Thermochemistry

intemal
Every chemical compound is accompanied by a certain amount ofchanges,
energy, which is called chemical energy. In physicalandandheatchemical
can be converted
heat
this chemical energy can also be converted into
both types of energies
" into chemical energy. The study of the relation between
is known as Thermochemistry. Chemical reactions, which are accompanicd by
chemical reactions, which are
1 evolution of heat are exothermic and
reactions occurring
accompanied by absorption ofheat are endothermic. Forreactions occurring at
while for
at constant volume, internalenergy E is used gencrally chemical reactions
constant pressure, enthalpy H is used. Since taking place at constant
occurr in open systems, thus, they must be
enthalpy H is more
atmospheric pressure. Hence, for energy changes
appropriate.
Let the following reaction is occurring at constant pressure
m,A tm,B=n,C+n,D
n, mole ofC and
Thus, m, mole ofA reacts with m, mole of Band gives
reaction is given
n, mole ofD. Mathematically, the enthalpy change during
by
reactants
AH = Total enthalpy of products - Total enthalpy of
=(n,He+n,Hp)-(m,H, +m,Hg)
respectively.
Where H, H, H- and H, are enthalpies ofA, B, Cand D,
Three conditions are possible, which are
Iftotal enthalpy of products is equal to the enthalpy of reactants, AH =0 i.e.
no heat absorbed or evolved during this reaction. These types of
reactions are called thermo neutral reactions.
 "inealu in uraburdin Beatun
Iatot,pnatat engtdute
aemialreatin atans
Iatutealirnthalpy
The itcat
diflere af
agien
323K n u
ahealeaton ablte teatti
and letneeu te trgerue
uresure by mperature
reattisg
thentalpies
tempeatue als
isknwnas and ad deends
ofreaction
due
stoiehioetrie prrsure,
toneete atn l futm
peute un
ofreaclants
eat is
h
of reattioH
the reprecited
lemperatue chanysshet in
reactinn, mol anount toyive
and
troducs betwemoles
olccts of mole I in
tlercac
J heat suhscrid and
liauidiA rESSu
utnd releaed
a g

Siyu deyree
calorieyu heat
between
intemieliy h
Themietet chemikal Thermminsr
CoVEutioUs in WIile
locaction-W| Ileatof of rection,
The
carily solution, tiny
rC temperature the rectuns
heat is Stirrer
he then teigetatut,
ehanpes since
Theroclemstry rise of
thewater Vip
in
inlemperature amount 2.1 rte,
cheuical rises
:Water
Calorie becaue
of
teactoS,
heat
of ealorimeter It
water albsorbed
ofheatis wlrt
Reacti

two Specilic hete,

releaed
by reactvn
after(b)
theoes chamber
water atn
hcat
of isdue before
re
water cqual to atet
evident reatun
to and
is the
1 (a)
 Physical Chemist
releasedheat Thermochemistry
the
absortbedor during aty 67
According tothis,like
theory-
Oldr products
cpressedwith
(g)+
393.SkJ
relea heat is sed
H, (e) ;0, 2) -H,00.
rcaction is
+0, (g)-C0, theory,absorbedor The heat evolved in the liquid
C(s) phase of
Accordingtothis separately, like phase becausc
bec
the extra heat, H,0 is more than the heat evolved
theory- expressed in vapour of
also in thewhich
New 393.5 kJ condensation is
cxpressedwith
productsbut
CO, (g):
vapour to liquid is liberated
form of heat during the
sign of hcat of of reacticn
C(s) +0,(g) in boththeories, the inendothermic rcaction H,O g) = H,o ():.
worth nothing
that
It is meaningremainsthe
same. For
example rcactions Similarly. LH 4.01 kJ
kJ s (Monoclinic) +0, g)-
changes but
(g)2NO(g)-179.9 AH+179.9 k SO, (g):. AH-300 kJ
N, (g) +O, s (Rhombic) +0, (g)= S0, (g):
(g) -2NO (g): 131.4 KJ t difTerence between heats of both rcactions AH-297.50kJ
N, (g) 0, *CO(g) + H, (g) - is due to
AH= 131,4kt
C(s) + H,0(g) sulphur. Thus, transitian of
-C0 (g) + H, (g):
or
C(s) +H,O(g) reactions s(Monoclinic) - S(Rhombic).
H
exothermic The amount -25kJ
for of heat required in
In this wav, + 92.0 kJ convertingI mole ofan allotrope into
(g) - 2NIH, (g) ole of another allotrope is called heat of transition 1
N,(g) " 3H,
AH: 92.0k
(g)- 2NH, (e: aY Reactions taking place at constant pressure or
of N, (g) +3H, nse a reaction is taking place at constant constant volume
+286.2kJ pressure and there is
volume of system tncreases, then work is done by change in
0, (g) -H,0()
me If the
H,(g) if volumne of system decreases, then the work system and
tant nressure, if volume done on the stem Ar
AH-286.2 kJ does not change o reaction occurs constant
H,(e)0,(g)H,00:
alme. then no work is done. 1hus, heat of
reaction at constant pressure,
ie different from the heat of
more applicable beca reaction at constant volume, AE. and the
difference between the energies is equal
more relevant, which is molecule to the work done and
Currently, new theorv is only by balancing hanee in volume. If the reactants and products are in solid and depends upon
equations of chemical reaction are expressedheat generated in a chemiest liguid states.
the
substances, not by heat. Thus, the then thedifference between heats of reaction is almost
volume is negligible. But if he sutbstance is in gaseous negligible
as change in
of different separateiy. state in a system, then
fcaction must be expressed the change ofvolume during a chemical reaction is more, so the difference
Reaction
Factor affecting the Heat ofa upon many factors between AH and LAE becomes more important. We know that
for any reaction depends
The heat of a reaction discussed
factors are below AH- AE+ PAV ...(2.1)
Some of the main substance, which
and Products- Ifany From thermodynamics, we know that
Physical state of Reactants
reaction are in different forms of
has participated or produced in a chemical different; because it comprises AH 4,and AE =q, thus q, -4, +PAV
physical state, then the heat of reaction is also Where AV is the change in volume at constant pressure P
of substance taking
of the heat released due to the change in physical state Let in a reaction, n, are the moles of gaseous reactants and n, are the
part in the reaction, like moles of gaseous products and their volumes are V, and V respectively. If
AH=-241.82 kJ the reaction occurs at constant pressure and temperature, then
H,(g)+0, (8) =H,0(g): PAV -PV,-v,)- PV,-PV,
 Physical Chens
Thermochemistry 69

