
 f HΘ(CH ) = –17.8 kcal/mol

4
Θ
Now find the  f HΘ of the required equation using f H (CH ) .
4
 r HΘ  [f HΘ (C3H7 NO2 )  0]  [2  f HΘ(CH 4 )  f HΘ(CO2 ) ]
  r H Θ  ( 133.6)  2( 17.8)  ( 94.0)  4.0 kcal / mol

Now calculate
15 1 7
c HΘ (C3H7 NO2 ) : C3H 7 NO 2 ( s )   3CO 2 ( g )  N 2 ( g )  H 2O()
O2 ( g ) 
4 2 2
7
c HΘ (C3H7 NO2 ) = 3( 94.0)  ( 68.3)  ( 133.6)  387.45 kcal / mol
2
 1
Find  r UΘ   r HΘ  n g RT  387.45      2  10 3 (298)
 4
  1  5 
 387.6 kcal / mol  n g   3  2   4 
   
Illustration - 16 From Navogardo atoms of an element A, when half the atoms transfer one electron to
another atom, 405 kJ/mol of energy was found to be consumed. An additional energy of 745 kJ was further
required to convert all the A– ions to A+. Calculate the ionisation energy and the electron affinity of atom A
in eV.
SOLUTION :
Let I.E. be x eV/atom and E.A. be y eV/atom (magnitudes)
 A+ + e–
A  ; rH = I.E. = x A + e– 
 A– ; rH = E.A. = – y
405  103
I: Energy absorbed in eV =
1.6  1019
405  103 6.02  1023 6.02  1023

  x y . . . . (i)
1.6  1019 2 2

A–   A+
 A 
745  103
II : Energy absorbed in eV =
1.6  10 19
745  103 6.02  1023 6.02  1023

  x  y . . . . (ii)
1.6  1019 2 2
Solve for IE and EA using (i) and (ii), IE = 11.93 eV/atom and EA = 3.52 eV/atom (Magnitudes)
Illustration - 17 In order to get maximum calorific output, a burner should have an optimum fuel to
oxygen ratio which corresponds to 3 times as much oxygen as is required theoretically for complete
combustion of the fuel. A burner which has been adjusted for methane as fuel (with x litre/hour of CH4 and
6x litre/hour of O2) is to be readjusted for butane, C4H10. In order to get the same calorific output, what
should be the rate of supply of butane and oxygen ? Assume that losses due to incomplete combustion etc. are
the same for both fuels and that the gases behave ideally. Heats of combustion : CH4 = 809 kJ/mol;
C4H10 = 2878 kJ /mol.
SOLUTION :
First calculate the amount of energy required in the burner per hour using methane as follows :
809
 c HΘCH  809 kJ mol1  kJ / L (at 25C)
4 24.48
 1 mol CH4 ( 24.48 L at 25°C) on combustion produces 809 kJ
x
 x L/hr CH4 on combustion produces energy =  809 kJ / hr
24.48
Now, this much energy will be required by burning of butane and we can find its rate of consumptiom as :
2878
 c HΘ C H  2878 kJ mol1  kJ / L (at 25C)
4 10 24.48
x
 809
L
 Required Rate of combustion of propane  24.48  0.28 x L / hr
2878 hr
24.48
13
C4H10(g) + O (g)  4CO2(g) + 5H2O()
2 2
13
 1 mol CH4  mol O2 (theoretically)
2

