UNIT 7 THERMOCHEMISTRY

Structure
7.1 btroduction
Objectives
7.2 Relationship between ArU and ArH
7.3 Standard Enthalpy of Formation
7.4 Hess's Law of Constant Heat Summation
7.5 Enthalpy Changes in Different Processes and Reactions
7.6 Experimental Determination 'of Enthalpy of Combustion
7.7 Kirchhoff's Equation
7.8 Bond Eathalpies and Estimation of Enthalpies of Formation
7.9 Summary
7.10 Terminal Questions
7.11 Answers

7.1 INTRODUCTION
The branch of science dealing with heat changes during a chemical reaction is known as
Thermochemistry. In this unit, we shall deal with heat change accompanying a chemical
reaction when it is carried out under constant volume or constant pressure. We shall
define standard enthalpy of formation and enthalpy changes in different chemical
reactions. We shall discuss the experimental method of determination of enthalpy
changes. We will list some of the applications of Hess's Law of constant heat
summation. Finally, we shall derive Kirchhoff's equation and discuss its importance:

Objectives
After studying this unit, you should be able to:
dcrive the relationship between ArU and ArH and make calculations based on this
relationship,
define standard enthalpy of formation,
state Hess's law of constant heat summation and explain its significance,
calculate the enthalpy of a reaction using enthalpies of formation of compounds,
describe an experimental method for the determination of enthalpy of combustion,
derive Kirchhoff's equation and state its signifi@nce,
define bond enthalpy, and
calculate enthalpies of reactions from bond enthalpies.

7.2 RELATIONSHIP BETWEEN A,U AND A r H

A chemical reaction can be carried out in two ways:
i) In a closed vessel, so that there is no volume change.
ii) In a pressure regulated vessel, so that there is no pressure change.
Accordingly, the heat change accompanying a chemical reaction can also be measured
in two ways, viz., heat change at constant volume (9,) and at constant pressure (9,).
From Eqs.6.25 and 6.34, q, = A U and q, = AH. In thermochemistry, the enthalpy
change accompanying a chemical reaction is called the reaction enthalpy and is denoted
by the symbol ArH. Similarly, the internal energy change accompanying a chemical '
reaction is given the symbol A$. The subscript rafter A sign indicates a reaction. To
denote formation, combustion and vaporization processes, subscripts used are f, c and
vap, respectively. As in the case of Eqs. 6.25 and 6.34 we can write,

9, =Aru ...(7.1)
and q, = ArH ...(7.2)
The significance of A,U and ArH can be explained by the following equations:
AJJ = u~roducts-u~eactants ...(7.3)
A rH = H~roducts-H~eactants ...(7.4)
Chemical Thermodymmb Since most reactions are carried.out at constant pressure A,H is more commonly used
than ArU.
Thermochemical Equations
In a thermochemical equation, in addition to the chemical reaction, the physical states
of the various chemical species and the energy change are also specified. For example,
H2(g)+4 O2(g> H20(1)
+
ArH = -285.8 kJ mol-' ...(7.5)
C(gra~hite)+Oz(g) CO2(g)
+ ArH = -393.5kJmol-I ...(7.6)
are thermochemical equations. In such equations, s, I and g, .refer to solid, liquid and
gaseous states, respectively. If a substance can exist in various allotropic forms, the
particular form must be mentioned.
Relation between ArU and ArH
If in a chemical reaction, the enthalpy of the system changes from H I to H , and if U , ,
p i , V, and U2,p2, V2are the corresponding internal energies, pressures and volumes,
then
HI = u , . +plV1 ...(7.7)
and H2 = u2 +p2V2 ...(7.8)
ArH=H2-HI=i/,+p2~2- Ul-plVl=U2-Ul+ (p2V2-p,Vl)
Hence, AJl= ArU+ (p2V2- plVl) ...(7.9)
At constant pressure (pl=p2=p),
ArH = ArU+ (pV2-pVl)=ArU+p(V2-Vl)
AJl=A,U+pAV
Using Eqs. 7.1 and 7.2,
qp=q,+pA V
For solids and liquids, p A V is neg- If we assume that (i) all gaseous reactants and products are ideal and
ligible. Thus for reactions in (ii) there are nl and n2 moles of gaseous reactants and products, respectively, then,
densed phases. A,H = P , U .
plVl=nlRT and p2V2=n2RT
Hence, p2V2-plV1=(n2-nl)RT
Since pressure is constant,
p(V2-Vl)=pA V=(n2-nl)RT
Replacing (n2-n,) by An, to represent the change in the number of moles of gaseous
species in Eq.7.12,
pAV=An,RT ...(7.13)
Using this in Eq. 7.11,
qp=qv+ An$T ...(7.14)
or A,.H= A,U+An$T ...(7.15)
The subscript g in An, signifies that only the gaseous reactants and products are
considered in the calculation of An. It may be noted that An, can be
positive, if the number of moles of gaseous products is more than those of gaseous
reactants
negative, if the number of moles of gaseous reactants is more than those of gaseous
products
zero, if nl=n2.
For example, consider the following reactions:
H2(g)+102(g) + H20(C) ...(7.16)
C(graphite)+Oz(g)