sdealls,then For Exannple

hves
gas NaCl(s) aq- NaCl(aq.
1fthe SH-s 15k1
HCl(s) aqHCl(aq)
Thus , nRT
H,S0, () aq H,SO, (aq): SH
cxcess of water
Here ag. represents
and
eguathn(2 1)
From n,RT-n,RD) enthalpy change due to dissolving any solute n any solvent
SH- AE The upon concentration
derends nof solution. Thus, the concentration of volutinn
must also e expressed
with the enthalpy change For this, term integril heat
An.RT
number of moles
of gaseous products (n of solution i S
used. On dissolving I mole of solutein pure colvent. the change
formation of a specifie concentrate enlution is called
Total (n,) in enthalpy due
Where An gascousreactants of Solution. For exarmple, when I mole of potassam chioride
numher of moles
of three possibilities Integral Heat
equation (22 and 2.3). there are dissolved in 200 nofes ofTwater, I8.5S8 kJ heat is absorbed At ths concentration
From positive, then thisis
termed as Integral heattof soiution of KC1. It is clearthat if the smount
ic. An is is also different
When n, n, tsater is ditterent, the hcat of solution
AH> AE or 4,9. constant pressure.
KCI() +200 H,0) -KCI(200 H,0):
rcaction is more at
ic heat of then Similarl.
Sn is negative,
W hen , n, Lc. HCl(g) +200 H,0() -HCI(200 H,0) SH
AH AE or9, 9, volume. The heat of solution for some substances are given in Table 2
reaction is morc at constant
ic hcat of Table 2.1:The hcat of solution for some substances in water
=0, then (in kilo Joule mole)
When n,n, Le.An
SH AE or 9, 4. ha.
volume, it has sarme Moles of Heat of Compound Moles of Heat of
in which there is no change in Compound
Lc reaction volume. water solution H.0 saiution
pressure or at constant
tcaction either at constant
in solution- We know 6
7Concentration of reactants and products 200 5.35 HCI 200 0
released or absorbe NaCl
heat is cither
whet as solute dissolves in any solvent. in heat i. KCI
200 + 18.58 HBr 200 $331
solute in solvent, there is changebecor
In ather words on drssolving solution n becomes ta 200 + 35.40 HNO, 200 3121
heat is evolved ie. KNO,
change it enithalpy of svstem. If solution becomes cool, the 200 55.60 NH,NO 200 -C652
ther AH will be negative. Ifheat is absorbed i.e., in solvent depe
KOH
SH will be postive The heat change on dissolving solute K_SO: 400 +27.40 CuSO. 800 66 50
upot the amountnt of both: solute and solvent. Thus, this is important th
the moles of solute are fiscd to Imole, then the heat change depends ce Na,SO. 400 + 23.02CuSO,.5H,0 - 11.71

upon rumber of moles of solvent. Therefore, when any reaction is tak Na-SO,. l0H,0 390 +79.10 CaCl; 400 78.60
places in soltion, then the heat of solution of reactants and products is a NH, 200 35.35 CaCh.6H,0 13.8
fiecessarily ingorporated. Heat of solution, is the amount of heat released
aborbed, when I mole of solute is dissolved in excess of water, so that e It is clear from this table that when guses (like HCI, NH;. HB:, ete.) are
furher dilution, to exchange of heat is observed in solution," dissolved in water, then heat is evolved and value of sH is negative In the
fomation of solution of many salts like KCl, CaCl, 6H.0, etc. heat is absorbed
ic., AHis positive. It is cicar that heat so absorbed, is trom the solution, as a
 this, Some
salts Pikehysical Che Thermochemistry
sltin
from
Art
humso t Dogative i.c.,
sHis
heatis
is evolved and.
CaCl,. Here. AC, is the difference betwcen heat capacities of
rutthe solutionfor uhich reactants and
foms nroducts at constant pressurc. This equation is called Kirchhoffs equation
et SH,0
SH.0=CuS0,fomationoffhydrate of Similarlv for reactions taking place at constant volume, we can write it
homs ho.

Itssalcalts ou,
CuSO, the
eHeat of Hydration.
as
releasedisdueto
calledthe hydrated AE-EpEA
Thisheat thisraesis solutionof and anhy
during of
releasd
heat integralheat Where E, and E are the internal energies of reactants and products.
by Anowing respectively and AE is the diference inin inte
internal energy.
Spossible of solution of
any
aks
ner moleheat between solute deh
two integral
On differentiating it with respect to temperature (keeping volume
As
discussedearlier dillerence
Thele ic solution of 1 mole solute, constant)
concentration of solution.
uponthe solute
solutions of any another, then the enthalpy chan
of solutionfor
diluted from one
concentrationto
hkt
(2AE
T
(aAEA
as Heat of dilution,
Occurred is known
KCI(s)+20H,0()-
KCI(20 H,0):
H,0(0=KCI(20H.0):
AH-+159,
AH+185 (AE)
T y -(C,)a-(C,)a
or
KCl(s)-200 H,0):
Thus,
KCI(20H,0)-180 H.O()=KCI(200 AH +18.58 - 15.90 =28
KCI in 20 AC, 25)
diluting the solution, having I mole diluti
on
This shows that moles in the solution, -2.68 KJ heat of
180
of water by adding Here, AC, is the difference between hcat capacities of reactants and
released. Bis occurins fucts at constant volume. It is the other forn, of Kirchhofr's cquation
products
EfTect of Temperature- Suppose aprocesS A’
Li) (initial state Ifwe assume heat capacity C, to be constant (temperature range between
constant pressure. IfH, and H, are the enthalpies of rcactants
then change in enthalpy is T, and T,). then on integrating eq. (2.4).
and products (final state B), respectively
AH=H,-H
On differentiating it with respect to temperature (keeping
pressy dAH = AC,dT
H.
constant)

CAH OAH (AH, or AH, - AH, - AC, (T,-T)

or
ACp
AH)-AH,
T;-T
OAH
or
=(C,le-Cp)a
Similarly AC, = AE)-AE
...27)

(OAH
cquations.
at ...(24 Eq. (2.6) and (2.7) are known as Kirchhoff's
the value of C, changes in the
If the temperature range is high, then
following way
 re

