®
50 JEE-Chemistry ALLEN
4. THERMO CHEMICAL EQUATION
It represents a balanced chemical reaction in which the physical state along with allotropic form of all
the reaction components as well as heat involved in reaction, are given.
C2H5OH(l) + 3O2(g) ¾¾® 2CO2(g) + 3H2O)(l) ; DrH° = –1367 kJ/mol
The above equation decribes the combustion of liquid ethanol at constant temperature and pressure. The
negative sign of enthalpy change indicates that this is an exothermic reaction.
The coefficients in a balanced thermochemical equation refer to the number of moles (never molecules)
of reactants and products in the reaction. Per mole of DrH° defines the mole of reaction. For above
reaction per mole means per mole of C2H5OH(l), per 3 moles of O2(g), per 2 moles of CO2(g) and
per 3 moles of H2O(l).
5. ENTHALPY CHANGE OF REACTION OR REACTION ENTHALPY (DrH)
Enthalpy of reaction is defined as the quantity of heat evolved or absorbed when molar quantities of
substances react completely in amounts represented by chemical equation, all components being main-
tained at same pressure and same temperature conditions.
For example : H2(g) + Cl2(g) ® 2HCl(g) ; DrH = –183.92 kJ
Thus, when one mole of gaseous hydrogen reacts completely with one mole of gaseous chlorine, 183.92
kJ of heat is evolved.
DrH = SHproducts – SHreactants = [2 × Hm(HCl, g)] – [1 × Hm (H2, g) + 1 × Hm(Cl, g)]
where Hm = molar enthalpy
5.1 FACTORS AFFECTING HEAT OR ENTHALPY OF REACTION :
The enthalpy change of reaction (DH) depends upon the following factors :
(i) Physical state of the reactants and the products : The DH of a reaction depends upon the
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physical states of reactants and products. For example, when hydrogen and oxygen gases combine
to give liquid water, the heat of reaction is different than when they combine to form gaseous water
at the same temperature and pressure.
H2(g) + O2(g) ® H2O(l) ; DH = –285.83 kJ
H2(g) + O2(g) ® H2O(g) ; DH = –241.82 kJ
(ii) Quantities of reaction components : The amount of heat evolved or absorbed depends upon
the amount of components involved in the reaction. For example, the heat of combustion of 2
moles of carbon is double than heat of combustion of 1 mole of carbon.
(iii) Allotropic forms : The amount of heat evolved or absorbed for different forms of the same sub-
stance are different. For example,
C(diamond) + O2(g) ® CO2(g) ; DH = –395.41 kJ
C(graphite) + O2(g) ® CO2(g) ; DH = –393.51 kJ
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ALLEN Thermochemistry 51
(iv) Temperature :The heat of reaction depends upon the temperature of reactants and products.
H2O(l) ® H2O(g) DH = x kcal at 298K
H2O(l) ® H2O(g) DH = y kcal at 373K
The dependence of reaction enthalpy on temperature is given by Kirchoff's equation :
T2
D r H 2 - D r H1 = ò D r ( C P ) × dT
T1
T2
and D r U 2 - D r U1 = ò D r ( CV ) × dT
T1
However, DrH and DrU do not change significantly on changing the temperature.
(v) Measurement at constant pressure or volume : The heat of reaction depends upon the conditions
of measurement of heat at constant pressure or volume, as,
DrH = DrU + Dr(PV)
DH may be equal, greater than or less than DrU.
For reaction involving gaseous components,
DrH = DrU + Drng . RT
(vi) Pressure : Enthalpy of any component may depend on pressure and DrH may change on changing
the pressure. As, the enthalpy of an ideal gas is independent from the change in pressure, for the
reactions involving ideal gases, DrH is pressure independent.
EXERCISE-I
1. Consider the reaction : N2 + 3H2 ¾® 2NH3 carried out at constant temperature and pressure, if DH
and DU are the enthalpy and internal energy changes for the reaction, which of the following expressions
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is true ? [AIEEE-2005]