+
+

1
2
-
CO2(g)
3
In Eq. 7.16, A<= (0- (1 -))= -;there are no gaseous products, but one mole
2
of hydrogen and half a mole of oxygcn are present as gaseous reactants.
...(7.17)

In Eq.7.17, An, = (1- 1) = 0, since there is one mole each of gaseous reactant and
product.
Using the above ideas, answer the following SAQ.
SAQ 1
Calculate An, for the following reactions:
7.3 STANDARD ENTHALPY OF FORMATION
The standard enthalpy of formation of a compound is the enthalpy change
accompanying the formation of one mole of the compound from its elements in their
most stable state, all substances being in their standard state (1bar pressure and any
specified temperature). The standard enthalpy of formation is denoted by AfW. The
superscript " indicates the standard state and the subscript 'f' denotes formation
reaction. Although we do not know the absolute enthalpy of the compound, we know
its relative enthalpy with respect to the elements from which it is formed. Therefore, we
adopt an arbitrary convention that the standard enthalpies of formation of all elements
is zero at any specific temperature at 1bar. If an element shows allotropy or exists in
different phases, then the enthalpy is taken as zero for the most stable allotrope or
phase. Phosphorusis an exception (yellow phosphorus is taken as standard). As aresult
of this, the enthalpy of any substance in its standard state is equal to A f W ,
the enthalpy change of the reaction in which one mole of the substance is formed from
the elements in their standard state. For example, the enthalpy of the reaction:
C(graphite)+02(g) --, C02(g) is ArH"=-393.5 kJ mol-'
Thus, we have
A rW=A fW(C02)- A ,IT (graphite) - A fW(02)
= A fW(C02)-0-0= AfW(C02)

Therefore, the standard enthalpy of formation for C 0 2is equal to A,W which in turn Earlier the standard state was
is eaual to -393.5 kJ mol-I. If temDerature has also to be indicated. then it is shown in defined as 1 atmosphere and any
the parenthesis. Thus, A f W ( 2 9 8 . i ~K) meansstandard enthalpy of formation at 1 bar
; ~ ~ ~ ~ thed ~ ~ ' "
and 298.15 K. Most of the data are available at 298.15 K i n thermodynamic tables. standard state as bar at any
Standard enthalpy of formation of some substances are given in Table 7.1. specified temperature. Since 1
Table 7.1: Standard Enthalpy of Formation of Some Selected Substancesat 298.15 K atm. is equal to 1.01325 bar, it
, does not cause much change in
AfW, specially for substances in
AfW(298.15K) AfW(298'15 K, liqyid and solid states.
Substance Substance
kJ mo1-' kJ mo1-'

-285.8 H202 ( 0 -187.8

-241.6 N2H4 (1) + 50.6
-393.5 No2 (g) + 33.2
- 46.1 NZO, (g) + 9.2
- 74.81 NaCl (s) -411.2
- 84.68 KC1 (s) -436.8
-238.7 Glucose (s) -1268.0
+ 49.0