C,*a+pT+yT'+..
Physical Che
which depend upon the Thermochemistry
73
Where a,B and yare constants.
substance. nature o nt constant pressure. Hence, the total change in heat in the complete
Thus, 4C, - Aa +TAB +T²Ay t. (2.S) in (2.4) and cess
pro
Or putting value of C, from
equation on AH, CF(1,-T)
between T, and T, integre h) For second path, assumning that the temperature of A is changed from
T. oT,, then the heat absorbed in this process will be cqual to C(T, -T.
while Cp is the heat capacity of reactant at constant pressure. Now at
temperature T, Ais converted into B. If thc hcat of reaction is AH, then the
otal change in heat in the complete process is
C,(T,-T,) +AH,
Now since, same changes occurred in a system from both the paths that
=(Aa +TAß+T´Ay
+.)dT means reactants at temperature 1 converts into products at temperature T,.
or
AH, - AH, Hence, according to law of conservation of energy, the heat change is equal
from botlh the paths. Thus,
AH, +C;(T,-T)=AH, +C,(T, -T)
-T)+ -T)4r}-) (T;-T)(C-C,)- AH, - AH,
-Aa(T;
Equation.
Equation (2.9) is called Integrated
Kirchhoff's or AC, =Cp'-Cp =All, - AH,
T;-T,
Alternative Derivation of Kirchhoff's Equation Hence, the change in hcat of reaction by change in one degree termperature
completed in twe.
constant pressure. reaction A -’ B, can be at constant pressure is cqual to the difference between heat capacities of
At
according to Fig. 2.2. products and reactants at constant pressure.
Ifthe reaction occurs at constant volume, then it can be proved similarl
as
AH.
AC, =C,'-C, = AE, - AE
CT,-T) |cT,-T) It is clear that the change in heat of reaction by change in one degree
-T AH, temperature at constant volume is equal to the difference between heat
capacities of products and reactants at constant volume.
AC, =0 or AC, =0 i.e., if the heat capacities of reactants and products
Reaction coordinate are same, then there is no effect of temperature change on heat of reaction.
Fig, 2.2 Thc conversion of reactant A
at temperature T., into nroduet Ba Standard Heat ofReaction
temperature T, by two different paths The comparison ofheats of different chemical reaction is only possible.
(a) AAssuming that AH, be the heat of reaction in conversion of Ato Bz when they all are measured at the same standard temperature and pressure.
temperature T,. Now the temperature of Biis changed from T, to 25°C i.e., 298.15 K temperature and I atmospheric pressure is most likely to be
absorbed will be equal to C; (}-, while C is the T,, then hea state. Thus, The standard heat of rcaction is the heat of reaction
heat capacity of aforstandard
reaction takingplace at 1atmospheric pressure and 298.15 Ktemperature
 Physical Chemis Thermochemistry
Since, every rcaction is hr 74.85 kJ
AH-
At081s 0r such reaction
Thus, -AE+(-1 mole)
represcnted as
thus, for
lemperature,temperature
measurement
rcaction.and then with the hel (8314 × o kJ
and it is
completedat this
donc at the
of
into
standard pressure AE=-72.37J Kelvin mole) (298
heat of
rection is
it can be
converted
Example 3. On dissolving I mole
Kelvin)
Kirchhofl's cquation, HClin 2 mole water, the
of burnt in oxVgen gas at solutionAH is --47.99 kJ. When Ii n mole
Iemeralure nanhthalene was
waterat 25°C. The heat constay SHis--63.09 kJ. (Calculate the heat of dilution.dissolved in 5 integral heat of
HClis
mole water, then
Example 1. I
moBe
carbon
of
Iiquid
dioxidegas and the enthalpy
volumelo give 5138.8 KJ. Calculate
1evolver
f reaction at const
thermochemical cquations for above solutions are-
Solution: The t
o HCI(g) +
wAs found to be
forabovC
reaction i. 2H,0()=HCI(2H,0),
pressure.
Solution: The
themmochemicalequation
(0: AH=-5138.84
i) HCIg) +5H,0() -HCI(SH,O);:
AH-47.
AH-63.09 99kJkJ
120, (g) =10C0, (g)+4H,0 On subtracting equation () from (ii
CoH,(s) +
We know that
AH=AE+ AnRT
HCI(2H, 0)+3H,0()=HCI(2H,
AlI: -63.09(-47.99) 0);
kJ -15.10kJ
Thus the heat of dilution = S.10 kJ
Here AE=$|38SI
R-8314J Kelvinmole!
mole Example 4. AH for the reaction H, (g)+
-8314× 10-'kJ Kelvin
I-298K
en
Calculate heat of reaction at 60°C. ;O,e)-H,0()
al
At constant
a2$°C is
of moles of gaseous
products) nmmerature range 25-60C, the Value of molar heat capacities pressure and in
An =(Total number gaseous reactan
of H,(g), 0.0)
and H,O(), respectively, are b.90, 7.05 and 18.00 cal Kelvin-l
and (Total number of moles of Solution: We know that
-(10)-(2) =-2
kJ)
AH, -AH
Thus, AH =(-5138.8 mole) (298 kek.
+(-2 mole) (8314 x10- kJ Kelvin
-S143.76 kJ SH, AH, +aC, (T, -T)
is fomed f
4.8$ kJ heat is evolved, when I mole methane
Example 2. Calculate hea
temperature and I atm pressure,
its constituents at 25°C constant volume.
fomation of methane at
for above reaction is
Solution: The themochemical equation AH=-74.8$ -18.00-|6.90 + 2
C(s)+ 20, (g) CH, (g):
From AH=AE + AnRT =7.575 Cal Kelvin
Here AH=-74.85 kJ -7.575 x 10-kCal Kelvin
R-8.314 x 10kJ Kelvin' mole AH, --68.32 kCal
T=298 K
T,=25°C- 298 Kand T, =60°C =333 K
and An -(l)-(2) =-Imole
AH, =-68.32 +7.575 x10' (333-298)
--68.055 kCal.
 Physical Chemin Thermochemistry
3H,(g)’2NH,(g)
6
reactionforN,
heat of reactionat 50°C.
(g) +
)a27a
Attconstant pressure : and Table 2,2 Standard heats ofI
77
capacitics ofN
Eample5.The (N,(g), 1,g) a Joulecombustion
(in kilo for
of
Caleulateheat molar hcat degree per mole) some substance
-9).96KI. range,the value of and37.08Joule per
is ature 28.33 Compound
this temperature
respectively are28.71, AH29g Compound
NH.(e).
AH, -AH,
AC, (T;- T)
+3*CrlM,(e)nl
Methane CH, (g) -890.35 Benzoic acid
Solution: -pIN:(8) 3226 60
C,H,COOH (S)
Here 4c, =2Cp|NH(RI 28.331
-237.08-(28.71 +3 x
Ethanc C;H, (g) -I560.60 Salicylic acid
-3025 45
--39.54J Kelvin'l Ethvlene C,H, (g) CsH(OHCOOH (s)
Kelvin! Acctylene C;H, (g)
-1410.97 Sucrase C1H0,,() -S644 20
*-39.,54x 10&J 1299.10 Urea CO(NH,, (5) -538 90
AH, -9l96kJ
Propane C;H, (g)
n-Butane C,Ho (g)
-2220.03 Glucose C,H,0,() -2822.20