(A) DH = DU (B) DH = 0 (C) DH > DU (D) DH < DU
2. For which of the following change DH ¹ DU ?
(A) H2 (g) + I2 (g)¾® 2HI (g)
(B) HCl (aq)+ NaOH(aq) ¾® NaCl(aq) + H2O(l)
(C) C(s) + O2(g) ¾® CO2(g)
(D) N2 (g)+ 3H2(g) ¾® 2NH3(g)
3. For the reaction : N2(g) + 3H2(g) ¾® 2NH3(g), DH is -
(A) D U + 2RT (B) D U – 2RT (C) D U + RT (D) D U – RT
E
EX0
*
↓
M
Endo
Standard
>
-
Enthalpyx
:
-
In
E
9
®
52 JEE-Chemistry ALLEN
5.2 MEASUREMENT OF DU AND DH : CALORIMETRY :
We can measure energy changes associated with chemical or physical processes by an experimental
technique called calorimetry. In calorimetry, the process is carried out in a vessel called calorimeter, which
is immersed in a known volume of a liquid. Knowing the heat capacity of the liquid in which calorimeter
is immersed and the heat capacity of calorimeter, it is possible to determine the heat evolved in the process
by measuring temperature changes. Measurements are made under two different conditions:
(i) at constant volume, qV
(ii) at constant pressure, qp
(a) DU measurements : For chemical reactions, heat absorbed at constant volume, is measured in
a bomb calorimeter (Figure). Here, a steel vessel (the bomb) is immersed in a water bath. The whole
device is called calorimeter. The steel vessel is immersed in water bath to ensure that no heat is lost
to the surroundings. A combustible substance is burnt in pure dioxygen supplied in the steel bomb.
Heat evolved during the reaction is transferred to the water around the bomb and its temperature
is monitored. Since the bomb calorimeter is sealed, its volume does not change i.e., the energy changes
associated with reactions are measured at constant volume. Under these conditions, no work is
Thermometer
Firing leads
Stirrer Oxygen
inlet
Sample
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Bomb
Oxygen
under
pressure
Water
Figure : Bomb calorimeter
done as the reaction is carried out at constant volume in the bomb calorimeter. Even for reactions
involving gases, there is no work done as DV = 0. Temperature change of the calorimeter produced
by the completed reaction is then converted to qV, by using the known heat capacity of the calorimeter
with the help of equation 6.11.
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ALLEN Thermochemistry 53
(b) DH measurements : Measurement of heat change at constant pressure (generally under atmospheric
pressure) can be done in a calorimeter shown in figure. We know that
DH = qp (at constant p) and, therefore, heat absorbed or evolved, qp at constant pressure is also
called the heat of reaction or enthalpy of reaction, DrH.
In an exothermic reaction, heat is evolved, and system loses heat to the surroundings. Therefore,
qp will be negative and DrH will also be negative. Similarly in an endothermic reaction, heat is
absorbed, qp is positive and DrH will be positive.
Thermometer
Foamed polystyrene
cup
Reaction mixture
Figure : Calorimeter for measuring heat changes at constant pressure
(atmospheric pressure)
Ex.1. 1g of graphite is burnt in a bomb calorimeter in excess of oxygen at 298 K and 1 atmospheric
pressure according to the equation
C (graphite) + O2 (g) ® CO2 (g)
During the reaction, temperature rises from 298 K to 299 K. If the heat capacity of the bomb
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calorimeter is 20.7kJ/K, what is the enthalpy change for the above reaction at
298 K and 1 atm?
Sol. : Suppose q is the quantity of heat from the reaction mixture and CV is the heat capacity of the
calorimeter, then the quantity of heat absorbed by the calorimeter.
q = C V DT
Quantity of heat from the reaction will have the same magnitude but opposite sign because the
heat lost by the system (reaction mixture) is equal to the heat gained by the calorimeter.
q = – CV × DT = –20.7 kJ/K × (299 – 298)K = –20.7 kJ
E
What does this mean ?
Lesser the RE
,
that means
,
RU is close
o the
true structure
less
That
implies ,
resonance was there.
OR,
the RE RH
very far from
More
,
is true structure :
That means
, resonance was more .
·
REL &
Extent
of of
ease
resonance resonance
Calculation f RE heat
by of hydrogenation
:
+ - :A
-2 bed
=
[T [] hal
58
; gn
-
+ 2 - =
mal
·
BuED I
+ -
:
&H
(expected) = -
58kce/mol
Al Lactuel) = -
55 56 .
kcal/mol
Again ED + -
[]
, Al (expected) = - 87 k cell mot
* (actual) = -
51 kcal/mol
Let's draw
energy diagram ,
an
I
&
"58 #T
"
Ef
56
↑ 55
.
Energy
[O]
51
FT
Ya
[]
vvv
REbenzene(D) :
D S RE =
n(rn) -
Du(RS)
=
(51 -
87) keel/mol
==
36
ka/mal
Rfe) :
RE An (RM) -
H(Rs)
=
=
(55 .
56 -
58)kcd/mol
-2 44 h
cal/mot
=
.
-
& III An = =>
EJ : an =
56
[0] u B
=
RE =
B- 5
& Arrange the
following
in RE order :
>
6)in)
"
II FIN FI
②
B
based
> C
on
> A
extent
of
resonance
9)x0 =
>
-
=
10
& They are
forms F
2 canonical
same molecule