Calculationof Reaction Enthalpies

It is possible to calculate standard reaction enthalpies using thermodynamic tables such
as Table 7.1. The principle is that,
A r m = (Sum of A f W values of products) -
(sum of A f W values of reactants) ...(7.18)
This relationship can be explained using general reaction of the following type:
pA+qB+rC+sD ...(7.19)
wherep, q, r and s are the stoichiometric coefficients and A , B, C and D are reactants
and products. Let the standard enthalpies of formation of A , B, C and D be represented
C~TbamodynuDics by A ,W(A), A fW(B), A &"(C), and A ,W(D), respectively, The standard reaction
enthalpy for the reaction mentioned in Eq.7.19 is given by,
AW' =( r ) (
+ s A p ( D ) - PA@('A) + qAfw(B) ) ...(7.20)
Let us illustrate the calculation of A,W using an example.
Example 1
For tee reaction given in Eq. 7.21 let us calculate
A,W at 298.15 K.
C,&(g)+802(g) + 3CO2(g) + 3H2O(I) ...(7.21)
Given that : A f W values of propene, carbon dioxide and water at 298.15 K are 20.42,
-393.5 and -285.8 kJ mol*',respectively.
From Eqs. 7.18 and 7.21,
A g = ( 3A@'(C02)+3AfW (H20) )-( A f W (c3H6)+8 A f W (02) )
= 3~(-393.5)+3 x (-285.8) - (1~20.42)
(since the standard enthalpy of formation of
oxygen is zero.)
AJiP=-2058 kJ
Hence, we are in a position to calculate A,W for a reaction using A f W values.
Enthalpy is a state property; its value changes by the same amount irrespective of the
path from the reactants to the products. Hence, it IS possible to calculate A,W of a
reaction from a sequence of reactions.
This is generalised as Hess's law of constant heat summation; we shall study this law in
the next section.
" SAQ2
Express the standard reaction enthalpy of the reaction,
GHs (g)+%0 2 (g) 2C02 (g)+3H2O(I)
+

in terms of the standard enthalpies of formation of the components.

7.4 HESS'S LAW OF CONSTANT HEAT SUMMATION

Hess's law can be stated as follows:

The standard enthalpy change for a reaction is the sum of standard enthalpies of a
sequence of reactions (at the same temperature and pressure); the overall reaction
should be capable of being represented by the given sequence of reactions.
Hess's law is a direct consequence of the law of conservation of energy. It is not
necessary that evev reaction in the given sequence should be conducted in a
laboratory. A particular reaction can also be imaginary. The only requirement is that
the individual chemical reactions in the sequence must balance and add up to the
equation for a particular reaction. Also Hess's law enables arithm6tic operations of
chemical equations. This law is helpful in calculating enthalpies of reactions which
cannot be experimentally determined; what is required is to select a correct sequence
of reactions. We give below the use of Hess's law in calculating the enthalpy of
conversion of graphite to diamond which is very difficult to determine.
Example 2
C(graphite) + 0 2 (g) CO2 (g)
+ A,H, = -393.5 k~
C(diamond) + 0 2 (g) + CO2 (g) A,H2 =-395.4kJ
Then subtracting, we get
C(graphite)-C(diamond)=Oand A,H=A,Hl-A,H2=-393.5 kJ-(-395.4 kJ)=1.9kJ
Hence, we can write
C(graphite) -,C(Diamond) A,H = 1.9 kJ
We shall consider many examples of the use of Hess's Law in the next section. Before
proceeding to the next section, answer the following SAQ.
SAQ 3
Calculate A for the reaction,
C (graphite)+f Oz(g) -* CO(g)
at 298 K, using the following thermochemical equations:
C(gra~hite)+oz(g)-* COz (g) A,W = -393.5 kJ
co (g)+i 0 2 (g) -* COz (g) A r W = -283.5 kJ