I, 300Kand T, -
323 K
10)(323-300) n-Pentane CçH2 (g) -2874.,74|Naphthalene CiGH, (s)
-3536.15Glycerol C,H, (OH)h () S138.70
-91.96+(-39.54 x -Hexanc CH, (e) -l666.10
sH, 4163.08| Benzene ClL, (g) -3293.64
92.87 kJ Methanol CH,OH () -726.63 Benzene C,H, ()
Ethanol CH,OH () -3267.62
Various Heats of Reactions offchemical reaction, various names have 1366.67 Toluene C,li,CH; () 3910.00
nature of
On the basis ofreaction, like heat offcombustion, heat solution Formic acid HCOOH () -262.70 |Nitrobenzene
of
vaporization
he -3097.41
given to the heat
of
heat of fusion, heat of sublimation, heat
Some ofthem s C,H,NO, ()
Aeotic acid CH,COOH () -869.80 Phenol C,H,OH (s)
heat of fomation, neutralization, heat of ionization, etc. 3062.69
transition, heat of Oxalic acid (COOH): (s) -25L.46 Xylene C,H, (CH;) () 4552.19
Heatof Com bustion mole of..
accompanying complete oxidation of I
Ethyl acetate
CH,COOC,H, () -2254.50|Hydrogen H; (g) -285.83
The enthalpy change combustion of that substance. The he
substance is called heat of at standard state i.e.,
25°C tempera Acetaldehyde -1164.40C (Graphite) -393.51
combustion for a certain substance For examnle CH;CHO ()
atmospberic is known as standard heat of combustion.
and I Acetone CH,COCH, ()
AHs98 -890.35M
|-1782.88C (Diamond) -395 39
2H,0(): Diethyl ether -2735.80s (Monoclinic)
CH, (g) +20, (e) =C0, (g) + (CzH.),0 ()
-300.00
1 atm pressure, the comple.
This equation shows that at 298 K and
standard heat of combustir S (Rhombic)
combustion of methane gives 890.35 kJ heat. The -297.50
. Table 2.2,
of some substances is listed in CO, (g) -282.98
Determination of Heat of Combustion
the platinum wire W is connected between the rods Rand G Aweighed anmount
The heat of combustion of any substance can be determined with of substance, whose heat of combustion is to be determined is taken in platinum
help ofBomb Calorimeter, made by Berthelot in 1881.According to Fig. 2.3, the cup C. Now the bomb is tightly closed and oxygun is filled in it through pipe
inner chamber Ais made up of strong stainless steel, which is called bomt T. ill the pressure of about 20-25 is attained. After closing thein stopper, the
(due to its shape), The inner surface of bomb is enameled with platinum s bomb calorimeter is put intoB.A known amount of water is taken calorimeter
that oxidation of steel is prevented. The bomb consists of an air stopper Sand and a mechanical stirer and themometer (Beckmann Thermometer) is attached
tube T. A small platinum cup C also, which is supported on a rod R. A tht to it.
 system
constantcalorimeter,
found
Example
to
calculated
bethisby
measured
Since,
the
Thus, calorimeter combust
Ittemperature
heat is Suppose
ipurpose, ed ved water risesubst:nce
on bumievolng vcbser excess complete
Witplhrrough
aeTh.teinum
of
combustion clectricignisubst
in
ol
temperThe maiatunrteawaiadinstuedcondi
isead.nce
tednotbecomes eof tedis The
rrWhabatoenunditihceonnisgolcalorimeter
iathtaso
generalatlyknown calThe otriemperat
mdue eter ureoNygen
was a
volume rise bvsteady.
found
bythe AH-AEAnRT + by this evolved equzl is
donc
is
from
0.55°C. 6.
temperature On method
Heat then
C
constwant heat to Currentpassing
23.85
to(i:)
be at complete following
Calculate
constant
the process
is.
-AE(-7,)M
occurs
in
burming heat
the
to
absorbedcalorimcter
ofgm weiyht
benzoi
substancevolume ofa
c capacity
heat
is oand in of
it
is its

evolofved by acid of
kI combustion
the
of
equation. Heat of at rises of of e issubst
- ance th Fig. Stir er
pressure,
K the
calorineter constant one system
hea: mole due ar 7kJ calorimeter
from mol3226.
high 2.3:
combustion at - of
gradeknown Bomb
The ofof0.5^ toC(T, T,mass
Aw. R
combustion volume, of
heai system
burning
substance to Mpepurity
r and
gof
-
I) T,. is mole heat calorimeter
capacity(including
benzoic the of burnt
II of is its
of constant
pressure ca
heat is W the taken, svstem
benzoic gm heat
and combustion Pl1ysical
Chemig
of acid of is
calorimeid water) combustins of after whose
acid in substanrs capacit obta -Platin
cur
...(2.10 h Wate.
(i)a was bot a h E

calculate
pressure.
constant volume, acid. 2.13
heat of calorimeter cauatiori equation
following
and Here, Solution:
We
the
K.
the Example
In
C,HCOOH h Here, TherSolution:
mochemistry
know temperature an combustion At
heat another at Constant
ekJ w
E-3226.7mol=0,855 that ()
combustionfor of
25°C,AH=-320067 T-298 K mole
R-8314
7. An-7-7.5--0.5 AnRT
AH-AE+ -
AEgmole!
M=122 T,-1,0.55 KC= -AE
()
calculation On (s) 23.85
-AF combustion the -3201.9
experiment,complete mole kJ 3200.67molekJ - know We
g:
was +7.50,(g)
x of pressure, 3200.67 (23.85 CI-T)M
kJK-!
temperature 10: benzoic
122gmole:T, found
of combustion + kJ kJ kJ that
naphthalene
heat for (-0.5) heat mole! Kelvin
to on Kelvinmole =7C0, acid heat
-)M benzoiccomplete
rise of of
capacity (8.314 w=0.50 g of
the involves combustion combustion
by of0.625 (g) (0.50g)(0.55
)
acid calorimeter
()combustion
1.89 ×
-T-1.89
of at 10)(298) 3H,00).
calorimeter constan: is- K. g follow Kelvin)x
can
3226.7 At of at
25°C
naphthalene
was AE ing calculated by
be constant
volume of0.855 (122
K and kJ found thermochemical
its mole, and 320067 kJ g. volurne
and constant g to in mole
system benzois rise a
(ii) then bomb the
at by 79
 s0

that assumedseries,
ofany itthe order kJseries,
Applications
pressure
is and
clearvalue (Table The (i) Agafroinm:-AE () Thus,
meber the () Here, Ciot,
knowth1Wate
member ttowo after
Determination thermochemi(s) -calCalculation AE- Calculation -L.964 k C

(32 %7kImole)-
that of heat
T,w--2,013626g,
I, K
can successive
be
of the
bethis heat
heat heat
this 2
for
2).
For of Heat
of
AH=(-5218 AnAH
= AE 12
AF
C=I1.964NK of
easily combustion combustion of of combustion
every
example, the of le 10-12
-5223,94 mokJ + 0,
() 5218.heatof984 1964 heat
M
C(G-T)M combustion
homologous members Com of
of
ofstructure AnRT equation
combustion
determined. consecutive
bustion 984) =-2 10Co, of kJ kJ 128
=
mmole Kelvin
series
differed
of-CH,-
decreases
are is
additive member
an heat of
organic
of
oforgan
+(-2)
(83
mole
(g)
+
combust
for ion
the
!
(0.6)x(2.13
25 g)
mole!
g
for
Cx(189
is combustion
known, approximately compounds ic
14 3H,0 ion
combust naphthalene
r
K)x
0.855 g)
by
group.property.
-CH,- paraflin
compound-
of 10)(298)
x
():AE
for
K) (12 #g
then
for naphtofhalene (028 mole')physical
Chemi
molecular heat If Since
group, dccreases
methane
by
hydrocarbon In
=-S218.napht984halen- g constant
at