 13 
  3   mol of O2 is required/mol of CH4 (practically) [Given]
 2
 39 
 rate of O2 per hour = (0.28x)     (5.48 x ) L O 2
 2 
Bomb Calorimeter
Calorimetry is study of heat transfer during physical and chemical processes. A calorimeter is device for
measuring energy transferred as heat. The most common device for measuring U is the adiabatic bomb
calorimeter, shown in figure (figure 1 & 2). The inner vesel or the ‘bomb’ (figure 2) and its cover are made
of strong steel coated inside with gold or platinum or some other non-oxidisable material. The cover can be
fitted tightly to the vessel by means of a metallid screwed down on a lead washer. A weighed amount of the
substance is taken in a platinum cup C which is supported on a rod R.
Stirrer
T
O2
Water
Bomb G
R Platinum cup
W
Figure 1 : The Bomb Calorimeter Figure 2 : The Bomb
A thin platinum wire W is connected between the rods R and G as shown. This serves to initiate the
combustion when heated electrically. The bomb is tightly closed and oxygen introduced through the inlet
tube T unit a pressure of about 20 – 25 atmospheres is attained. The bomb is then lowered in water placed
in a double jacketed and polished metallic calorimeter so as to minimise error due to radiation. The
arrangement ensures that there is no net loss of heat from the calorimeter to the surroundings (the bath) and
hence that the process is adiabatic. A mechanical stirrer is provided as shown. When the temperature of the
water become steady, the substance of inginited by calorimeter is noted after every minute by means of a
Beckmann thermometer graduate to read up to hundredth of a degree. The final temperature when cor-
rected for the radiation error in the usual way, minus the initial temperature, gives the rise of temperature.
The heat capacity of the calorimeter system, called the calorimeter constant, C, is obtained by burning a
known mass of a substance of known enthalpy of combustion. For this purpose, usually benzoic acid of high
grade purity is taken. Its qv which has been very carefully measured in taken as – 3226.7 kJ mol–1. Suppose

the thermal capacity of the calorimeter system including water is C and  is the change in temperature
produced by burning a quantity m of the given substance of molar mass M. Then, the constant volume heat
of combustion, qv of the substance is given by C  q  M/m. The enthalpy of combustion qp is then
obtianed with the help of the equation qp = qv + ngRT.
Illustrating the concepts :

(i) 0.50 of benzoic acid was subjected to combustion in a bomb calorimeter when the temperature of the
calorimeter system (including water) was found to rise by 0.55oC. Calculate the enthalpy of combus-
tion of benzoic acid. The T calorimeter constant was found to be 23.85 kJ K–1.
qv = C  q  M/m
= 23.85 kJ K–1  0.55 K  122 g mol–1 / 0.50 g
= 3200.7 mol–1
= – 3200.7 kJ mol–1 (Heat of combustion has alwas a negative sign)
15
C 6 H 5COOH(s)   7CO 2 (g)  3H 2O()
O 2 (g) 
2
We know that q p  q v  n g RT ; n  7  7.5  0.5
q p  3200.7 kJ mol 1  ( 0.5)(8.314 10 3 kJ K 1mol 1)(298K)
 3201.9 kJ mol 1
(ii) Explain why the following statement, made by a student doing an experiment on bomb calorim-
eter, is wrong : “H = U + PV. Since in the experiment, V = 0, hence, H = U.”
The error is due to the fact that the student has applied the equation H = U + PV, which holds at
constant pressure, to a process which occurs at constant volume.
We know that H = U + PV
 H = U + (PV) = U + PV + VP
For a constant pressure process, P = 0 so that H = U + PV
However, for a constant volume process, V = 0 so that H = U + VP
We many meantion here that a calorimeter for studying processes at constant pressure, called an
isobaric calorimeter is also available commercially. A simple example is thermally insulated vessel open
to the atmosphere ; the heat released in the reaction monitored by measuring the change in tempera-
ture of the contents. For a combustion reaction, an adiabatic flame calorimeter can be used
to measure T when a given amount of substance burns in oxygen.

Enthalpy of Polymerization :
The difference between the enthalpy of one mole of monomer and the enthalpy of the products of the
polymerization reaction. Addition polymerizations are exothermic, values ranging from about 35 to 100 kJ/
mol
Let us consider an example of polythene.
n  H 2 C  CH 2  
 ...........  CH 2  CH 2  CH 2  CH 2  .............
H (Per mole) = B.E. of Reactants – B.E. of Products
(B.E. of C = C + 4  B.E. of C – H) – ( 2  B.E. of C – C + 4  B.E. of C – H)