7.5 ENTHALPY CHANGES IN DIFFERENT PROCESSES

AND REACTIONS
Enthalpy changes take place in almost all physical and chemical processes. Due to their
importance in science and engineering, special names have been assigned to enthalpy
changes of some such processes. We define below the enthalpy changes for some of
these processes.
Enthalpy of Combustion
The change in enthalpy during the complete combustion of one mole of a substance in Combustion is the process of
oxygen is called its enthalpy of combustion (A,W). The final oxidation products for a burning a substance in excess of
compound containingonly C , H , 0 and N are COz(g), H20(Z) and N2(g); if a compound oxygen.
also contains C1, Br, I, F, S, P, the final products include the aqueous solutions of HCI,
HBr, HI, HF, H2S04and H3P04at infinite dilution. Thus, the enthalpies of
combustion for methanol and urea are represented by the reactions:
CH30H(f)+1 .5O2(g) -* C02(g)+2H20(1) A,W=-726.1 kJ mol-'
CO(NH2)2(s)+l.5o2(g) -* C02(g)+2H20(l)+N2 (g) A,w=-633.4 kJ mol-'
The enthalpy of combustion is quite useful to determine the enthalpies of formation of
those substances which are difficult to measure experimentally. Here again we make
use of Hess's law.
Example 3
The enthalpy of combustion for methanol at 298.15 K is -726.1 kJ mol-'. What is its
enthalpy of formation? Given: AfW(COZ)= -393.5 kJ mol-' and AfW(H20)=
-285.8 kJ mol-'.
The combustion reaction of methanol can be wdtten as,
+
CH30H(r) 1.50z(g) -* C02(g) + 2HzO(Z) A,W= -726.1 kJ mol-'
Using Eq.7.18,
A f l = AcW(CH30H)=AfW(CO,) + 2AfW(H20)- AfW(CH30H)
( since A ,W(OZ)=0 )
Hence, A f W(CHIOH) = AfW(COz)+2AfF(HzO)- A c W CH3OH ( )
=((-393.5)+ (2x(-285.8)) 726.1) kJmol-'+
= -239.0 kJ mol-'

It can be seen that it agrees with the value given in Table 7.1.

Enthalpy of Solution
The formation of solution (by dissolution of a solute in a solvent) is also
accompanied by heat changes, but these heat changes are dependent not only on
the nature of the solute and solvent but also on the composition of the solution.
Therefore, the enthalpy change accompanying the complete dissolution of one mole
of solute in a definite amount of the solvent so as to give a solution of a specified
concentration is defined as the integral enthalpy of solution (or integral heat of
c h e n l & a l ~ ~ solution). As an example, consider the dissolution of 1 mol of NaCl in 200 mol of
-
water as represented by the equation,
NaCl (s) + 200H20 ( 0 -t NaCl (200 H 2 0 ) A,,,,,H = 5.36 kJ mol-'
whereA,,,H = 5.36 kJ mol-' represents the integral enthalpy of solution. In
general, it can be positive or negative depending on the nature of the solute and
solvent. A special case of enthalpy of solution arises when a sufficiently large
amount of solvent is used so that further dilution does not bring any heat changes.
This is defined as the enthalpy of solution at infinite dilution. For aqueous solution,
this reaction is represented by,
Urea(s) + H20(0-+ Urea (aq)
The symbol (aq) is used to represent an aqueous solution which is so 'dilute that
additional dilution is not accompanied by any heat changes.

In contrast to integral enthalpy of solution, we define a quantity called differential

enthalpy of solution. This is the enthalpy change when 1 mol of solute is dissolved
in a sufficiently large volume of solution of concentration, c, so that the final
concentration remains almost unchanged. The differential enthalpy of solution
depends on the concentration of the solution. It can be calculated from the integral
enthalpy of solution.
Another type of enthalpy term often used in solutions is the enthalpy of dilution,
AdilU.This is defined as the enthalpy change when a solution containing one mole
of solute at concentration c, is diluted by the addition of solvent so that the final
concentration is c2. It is obvious that the enthalpy of dilution depends on both cl
and c2.
Enthalpy of Neutralization
The enthalpy of neutralization of an acid is the enthalpy change which accompanies
the complete neutralization of a-dilute aqueous solution of an acid containing one
mole of H+ ions by a dilute aqueous solution of a base containing one mole of OH-
ions. An example is given below:
HCl(aq) + NaOH (aq) -, NaCl (aq) + H20 A,,,,H"=-57.3 kJ mol-'
It is observed experimentally that the enthalpy of neutralization of strong acids or
bases (with strong bases or acids, respectively). is essentially the same (i.e., -57 kJ
mol-'). This is because of the fact that strong acids and bases are completely
dissociated in their aqueous solutions, and the process of neutralization of strong
acids and bases is represented by
H+ (aq) + OH- (aq) -, H 2 0 A,W = -57.3 kJ mol-'
Hence, the enthalpy of ~leutralizationof strong acids and bases is the enthalpy of
formation of one mole of water from one mole each of H + and OH- ions.
When a weak acid or base is neutralised, the enthalpy of neutralisation deviates
from the value of -57.3 kJ mol-'. This is due to the low dissociation of weak acids
and bases; a portion of the energy is utilised in the process of dissociation of the
weak acids and bases. So far, we defined enthalpies of some processes; let us now
study the experimental determination of enthalpy changes.