of in
661.07 the mole
homologou
661.07 at
combustiz
formulao homolozo
is in l vol
kJ.
a
kI .
serin 8903 fixe
k Thy
standard elerments
standard determination
transition
determined
Formation
Heat of organic not substances,
differentavemee eneroy lowcombustion
enlorific
heat
On of saturated Here Heat
ofa .a
Thermochemistry
The (iii) by a) So, (iii) cost
Calorifie
value bv
their person to using Calorific ofhydrocarbon
heat states compounds food and value. unknown adding n of
enthalpyis Calculation
of our
dircctly
from price, we of n(661.07)-
1984,67
n3 combustion
is
ofheat substancesneeds body.efficient 3(CH,)-’C,Ho hydrocarbon the
called different less -2874.74-890.07-
CH,+ n(661
07)
of(25"C The one 3(CH,)
H,
formation
may
fuel.
(g);0,
H, Heat
change, 300 have By fuel
value
highpoundcompound number
ofcan
(g)+ and allotropes
formation. of
kCal knowing
In
calorific
this of in can
of
l experiments.
of be
heat
according anfood-
Food of for of
fuels- methanc, be of
and atm when
formation.
is- unknown
calculated way, any determined.CH,
0,(e)- -H,0(0:(g) it
pressure),
is I can reaction-
of per idea industries.
day.about the known
value
substance Thebutane
is 2874.74
denoted mole Similarly the
to
heat amount member
group,
also their In of
HCI(g): If of
then the any
easily; ever the calorific any
molecular
For
kJ.
bc Since oxidation
substance ofon is Thus
by
detemined,
from importance dayenergy
combustion fucl
knownofheat examplewhich (AH)
AH,.For reactantsthe
substance hence
heat the life, implies formula
heat value released on
provided
one as the -890,07
of of itheat addition
i.e., helps more s it
--285.83
AH, kJ formation and is combustion, can of should
example of of heat
AH, formed which thermal due
-n
products combustion be calorific different production in
compound
by of to
-92.31 kJ cannot
used incorporate
them.
purchasing to combustion (661.07)
is fron provides complete
value CH,,
called are heat in value,
food is
be ofthe of An the
inits of or 21
 Physical Chemi Thermochemistry
tempe,
articular
cnthalpy at a absolute value of 83
hasa certain to calkulate
Even substance
is
difticult
Anowthat it calculatedecasil.
enthal Table 2.3 Standard heat of
o
formation
(in kJ per of
mole) some compounds
pressure. We canbe
enthalo enthalpy of eeverv frec
relative pressure, the compona Compound
but atm enthalpies of AH, Compound
25Cand I
Forthis, at therefore,ihe example-the
is Z5umed
to e zero and formation, For
standardheat
of 25°Cand I atm:pressure is
thermochemi Inorganic AH,
ual to their
ot
fomation of CO, at H.0) -285.83 C(Gaphite)
eQuationfr heat 0 00

tolkws sH-393 51
H.0(8)
HCI (g)
241.83|C(Diamond)
9231S (Rhombc) 1.895
C()+0.(g)-COr(g). L
of CO, is- 393.51 -3640 S(Monoclinic) 0.00
of formation HBr (8)
That means thestandard heat HI (g) " 2648| AgCl (s) +2 50
12707
We know that HNO, (/) 173 20 AgNO, (s)
- 124.39
#,S0, (0) -811.30| Ag0(s)
(Enthalpies of reactants) S0, (g) - 296.83| Fe0 (s) -31,05
products)
(Enthalpis of dioxide)-(Enthalpy of carbon Enthaloy of
+ 266.30)
- oxyg SO; (g) 395.72 Fe,(0, (s)
(Enthalps ofcaton is equal to zero, thås -110.53 Fe,0, (s) -824.20
clements,enthalpy CO (g)
|1840
Singe for free CO, (g) -39351 KCI ()
dioxide
H,Enthalpy of carbon NO (g) +90.25 KOH (S) -436.75
dioxide - 424.76
offormation ofcarbon (AH, )- Enthalpy NO, (g) +33.18| NaCl (s)
heat -4|1.15
rthe standrd NH; (g) -46.11| NaOH (s)
carbon dioxide -425.61
thermochemical cquation H,S (g) - 2063 NaCO, ()
ing 1130.93
Similarly for follow AH=-296.83 CuO (g) -IS7.30 PbSO, (s)
S(9)+0,(g) =SO,(g): CaCO, (s)
-91420
- 12069
Ho,(e)
AH, =Hso,g) -Hss, t Organic
enthalpy is taken as zero, thus Methane CH,(g) 74.81| Benzene CH, (g)
Since for free elements, Ethane C;H, (g)
49.00
-89.20Methanol CH,OH () -238.60
AH -Hso.g) -296 83 kJ Propane C,H, (g) - 103,85 Ethanol C-H,OH () -277.69
enthalpy of SO, is equal to n-Butane C,Ho(g)
Hence at 25°C and latm pressure, the - 126.72 Ethanol C,H,OH () -236.40
standard heat of formation. n-Pentane CçHp(g) 146.44Acetic acid CH,COOH () -487,00
enthalpy of every substance
It is clear from above examples that n-Hexane CH4(8) - 167.20 Naphthalene CyoH_ (s) + 60,00
The standard heats
cquivalent to its standard heat of formation (AH,). n-Octane C7 Hs (g) -208.40 Oxalic acid (COOH}; (s) - 827.20
formation of various compounds are listed in Table23. Ethylene C,H,(g) + 52.26 Sucrose CpH,,0, (s) -2222.00

Acetylene C,H;(g) -226.73| Urea CO(NH,a (s) -$38,90

 equations. s4

On Solution: (u) (0)

chemical otherInposianentd tihvale pies
are
constituentindicates called present words,likely ofI
mole constit uent
cnthfoalrpmvation The
Example Thi s
exotCompound.
htheratmic chemiH, incal beH, to Thust
,he
adding KOH K(s) bondwords, cntlesshalpy means of of
negatofivae
(e) H, present st abl e . ele ment s. more an0
d.5 ele ment s
0,. bondstableenthalpy H,compound
0.5 or
K69*;0,
equationG)-; First, (S)
H,0aq.()+aq.
+
+ 8.
Calculate chemical Thus, ormole that compounds.
heat
is whic h (g) compound value
we in heat
H, the For
ahsorbed mol e of For is
(i)
and
have
KOH
=
heatH-Hor bond HIof enthalpy
(g) cxample have presentHence, O,Th.e mole I0,(g) example alwofavsentfrhomalpy
(ii) determine (2q):
to
- molformat
ofpresent ecule ion, and duri ngnegati
On ve in
of -
KOH fornation H. 0.5 of contrary, H,0 H,0
compound,
which OH,0 les its
H¡(g)- (2q) is
inless are mole mole
I
the is is H, constthanitiunentdicates
heat H-I called l, of
heat
much more less
is ().
KOH + of stable (g) fomatioposin tive of the
(9): formation AH=-48.
of
H,(g)I:kCa
anhydrous
weaker
is HI
(g) forvalmuateion strongerstable than addiclteioment
n s.
that
heat
htermi
han
cndotCompounds,
c is minimum
than has the n
of iss
k =-684kCa AH
AH-13.0 Ca
KOH
in
,HI,
: more
k compound
+264%AH from of(or than addition
H,. , AH evolved
ofInPhysical
Chen
ofKOH. and heat and enthalpies
from
compari50n than enthalpy),. chemical this
come ot of
folln molecule whit rbe. format f InO, cntha-28583
enthalo
chthalp during
state,
AH= othe
be of