Same logic can also be used in following reactions as well
nN 2(g)  nH 2(g) 
 ( NH  NH 
) n (g)
n(H 3C  C  C  CH 3 ) (g) 
 ( CH 2  CH  CH  CH 2 
) n(g)
CALCULATING RESONANCE ENERGY Section - 7
Resonance energy, as we know, is the difference in energy between resonance hybrid and the canonical
form of the compound. It can be easily calculated using the following key points :
(i) If the resonance hybrid is more stable than the canonical forms, resonance energy is negative otherwise
positive.
(ii) Simply figure out, which of the resonance hybrid and the canonical form is more stable based on the
rH values as explained :
(a)  f H Θ : More negative is  f H Θ , more is the stability as this means when compound is formed,
energy is getting lost to attain lower energy than the reactants.
(b)  c H Θ or  Hydrogenation H Θ : More negative value in this case means less stability as more heat
released means this compound is more reactive.
Note : In (a), the compound under analysis is the product whereas in (b), that compound is the reactant.
(iii) Now, calculate H for the theoretical (canomical) and actual (resonance hybrid) compound and
calculate the difference between the two to get resonance energy.

Illustration - 18 The standard molar enthalpies of formation of cyclohexane() and benzene() at 25C are
156 and +49 kJ/mole respectively. The standard enthalpy of hydrogenation of cyclohexene() at 25C is
–119 kJ/mole. Use this data to estimate the magnitude of the resonance energy of benzene.
SOLUTION :
Given : C6H10 () + H2(g) 
 C6H12() ;  Hydrogenation H Θ = 119 kJ/mole
Find the actual heat of hydrogenation of benzene from Hess’s law as follows :
1. 6C(s) + 6H2(g) 
 C6H12() ;  f H Θ = 156 kJ/mole
2. 6C (s) + 3H2(g) 
 C6H6() ;  f H Θ = +49 kJ/mole
C6H6 () + 3H2(g) 

 C6H12() ;  Hydrogenation H Θ
 ( Hydrogenation H Θ ) = 156  49 = 205 kJ/mole

Actual
[Note :  Hydrogenation H  is always negative ]
 hypothetical heat of   heat of hydrogenation of 

Now,     cyclo hexatriene

 hydrogenation of benzene   
 heat of hydrogenation 
3   
 of cyclohexane 
= 3  (119) = 357 kJ/mole
Here, we have assumed that there are only 3 double bonds in benzene (kekule’s structure) and in
hydrogenating it, the energy obtained will be roughly 3 times of hydrogenating cyclohexene.
and
Clearly, heat of hydrogenation for theoretical benzene is more negative and thus, it is less stable. So,
Resonance energy should be negative (since actual benzene is more stable).
 Resonance energy = 357  (205) = 152 kJ/mole of benzene

Illustration - 19 Calculate the resonance energy of isoprene (C H ) from the data given.
5 8
Standard Heats of combustion of isoprene, carbon and water are 3186, 393.5 and 285.83 kJ/mole respec-
tively. Bond energies of C = C, C  C, C  H and H  H bonds are 615, 348, 413, 435.8 kJ/mole respectively.
Standard Heat of sublimation of graphite is 718.3 kJ/mole.
SOLUTION :
Calculate  f H Θ of isoprene from its heat of combustion (This will give the value for the actual isoprene
existing in nature).
5C (s) + 4H2 (g) 
 C5H8 (g) ; f HΘ = ?
1. C5H8 (g) + 7 O2 (g) 

 5 CO2 (g) + 4 H2O () ;  r H1Θ = 3186 kJ/mole
2. C(s) + O2 (g) 
 CO2 (g) ; rHΘ
2 = 393.5 kJ/mole
3. H2 (g) + 1/2 O2 (g)  H2O ()

 ;  r H 3Θ = 285.83 kJ/mole
Now operating 5(2) + 4(3)  1 to get the equation of heat of formation.
From Hess’s Law we have :
 f H Θ = 5 r H Θ Θ Θ
2  4  r H 3   r H1
  f H Θ = 5(393.5) + 4(285.83)  (3186)  (  f H Θ ) actual = 75.18 kJ / mole
 H 2C  C  HC  CH 2 
Now calculate heat of formation using the bond energies and structure of isoprene.  | 
 CH 3 
Note : Data calculations from the bond energy concept is always theoretical.
1. Bond Breaking : (H1)