. . - On the basis of the above material, answer the following SAQ.

SAQ 4
At 298 K, the standard enthalpies offormation of N02(g) and N204(g)are 33.2 and
9.2 kJ mol-'. Calculate the standard enthalpy of the following reaction:
N204 ( g ) '2N02(8)

7.6 EXPERIMENTAL DETERMINATION OF ,

ENTHALPY OF COMBUSTION
Calorimeters are used for determining the enthalpy changes in various processes.
As a matter of fact, calorimetry is the most important experimental technique in
thermodynamics and a lot of attention has been devoted to make it very sensitive.
At present calorimeters are available which can measure heat and temperature
changes accurately. Let us explain here the experimental determination of the
enthalpy of combustion.
The enthalpy of combustion is determined using a Bomb Calorimeter (Fig. 7.1).

The heat change measured using a

bomb calorin~eteris equal to the
internal engery change accompanying
combustion process. To calculate
c~~thalpy of conlbustion. use Eq.7.15.

Fig. 7.1: Bomb Calorimeter.

The method consists of the combustion of a definite amount of the substance in an

inner vessel called the 'bomb'. The bomb is placed inside a definite quantity of
water taken in an outer vessel. The outer vessel is thoroughly insulated. The
temperature readings of the water kept in it are measured before and after the
combustion using a sensitive thermometer. From the heat capacity of the
calorimeter, the amount of the substance taken and the temperature readings, the
enthalpy of combustion can be calculated. In general, using adiabatic calorimeters,
the enthalpies of reactions can be determined.

7.7 KIRCHHOFF'S EQUATION

For a given reaction, A r H and A r U generally vary with temperature. It is of great
importance to study these variations quantitatively so that these may be calculated
for any temperature from the known values of A r H and A r U at any other
temperature. The variation of A r H and A,U with temperature is described by
Kirchhoffs equation. Let us derive this equation.
IfCp is the heat capacity of a substance, then for a temperature rise dT, the increase
in enthalpy is given by Eq.6.36 (of Unit 6) as
d H = C,dT ...(7.22)
In the case of enthalpy of a reaction (ArH), we can rewrite Eq.7.22 as,
d (ArH) = ACpdT ... (7.23)
Where AC, = (sum of Cp values of products) -
(sum of Cp values of reactants)
Also, d(ArH) is the change in enthalpy of reaction due to change in temperature,
d T.
E.q. 7.23 on integration gives,

I I

Where AJ12 and ArH1 are the ~ ~ t h a l p i of

e s reaction at temperatures T2 and TI,
respectively. Eq. 7.24 is called Kirchhoffs equation. Similarly we can also obtain
the expression,
= AJl+ /:'
ACvdT ...(7.25)
Chemical Thermudynamics
Where A,U, and A,U2 are the changes in internal energy of the reaction at
temperatures TI and T2, and ACv is the difference in heat capacities between
products and reactants at constant volume. Let us now consider ihree of the special
cases of Eq. 7.24:
i) If AC, =0, then ArH2= ArHlimplying thereby that the enthalpy of reaction
does not change.
ii) If AC, is constant i.e. it does not vary with temperature, then
+
ArH2 = ArHl A Cp (T2- TI) ... (7.26)
i.e. ArH either decreases or increases regularly with temperature. For most
reactions Eq. 7.26 is valid for a small range of temperatures.
iii) If AC,, changes with temperature, then Eq. 7.24 has to be int_egrated by
expressing C, as a function of temperature. The variation in C, is usually
expressed in the following way:
C?; = a + bT + CT' + ....; the coefficients a, b, c, ....etc., are characteristic of
a particular substance.
Let us work out an example to show the use of Eq. 7.26.
Example 4 : ArH for the reaction.
c (graphite) + H 2 0 (g) CO(g) + H z ( ~ )
-+