Second
method
fomatare-327.
ethydrihoanolnogenof
, 0,
enthalpy
The Thus,

the
heat
subtracting
(92C
)+
On

2C
Mlrinly

(i)
have
Wei)
C(s)
2C toC,H, (g)H, First
0 Examplfformation
( talution: e Thus,
anhydrous
heat
K);0,g)*
subtracting
On
Thermochemistr
(S) by (S) *5O,(8)-H,0
calculateOH)+ +0,(g) -103.5Cal KG)0,(g)*;H,(s)-
of
terms of At
+;0, 3H, +
equation 2
formation and method- 94.0 29s equation
in 0,(g)+ (in) 50,g)=2C0,(g)
(g) (g);0,(g)
equation CO, and K,
(i) by It the KOH of (ii)
3H, + (g),
of 3 is 68.4k
cthanol 3H,(g) from
and given heat from
(ii)
(g)-2C0,(g) 0); of Cal H,
this.
can AH-188.0-2052=-3932kCal
AH=-3932
=66.2 -C,H,OH
then Cal. -1035k
AH-1165-(-130)
that 1, (g) i.
-C,H,0H
on
formation
respectivelyCaleulateAH-684-48.1--1165kCal
-KOH
written
be
adding 3H,0(): + q
k
=
(9); KOH -
Cal. (O): + of
as --327.0) 3H,00): both (), ethanol,
eauatinns AH-3270kclAH=-684KCalAH-94,0kCal k g).
=-66.2 carbon
the
AH
=9 heat
kJ ofand
 Physical Chen
Thermochemistry

formation gof compo

Heat of
AH=|2Ho0,(g) compoundI 12c(9)+ 1| H,(g) + 87

Weknow
Thus that
ennhalpyof
Mco.te-40OkCal 5.50,(g)-C,0, (9%. AH,-2222 kJ
Hy.ou) -68.4ACal
C.l,,0,(6)- 120,(B) -12 C0, (g) +1H,00.
zero,
5641&IA-5643,8kJ
ofclementsis rus. thc heat tormation
of of
mnle IL.Calculate the heatsucrose
cnthalpy is-
Since
Ho,e0 +3x(-68.9))-(Hcl.OMal of formation of KCl from following data.
-3270 =[2x(-394.0)
-662 k Cal
formation Al--68.4 kCal
to its hcat of
cthanolis cqual k Cal -HCl (ag.:
The enthalpv
of ofC,H,OHn-66.2 AH=-39.3k Cal
offormation reaction off sucrose (C,,H,.. (ii) KCI(s) aq -KCI (aq ):
So,thc heat heats of
Thestandard -2222,-393.5
and-285: s.8 kJ.respecti AH =+44k Cal
Exumple10. d KOH
carbon dioxideandliquid
standard
waterare
heat ofrenction
of
sucrose.
(aq.)-HCl(aq)=KCl(aq )+H,00%
AH=-13.7k Cal
Cakeulatethe (v) K(s) t,0,(g)+ H,(g)
Selution: Given aq- KOH (aq.):AH-16.S kCal
C(s)+0,(g)-CO, (g).
Al-393 Salution: have to find out Icat of formationof KCl thus
We
0
All 285
() 4,(g)
+0,(g)-H,0(): K6)Cl,(e)-KCi6)%,
2 AH -9
(g)=Ci:0S); aH, - On adding equation (ii), (iv) and (v)
+5.50,
(i) 12C(s) + H,(g)
We have to find
out K(G)+
12 CO,(g) +ll
H,O), AH
CpH,,0,,(6) +120,(g)= by ll and then these are
ads. AH=-393-13.7 -116,5 = -169.5kCal
multiplied by l2 and eq.it (i)
Eq. () issubtracting
On subtracting equation (i) and (iii) from this
eg (ii) from
followed by
(g):
AH -472. K(S) + Cl, (g)- KCl9);
12C(3) +120, (g)= 12 C0,
AH, =-3143 AH=-69.5 -(-68,4)-(+44)--105,5k Cal.
H,(g)+ 5.50, (g)=11 H,0(0: Hence, the heat of fonnation of KCl =-105.5 k Cal
Heat of Neutralisation
+11 H,O():
12C(9)+ 11H, (g) +17.5 0, (e) =12 CO, (g) The enthalpy change accompanying the neutralization of one gm
AH, -78651 equivalent of base by one gm equivalent ofan acid in dilute solutions is called
Icat of neutralization. For example
 Pysical Chemit Thermochemistry

(aq.)+H,00: AH Heatof loniation

HCI(aq)+ NaOH(ag)- NaCl
is
evolved in the comr S7,32k1 The enthalpy change
$7.32 kJ heat comple,
iC., in
dilute
solution,
equivalent of HCIby I
of
gm equivalent NaOH.
Bou. weak acid
or weak accompanying
base into ions in a solutioncomplete
isi termedionization of l mole of
neutralization of lgm represcnted by HA and In examples, in neutralization of as heat of
base is he fHCIby OH, 57.32 kJ heationizatinn.
acid, strong b¡y, obtained. TheNH,difference
strong strong only 51.46 kJ Jheat is
and then as but
If strong acid are dissolved in water,
released
in the ionization of NH.COH. should be
quivalent amounts complctely ionized in
water, so used,
NH,OHis5.86 kJ. Similarly, the Therefore,ofthe heat of (5.86 kJ) in heatifor
and their salts are
H*(a4) A' (aq.) +B´ (aq) +
OH (aq)
be represented as
follows. neutralization strong acid neutralizatbaseicn can
by weak

-B* (aq) A'

(aq) +H20(): AH=-S7.32 CH,COOH (aq) +OH
(aq.)CH, CO0 (aq)+H,00),
or
the(aq)
Thus,H + OH (a4)- H,o0:
neutralization AH-S7.32
of any acid and basc involves sonly one reaction,
Assuming that this reaction is
completed in two steps- AH-5523W
Ihis implies CH.COOH (aq)=Haq) +CH,CO0 (ag.)
form unionized water.
ie. H' and OH ions combine
strong acid
to
and strong base,
the
reactions
value oof heat
evolved y H* (a4) +OH (aq )- H,o(0); AHx
AH-57 32 kJ
neutralization of On addition
can he confirmed by following
same. This
HCI (aq)+ KOH (aq)
=- KCl (aq) H,0(0. All=-5745 CHCOOH (aq.)+ OH (24)CHCOo (aq) +H,0):
HCl (aq) +LiOH (aq) -
LiCl(aq) +H,00): AH=-5738L AH- (x-57 32) kJ
+ NaOH(aq )-NaNO, (aq) +H,0(0). AH 57.28\J Thus -55.23 kJ (x-57.32)k1
INO, (aq)
KNO, (aq.) +H,0(): AH=-58.03k X=+2.09kJ
HNO, (aq) +KOH (aq) =processes involves only one reaction : or