5 [ C(s) 
 C(g) ; +718.3 ]
4 [ H2 (g)  2H ; +435.8 ]

 H1 = 5 × 718.3 + 4 × 435.8
= + 5334.7 kJ
2. Bond Formation : (H2)
8[ C + H 
 C  H ; 413 ]
2[ C + C 
 C  C ; 348 ]
2[ C + C   C = C ; 615 ]
 H2 = (8 × 413 + 2 × 348 + 2 × 615)
= 5230 kJ

From Hess’s Law : (  f H Θ )Theoretical = H1 + H2
(  f H Θ )Theoretical = 5334.7 + (5230) = 104.7 kJ
 Resonance Energy = 75.18  104.7 = 29.52 kJ
NOW ATTEMPT IN-CHAPTER EXERCISE
THEN ATTEMPT OBJECTIVE WORKSHEET TO COMPLETE THIS EBOOK

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Vidyamandir Classes Thermochemistry

Self Study Course for IITJEE with Online Support Section 1 1

This type of system has no interaction with its sur-

(i) Intensive Properties :

(ii) Extensive Properties :

3. Internal Energy (U) :

2 Section 1 Self Study Course for IITJEE with Online Support

4. First law of Thermodynamics :

Self Study Course for IITJEE with Online Support Section 1 3

7. Exothermic and Endothermic reactions :

(b) Endothermic Reactions :

4 Section 1 Self Study Course for IITJEE with Online Support

8. Enthalpy Change at Standard Conditions :

Here, rH2 =2 rH1

Self Study Course for IITJEE with Online Support Section 1 5

Standard states of some elements :

6 Section 1 Self Study Course for IITJEE with Online Support

Heat of Reaction Section - 2

(a) Standard Heat of Formation (  f H  ) :

C(s, graphite) + 2 H2 (g) 

(b) Standard Heat of Combustion (  c H  ) :

C(s, graphite) + O2(g) 

Self Study Course for IITJEE with Online Support Section 2 7

Using the definition of enthalpy change as : rH = H(products) – H (reactants)

For the given reaction :  r H   (H  

f H 19.8 0 (–94.05) (–57.8)

  r H  = [6 × (–94.05) + 3 × (–57.8)] – [19.8] = – 757.50 kcal/mol.

(c) Heat of Dissociation (  bond H  ) :

 2H (g) ;  bond H  = 103 kcal/mol

 2C (g) ;  bond H  = 80 kcal/mol

(d) Heat of Phase change :

8 Section 2 Self Study Course for IITJEE with Online Support

(e) Heat of Atomization (  a H  ) :

(ii) For a diatomic molecule,  a H  is also called as  bond H  .

(f) Average Heat of Dissociation ( mean, bond H  ) :

Self Study Course for IITJEE with Online Support Section 2 9

(g) Heat of Lattice(  lattice H  ) and Heat of Hydration(  hyd H  ) :

 Na+ (g) + Cl– (g)

Na+ (g) + Cl– (g) (  NaCl ) 

 hyd H  = –783 kJ/mol

(h) Heat of Solution ( sol H  ) :

(i) Heat of Ionisation ( ionisation H  ) :

10 Section 2 Self Study Course for IITJEE with Online Support

(j) Heat of Neutralisation (  neutralisation H  ) :

H +(aq) + OH–(aq)  H2O ()

Self Study Course for IITJEE with Online Support Section 2 11

Hess’s Law of Constant Heat Summation Section - 3

(ii) H2O () 

12 Section 3 Self Study Course for IITJEE with Online Support

H+ (aq) + OH– (aq) 

1.  CH3COO– (aq) + H+ (aq) ;  Io n isatio n H   ?

2. H+ (aq) + OH– (aq) 

Now adding the two equations to get the equation of neutralisation ;

 CH3COO– (aq) + H2O () ;  Neutralisation H   50.6 kJ / mol

Self Study Course for IITJEE with Online Support Section 3 13

isomerization H   33.0 kJ mol1

14 Section 3 Self Study Course for IITJEE with Online Support

Heat of Reaction and Bond Energy Section - 4

Let us consider that the bond energy of AB molecule is x kcal/mol.