at 298 K is 131.2 kJ. The C, values are given below in the temperature
range, 298 to 348 K.
Substance C ? ~ Jmol-' K-'
Graphite 15.93
H2O (g) 30.04
co (g) 26.51
H2 (I?) 29.04
Calculate ArH at 348 K.
The C, values given above are independent of temperature; hence, we can find
ArH at 348 K using Eq. 7.26.
Let us first calculate AC,,
(:,is usually given in J mol-' K - ' A C , = { [ l ~ ~ , ( ~ O ) + l x ~ , ( ~ ~ ) ] - [ l ~ C ? , ( ~ r a ~ h i t e ) + l x ~ , (J K
~ ~- I~ )
units. You should remember to
convert it into kJ mol-' K - ' (by
division by 1000). if A H is in kJ (Since one mole of each component appears
I)
mol-' units. in the thermochemical equation)

=9.58 J K-'
= 9 . 5 8 ~10-%J K-' (Remember 1 J = I 0-' kJ)
AC, is expressed in kJ K-', since ArH at 298 K is given in kJ.
Using Eq. 7.26,
+
A,H at 348 K = ArH at 298 K AC, (348-298)
+
= (131.2 9.58 x x 50) kJ
= 131.7 kJ

Using the ideas developed above, work out the following SAQ.

SAQ 5
For the reaction.
C(graphite) + H,O(g) --, CO(g) + HAg)
Calculate AC,. if the molar heat capacities at constant pressure for various species
vary as per the equation, Cp = a + bT + c 7 where
2
c,,
is In J mol ' K I. The (1,
b, and c values of each of the substances are given below:
a b x 10; 10'
Graphite 15.93 6.52 0.0
H 2 0 (g) 30.04 9.920 8.71
co ( g ) 26.51 7.68 11.71
H2 (g) 29.04 -0.836 20.09
7.8 BOND ENTHALPIES AND ESTIMATION OF
ENTHALPIES OF FORMATION
Bond enthalpy is a useful concept in thermochemistry. It finds application in the
calculation of standard enthalpy of formation and standard enthalpy of reaction of
many compounds.

In a molecule, atoms are linked through chemical bonds. When a molecule Enthalpy of atomization is the
decomposes into atoms, the bonds are broken and the enthalpy increases. This is enthalpy change a ~ m p W ' i n ga
also defined as 'the enthalpy of atomization, AatomH, and is always positive. For wAon in which a is
shattered into its component
example, the enthalpy of the following reaction is the enthalpy of atomization of ,to,s.
ethane gas:
(g) -, 2C(g)+6H(g) Aato,H=-2828.38 kJ mol-I
On analysis of Aato,,,H for a large number of such reactions, it has been found that Enthalpy of atomization of
specific values of bond enthalpies may be assigned to different types of bonds (Table graphite is usefulin the
7.2). These bond enthalpies correspond to the decomposition of a molecule in the of Standard enthalpy
gaseous state to atoms in the gaseous state. Certain substances in the solid state of formation of organic
mnpund..
when sublimed are converted into gaseous atoms. Thus, graphite when heated is
converted into gaseous atoms, and the heat required for one mole can be called the
molar enthalpy of atomization of graphite which is equal to 717 kJ mol-'. If graphite
is considered the reference state for carbon, then the atomization can be written as
follows:
C(graphite) -, C(g) AatO,H=717 kJ mol-'
Table 7.2:Bond Enthalpies ( B )

B B B The sigdcance of bond enthalpy

Bond Bond Bond in deciding the bond strength
kJ mol-' kJ mol-' kJ mol-' has been discus~edin Unit 3 of
Atoms and Molecules course.
H-H 436 C-F 484 C=C 813
0-H 463 C-CI 338 N-N 163
C-H 412 C-Br 276 N=N 409
F-F 155 C-I 238 NEN 945
CI -Cl 242 C-C 348 0-0 146

Br-Br , 1 93 C=C" 612 0=0 497

1-1 151 C=Cb 518 F-H 565

C-0 358 CI-H 431
C=O 745 Br-H 366
I-H 299
a-in alkenes
b-in aromatic compounds
The enthalpies of atomization of some more elements which become atomized on
sublimation are given in Table 7.3.
Table 7.3 : Standard enthalpies of Atomuation at 298.15 K