These all neutralization and t Therefore. heat of ionizationof acetic acid +2.09 kJ
of H" and OH, hence, heat of neutral1zation is fixed
Therefors Measurement of Heatof Neutralization
cambination neutralization is taken as -57.32
kJ.
a1erage value for this bination of Igm of H" ion and l gm ofOH-ion. Vaceum Nask calorimeter- Vaccum flask
process, w hich involves com
is called neutralization
process. fask calorimeler, which is put in woodencalorimeter have a Desar
box and the empty 5pace
form I nole unionized water, thae een them is filled with some woolen
cloths or other insulated substance
then the heat of neutralization is less (Fig. 2.4). Since
But ifacid or base is weak, combination ofH andO
-$7.32 J, because the reaction acidinvolves not only heat Fo Dewar flask has dual
dissociation of weak or weak base, which requires
but also walls, there is
vaccum in between
example
HCl(aq)- NH,OH (aq)=NH,CI (aq )+H,0): AH--51,46J wo walls and the in
+H,0 (): ner surface is shiny:
HCOOH (aq)+ NH,OH (aq) HCOONH, (aq) thus, the heat loss Heat
AH -49.79k
via all the three me- Stirrer insulator
CH,COOH(aq)+ NaOH(a4) -CH,COONa (aq) +H,0(0: dia i.c., conduction,
AH=-5323 W radiation or convec
tion, is minimum. Dewar
AH=-12.13M Thenometer
HCl(a4,) +NaOH(a4) =NaCN(aq,) +H,0(0): Therefore, this calo
vaccum
lask
rimeter is more use
;H,S (aq) +NaOH (aq)=; Na,S (aq) +H,0(); AH- 15.99W ful for the measure
ment of heat of neu Fig. 2.4: Vaccum lask calorimeter
Iralization.
 Physical Chemia Thermochemistry
thrce steps Caleulationn of hcat of 91
90
process takes place in
complete ofwaterequivalentby
calorimeter. (ii) neutralization-
released in neutralization
The The heat nof 100
tempcrature mL of N-
T.then
()
Determ
m, gm
ination

athigher
in
wateris takentemperafureT,.
low
calorimeter atAferstiring,the final,
calorimeteris W, then
m,
temperahu
Thus, heat relcased in

1000o Calorie
neutralization HCI9Cal
mL of oN-rie HCI
of 1000
mixedinit of
water is
Ifthewaterequivalent I00

T, is recorded. T)- m, (T,-T,) or heat released in neutralization of !I gm

(m, W)(T, - orheatoofneutralizationn aofHCI 100 Calorie equivalent of HC|- 100Calorie
m (211
or
Wm, (T-1)

(ü)
Determination ofhcat
and I00
in
released
ml. N-NaOH
neutralization

aretaken in separate beakers,

both solutions :
sine.
AH = 10(200+
w-, 1)lcalorie (213)
100 ml. N.HCl temperature of arc notet
temperatures so and T, is the AH = 10(200 + W)
temperature of acid
both have diflerent
Now boh
that T, is
arately. Assuming mixed
are
the
d
temper or

neutralization of any 214)

ture of base. the tem Heat of acid or
base can be
nthe
calorimcter and
recorded .sluc of Win equation (2.13) and (2.14) calculated by putting
perature ofmof mixture is
These tempera Example 12. At 298.35 K. 1S0 mLof0.5 NHCIl and at 298.45 K, I50
per 30 second. iin Dewar
with reference
tutes are plotted (Fig 25), Af
r
0.5N NaOH issmixed Flask. Ifthe final temperature is 301.2 K, mlof
heat oofneutralization of
of then
to time on
graph calculate the
ofcalorimeter is 60 gm. hydrochloric acid. The water equivalent
ter mixing the temperature in
after reaching E T.
creases first but
at point 'd'
temperature starts Solution: Initial temperature 298.35 K+29%,4>984K
radiations
decreasing due to
extrapolated and Final temperature = 301.2 K
Lne 'c d' is Time (sec.)+
to tem
from ita line 'bfparallel Water equivalent of calorimeter =60 gm
perature axis is drawn
which in Fie. 25: Determination offinal temperatun The heat
from which no lo. released due to mixing of both solutions
tersects 2t point 'e it means that when there is
temperature T, is noted In simple words,
time oof mixing (h) of acid and base the
rea -(150+150 +60) x(301.2-298.4) x4.184J
the
ofheat due to radiations, then at calculation, the initial lemperature of mixturs - 4217.5 J
temperature is T. To simplify the
Heat released due toneutralization of 150 mL of0.5 NHCI=4217SJ
neutralization i_ Oel
is assumed to be (T, +T). If the heat released in Therefore, heat released due to neutralization of 1000 ml ofN HCI
then 4217.5x 1000
= 56233 J
150x 0.5
Q =(100+100 + Heat of neutralization ofhydrochloric acid -56.233 kJ

...(213
 processes complete nnore
thantwo as
Hess'
"1fa sV)
L exanple
reactcquat
ion in to heats
it
ion insource opposite heat
Aawsofheat heatTofhermcnergyochemiThe stry
of of
Assuming
shown
as change
given
co, CO
Similarly can
It

be
its by ofThis
can formircaction
constituents. ng is
()Lavoisiconscr
fowirmtformat erandvation,
ion red
hation requi two
H,(g) reversed.comoundaccordiare ngHCI(g)= inportant
chemical s's written be sign,
Law (g) (g) 0,()-H,00%
different
that is is ofto
in same,
6. a change of H,H,
Fig.2.change 0(g) +
+
as The not like that
cqualdissociLapbce'
ateTheserul
s es laws
whether (g)=CO{g)+
processes,Constant follows if same, firstto compouna to
-C0, importance
the from its of
R then law a
ifoflromaw(1th780+
ermochemiarestry
takes
the Summat
then ion (g) 0,(9):
heat
it
its of compound
heat
Pi
change the
place
H,0(gk+1,(gk const i
oftu ent
ofs is
reactionthermodynami cs,
in
this possible decomposition Accor its into
mn'eted
takes
heat(1840)-
released
one law
AHisand to clements," ils ding
place
or are
threuah severalsteps This signs that produce
then cline"Inments thisto based
by thor the
absorbed
two any
law =+48.95
einAH=-48,95 kJ AHAH=+285,83 k AH=-28S.83k
kJ again because -923IAH-923lk
are principlethe onoChemi
Physical
can themochem:
reversed dissoeienergy if
AH simpleWords .
magnitude
is
Theam
lay
differentprocess. by e
twoor statedbe uibou. but
t

Fipatrsth paths bv vreaches not final severalinthiin

contradicrteopeatr[yAH-ing(AcH,othnenverttilarly. amount
obta
AH
ined. thiinIn
sto Rthis into
edinto omust instate, respectively, P fsirsInta
s

NH,
(g)
reaction following
between
examplesdepend
Example

intermediate
l.
on of
from
states According
Ps

initial AH=(AH, AHAH tov

system to (AH,
this
cycle, suppose P
equal
beof a R
heat. singlecan AH=
Suppose+AH,(0H,
the
If I
steps.
heat then
orocess
process,
is
t
Thermochemistry
+ ammonia,
The
state Hess's
(AH, first + by to This wayconverted
sttheenp again be according
(AH, First AH.
aq aqueous law one
AH, t single AlH, is by converted AH, change R R
- and +AH, + contradictory + Supposing is can
NH, to t AH, ofcaAH)] (A H + ,
products. final does law, AH, thermodynamics. n step repeating
AH, + AH, converted
to
in be nt Fig. |AH,
(aq ammonium
solution
hydrogen of heat + + + AH,
into )> directly 2.6:
state. not AH,)
+AH,) AH,) produce amount and AH, H,. + ,+ AH, +different
Hess's
that
): of AH, + P >AH
The depend again th is to Hess's
reaction and unlimited to by
chlorideand verification otherIn amount of of AH,) This firstcycle, different and conversions second
law. A,in
changed
heat into R
converted H,)-AH) then
proves law reaction law
words, upon depends 1 can <
one process,A to
be AH. the of steps RPis
to P.
B
watchloride
er steps themodynamics.
obtained. validity can are Suppose
this ofheat only In
this unlimited
amount and sH,
and
R
by through produce finally,
AH=-35.IS KJ following can law of upon different in is
heat, this In
i. state
AH,converted hcat
be reaction
can of exothermic.
of
initial heat B
prepared bewhich which is can
Hess'
Rs and reaction of
converts
two done does and
way by
steps Thus, ca n (215)
to
i belaw. b In Ait F 93
 Tlhermochemistry 95

