_uowi ng may be considered as typical examples of

fhe 10 HNO (aq) + NaOH(aq) NN the heat of neutralisation.

J ~ a 0
HNO (aq) + KOH(aq) ~ KN 3(aq) + H20(/) 6.H == - 13.69 kcal
1 0iaq) + H 0(/)
HCl(aq) + NaOH(aq) ~ NaCl(- ) 2
6.H == - 13 .87 kcal
. aq +
HCl(aq) + L10H(aq) ~ LiCI( ) HH20(/) u
AH
== - 13 .68 kcal
aq + 20(l) 6./-f - 13 70 k
be concluded from the above data that the h t - - · cal
It maY. 13 7 kcal no matter which acid or bas . ea of neutralisation of a strong
e 1s - • acid and
strongba5_ with the help of the theory of ionisation.e If
' IS emplo d Th· •
1 HA, ye · is regulanty has been explained
satisfacto11 tase respectively and equivalent amounts of th . a~d B_OH repre~ent any strong
allY srrong _
acid and
+ . _ ese m dilute solutton be mixed, we have
W(aq) + A(aq)+ ~(aq)+ _oH- (aq) - - , A(aq) + B(aq) +H 0([) 6.H =
2
-13 .7kcal
. -eaardin
D1s1 o g the ions which are present on both sides of tl .
. • 1e equation, we get
H+(aq) ~ o~-(a q) - - , H20(l) tiH = - 13.7 kcal
r11us the heat of neutra h~atio n of an acid and a base is merely the heat of formation of water
drogen and hydroxyl 10ns.
{rolll hy
Wh en weak acids
. . or weak
. bases
. are neutralised bY strong bases or strong acids • respectively,
•
the heat of neutralisation differs widel Y from - 13.7 kcal. This is shown by the following
examples :
HCl(aq) + NH40H(aq) - - , NH Cl(aq) + H 0([) 6.H = - 12.3 kcal
4 2
HCN(aq) + NaOH(aq) ~ NaCN(aq) + H 0([) tiH = -12.3 kcal
2
HNOla q) + NH40H(aq ) ~ NH NOiaq ) + 1½0([) 6.H = - 12.3 kcal
4
HCOOH(aq) + NH40H(aq ) ~ HCOONH/aq) + H O(l) 6.H = - 11.9 kcal
2
In such cases the neutralisation process involves not only the union of hydrogen and
hydroxyl
ions but also the dissociation of the weak acid or base. The measured heat of neutral
isation is,
therefore, equal to the heat given out in the union of H+ (aq) and OH- (aq) ions plus
the heat
accompanying the dissociation of weak acid or weak base. The neutralisation of NH 0H
4 with HCl,
for example, can be represented as :
NH 40H(aq ) ~ NH; (aq) + OH-(aq) 6.H = Qkcal
and W (aq) + OH-(a q) + Cl-(aq ) ~ H 0(l) + CI-(aq) 6.H = - 13.7 kcal
2

NH 0H(aq) + H+ (aq) + c1-(aq ) ~ NH; (aq) + CI-(aq) + H O(/) Afl = Q-

4 2 13.7 kcal
But the measured heat of neutralisation is - 12.3 kcals. Therefore,
Q-13. 7 = -12.3
Q =13.7 - 12.3 = 1.4 kcal
Hence the heat of dissociation of NH OH is 1.4 kcal i.e., 1.4 kcal of heat is absorbed
when one
mole of ammonium hydroxide is dissociat~d into ions. In general, the heat of dissociation
of a w~a.k
a~id or weak base may be defined as the change in enthalpy of the system when one
mole of 1t 1s
dlSSociated into ions.
ENERGY CHANGES DURING TRANSITIONS OR PHASE CHANGES .
l . The three states of matter - solid, liquid and gas differ from one an_other in tl:e arrnn~~~1~n~
~>f
pru llc\l_cs ~~
~e1r constituent particles The magnitudes of intermolecular forces acting bet ween tl~c
ilesesiates are also differ~nt. It is a common observation that when ~• solid is conver~c~l mt?
w~t.e, energy is to be supplied This energy is spent in breaking the mtcrmolecular to1 ~es
Ill te
the i:u~
~~ltd_
Ii l~h are of high magnitude . Whenever there is a change in the state of
matter (~olld ~ iq~~ 01
i:U1d--, gas), the process is ~alled phase change or transition. It is also accompanied
by tie c ange
enthaJ
PY or heat content of the system .