AammH"
Z~bstance
kJ mol-I
C (graphite) 717
/

Na 6 ) 108
K (4 90
cu (4 339

~t should be made clear that bond enthalpy is not bond dissociation energy (as
discussed in Unit 3 of Atoms and Molecules course). This could be understood if
we consider bond dissociation energy of Water:
H~O (g) + OH (g)+H (g) D I 4 0 1 . 9 kJ mol-'
+
OH (g) -+ O(g) H(g) Dz = 423.4 kJ m0l-l
Chemical Thermodynamics
Bond enthalpy is the average
amount of energy required to
break One Of
present in different gaseous
atoms.
Note that in the place of bond
enthalpy, the enthalpy of
atomization is used for carbon
(graphite) and other elements in
the solid state.
YOU may use the following formula
to calculate the resonance energy of
n~olecules:
Resonance energy of a compound =
t h ~from ~bond~ ~iv)
( ~ ~offormatlon
rnthalpy data) - (Enthalpy of formation
from enthalp~esof combust~on)
To study about resOnance,go
Sec 4.5 of Unit 4 of Block 1 of Atoms
and Molecules (CHE-OI) Course,
The quantities Dl and D2 are the first and second bond dissociation energies and
Are different from the bond enthalpy given for 0-H in Table 7.2. Again, bond
enthalpy is some kind of average of a large amounts of experimental data. These
are of immense value in estimating the standard enthalpy of formation of a large
number of compounds being synthesized and also for estimating the standard
enthalpy of reactions involving these new molecules.
The following steps will help you in the calculation of standard enthalpy of
formation from the bond enthalpies and enthalpies of atomization of elements:
i) First write the stoichiometric equation; then write (the most acceptable) Lewis
structure of each of the reactants and the product.
ii) Use bond enthalpies from Table 7.2 and enthalpies of atomization from Table
7.3 to calculate the heat required to break all the bonds in the reactants and
the heat released when the atoms form the product. The bond enthalpy of X-X
bond can be denoted as B(X-X) in arithmetic expressions.
iii) The slmdard enthalpy of formation
= (Heat required to break all the bonds
in the reactants) - (heat released when ...(7.27)
the atums form the product)
Bond enthalpy values can be applied to compounds only if these are in gaseous
state; if the compounds are in solid or liquid state, molar enthalpies of
subli tion or vaporization also must be considered.
Example 5 : Estimate the standard enthalpy of formation 06 acetone vapour anE
acetone liquid. (Enthalpy of vaporization of liquid acetor~e=:: 29 kJ mol-')
Step (i) : The stoichiometric equation for the formation of acetone vapour is
3H2(g) + 3C(graphite) + 1)02 (g) --,GHsCO (g) ...(7.28)
In terms of Lewis structures, the equation is given below:
3H-H+3C+10=0 +
H
Step (ii) : The heat required to atomize the reactants
= 3B(H-H) + 3 A,,,H(graphite) + 4B ( 0 = 0 )
+ +
= [(3x436) (3x717) 4 (497)lkJ
= 3708kJ
The heat released when the atoms form the product
= 6B(C-H) + 2B(C-C) +B(C=O)
= [(6x412) +(2~348)+745]kJ
Step (iii) : A f W( a ~ e t o n e ( ~ ) (3708-3913)
)= kJ mol-'
= -205 kJ mol-'
Hence the standard enthalpy of formation of acetone vapour is -205 kJ mol-' and, the
actual value is -216 kJ mol-'.
Step (iv) : Let us now calculate the standard enthalpy of formation of liquid acetone.
The condensation of acetone (I), from acetone (g) can be represented by Eq. 7.29.
Note that for condensation of acetone (g), the enthalpy change
= - AH",,(acetone) = -29 kJ mol-'
ClHhCO (g) + C2H6C0( I ) ... (7.29)
Adding Eqs, 7.28 and 7.29,
+ +
3H2 (g) 3C(graphite) bo2(g) + C2H6C0(I)
Hence,AfHo(acetone ( I ) ) = A f W (acetone (g)) - AWvap(acetone). So, the standard
enthalpy of formation of liquid acetone is -234 kJ mol-I. Using the above principles,
answer the following SAQ.
Zi36
Calmlate the standard enthalpy of formation of hydrogen chloride gas. Use Table 7.2.

7.9 SUMMARY

In this unit, some of the aspects of thermochemistry have been discussed.

The relationship between A r U and A r H has been derived and its use in the
calculation of internal energy change and enthalpy change has been indicated.
Standard enthalpy of formation has been defined; the relationship between
standard enthalpies of formation of substances and standard enthalpies of reactions
has been explained with an example.
Hess's law of constant heat summation has been stated and, its use in
thermochemical calculations explained.
Kirchhoff's equation has been derived and used in the calculation of A,H at a given
temperature knowing its value at any other temperature.
Bond enthalpy values have been used in the calculation of standard-enthalpies of
formation.

7.10 TERMINAL QUESTIONS

1. For the reaction

+
Fe203(s) + 3H2 (g) -,2Fe (s) 3 H 2 0 (I)
A r H at 298 K is -35.1 kJ. What will be the enthalpy of reaction at 375 K, if the
'
difference between the sum of the C,'s of the products and that of the
reactants is 85.7 J K-' and, it is independent of temperature?
2. Using Table 7.1 for the standard enthalpies of formation for C02(g) and H,O(I),
calculate the standard enthalpy of formaiion for naphthalene, if its standard
enthalpy of combustion is -5153 kJ mol-'.
3. The standard enthalpy of formation of H,O(I) at 298 K is -285.8 kJ mol-I.
Calculate the standard internal energy change [AfU"(H20)]for the formation of
water at 298 K.
4. Calculate the standard enthalpy of formation of PC15(s), using the following data:
+
P(s) 1.5 C12(g) + PC13(I) A,W = -318kJ
PC13 ( I ) + ch (g) + PC15 ( 4 A r W = -137 kJ

5. Using the C, data given in SAQ 5, calculate A r H at 1000 K for the reaction:
C (graphite) + H,O(g) + CO(g) H2(g) +
A,H at 298 K is 131.2 kJ. Use the integration formulae given in Sec 6.6 of Unit 6.

7.11 ANSWERS
Self assessment Questions
1. (i) 1 (ii ) 0

3. C (graphite) + 9(g) 9 .C02(g) A r W = -393.5kJ

c o ( g ) + 3 0 2 (g) '2' co2(g) A r W = -283.5kJ

Subtracting (2) from (1) and rearranging, we get
c (graphite) + 3 O2 (g)C O (g)
+

A,W = (-393.5 f 283.5) kJ

A,W = -110 kJ
 Chemical Thermodyn~nb
4. 1Nz(g)+O2(g) (1) N02(g) A f W = 33.2k~mol-'

N2 (g) + 202 (g) ) N2°4 (g) A f W = 9.2 k ~ m o l - '

(1) x 2-(2), gives N2(g)+202(g)-N2(g) -202(g) +2NOz(g)-NzOdg)
i.e., Nz04(g) + 2NO2 (g)
and A,W = ((2~33.2)-9.2) kJ
= 57.2 kJ

5. +
A Cp = Cp(CO) Cp(H2)- Cp (graphite) - CP(H20)
9 ~ T? J K-'
= (9.58-9.60~1 0 - ~ ~ + 2 3 . 0lo-'

+
6 . 4 Hz&) f 2C12 (g) + HCI (g)
+
AfW(HCI) = 4 B(H- H) t B (CI -CI) - B(H-CI)
= (1 (436)+4(242)-431) kJ mol- '
= -92kJ mol-'

1
L
Terminal Questions
1. ACp is independent of temperature; hence, we have to use Eq. 7.26 to calculate
I
1 A,H at 375 K.
+
A$Z(375 K) = A,H(298 K) A C, (375-298) = -28.5 kJ

d
F
a,$ (cl,,~$
= lo A,W ( ~ 0+4~A) T ( -
1
!!
~ 2 0 )

A,W ( c , , , H ~ (because AtW (03

= 0)
I: Rearranging the above equation and substituting the valies we get,
2

3. An,=-1.5 mol, R=8.314 J mol-' K-' and T=298 K;

An,RTis to be divided by 1000 to get the final value in kJ mol-'
Using Eq. 7.15 we get,
AfLP (H20) = -2.82.1 kJ mol-'

4. Adding the two equations given, we get

P(s) + 2 c
12 (g) + PCl,(s)

A,W (PCI, j = -455 k~ mol-I

I

5. Using AC, value (calculated in SAQ 5) in Eq. 7.24,

(AC, is divided by 1000 to obtain the

value in kJ K-' units)