94 Pliysical Cheml c)+;,(g)-co(E),

sH-AH-AM-1559\,A5219h
SH xkJ
HCI(g) +aq. - HCl (aq ):
NH, (aq )+HCI (aq) - NH,Cl(a4.;
NH, (g) + HCl(g) +aq, =
NH,Cl (aq,): coe) *;O, (8) =CO,(g): AH- yk

Second path
NH, (g) +HCI(g) - NH,Cl(S):
NH,CI(s) +aq. - NH,Cl(a4.);
AH-AH 1=+1632\
76.15 Therelorc,
xty=-393.51 kÊ

change
involved in the combustion of
CO (g) and O, (g) to
and Iiits value is -282.98 kJ
The heat emeasured casily
NH, (g) +HCI(g) +aq, =NH,Cl
(a4.);
amount of heat
AH-159.
released in 83
both patha giveCO,
can
(g)
ber
x--393.51-(-282,98)
Thus, we can see that the total -110.57kJ
law is verified.
almost same. Therefore, Hess's done i. tevolved during the combustion of carbon to give carbon
Consider formation of carbondioxide. It can be Hence,theheat
monoxideis-10.57kI
Example 2.
ways form CO, directly. Example13. IfIfthe hcats offcombustion of carbon, hydrogen and ethane
burns in oxygen to
First path- Carbon -285.83and 1559.87 kJ respectively, then calculate heat of
C(s)+0,(g)- co, (g): AH=-393.51 -393.51,
reaction
forreaction.
carbon monoxide an art
in oxvgen to form firstcarbon (g)
Second path- Carbon burns with
combines oxveen to form dioxide. 2C(s) +3H, (g) =CH,
then carbon monoxide Solution:Given
AH-110.53 k (g) =Co, (g); AH-393.51 kJ
c)+;0,(g)-cOgk 0 C(s)+0,
H,o 0:
o H, (e);0, (g)-
AH-285.83 kJ
AH-282.98 k1
co(g)o,(e) =Co,(eX
AH=-393.5I k I55987kJ
C(s)+0, (g) = C0,(g):
same. oi) G,H, (s);°(8)-2 CO, (8)+ 3H,00: aH--
The heat evolved in both paths is 3H, (g) =CH, (g) AH=?
Applications of Hess's Law we have to calculate 2C ($) +
With the help of Hess's law
thermochemical equations are used as Moliolying cquation () by 2and () by 3and then adding both equations
subtraction, multiplication or dividsion.
algebric equations i.c., addition,
16451 kJ
2C(5) +3H, (e) +; O, (8) - 2C0, (g) +3H,0 (0): AH--
of
difficult to determine heat
() Calculation of heat of formation- It is

fornation experimentally. For example, in reaction C(s)+ 0, (g)=CO(e), Subtracting equation (iii) from
it
of carbon. 2C(s)+ 3H, (g) = ChH, (g): AH=-
1644.S1 -(- 1559.87) =-&4 64kt
it is dificult to measure AH experimentally because in the oxidation
arbon dioxide is also formed. According to Hess's law, 393.57 nf carbon, hydrogen and
some amount of carbn Example 14. At 25°C, the heat of combustion
J heat is evolved in the formation of CO, from I mole carbon, whether the 3267.62 kJ respectively. Calculate heat of
reaction occur in single step benzene are- 393.51,-285.83 and-
temperature.
AH=-393.51 kJ
fomation of benzene at this
C(s) +O, (g) =C0, (g):
or in two steps
96
equations can be
Physical Chemis
writlen as folle.
Thermochemistny

Onssubtracting
Solution: equation (i) ffrom equation (ii)
97

Solution: Thermochemical ciDiamond) C(Graphite

AH -1.88 kJ
6) c()+0,(g)-CO, (). AH-AH 3-28S83k
93.51\ the,heat of
Thus,
uansition ofC( (Diamond)
Calculationofheat of hydration- We
exothernic process and heat evolved
to C(Graphite)
know
.
that
--|,88 kJ
formation ofhydrates
/ii) a n during this
hydration Thus, the enthalpy relesed in the process is
of
i
salts s
of
as heatinto its final hydrated state is catled heat of
conversion of
hydration. For
H,00: AH--32676) < salt
(i) CH, (0+0,(g)=6 CO, +3
drous
anhs
CuSO, (s) +SH,0)- Cuso, SH,0(s). SH=-7821 kJ
We have to calculate the heatofhydrationofCuSO, is-78.21 kJ. The heats of hydratign
measured directly because the hydrated salt cannot be formed
Mence
6C (s)+ 3H, (g) - CH, (0: then adding both cquati bymixing
be quantities ofwater and salt (according to cquation ). Ifwe mix
Multiplying cquation (Ö) by 6and (ii) by 3and
not
canno
water, then water dissolves some anount of
in 5 mole of
ale CuSO, which. some amount of salt is hydrated and some
+3H,0(0: salt, out of Thus the heat of hydration is
6C (9) +3M,(g) +0,(g) -6C0, (g) .drous
anhyrou
t left
untouched. always measured
knowing the integrallheats of solution of anhydrous and hydrated
AH-3218.55 By
adirecly ssible to calculate
heat .of hydration for that salt.
Suppose we want
pos: o
Subtracting equation (ii) from this, we get is
salt,it ofhy dration of anhydrous CuS0, Following thermochemical
pacalcular heat wrilen
6C (s) +34, (g)CH,(0): on can
guation can
be
H.O)
AH-3218.55-(-3267.62) =+ 49.07k
CusO, (s) +800 H,O)=CuSO, (800 AH-66 50KJ
Thus at 25°C, the hcat of formation
of benzene =+49.07 kJ "cuSO,.SH,0(s) +t 795 H,o() =CuSO, (800 H,), aH-+|171k!
know that the transition of one (u) from equation (i)
(ii) Calculation ofheat of transition- We rate that it is impossible to Oe subtracting equation ();
allotrope to another takes place at such a slow the help ofHess's law. it is CusO, (s) +SH,0() " CuSO,5H,0 AH=-7821 kJ
measure enthalpy change experimentally but with he valuc of heat of hydration for CuSOSH,0 from CuSo, is
possible. For example- We know that the heat of combustion of rhombic sulphur
and monoclinic sulphur are known to be -297.5 and- 300.0 kJ, respectively
mnle 16, L62 J heat is evolved when 10 gm anhydrous NaSO, is
on
AH=-300,0 kJ ed in excess of water, whle similar amount of Na,S0,.10H.0 of
S(monoclinic) +0, (g)= S0, (gl: of hvdration
0)
AH--297.5 kJ irnlsing. 1580 J heat is evolved. Calculate Sheat= 32, 0-16and H=)
() S(rhombic) +O, (g)= S0,(g): SO. 10H,0 from Na,SO,. (atomic weight Na =23,
32 +(I6 x4)
On subtracting (i) from (ii
Solption: Atomic weight of Na,SO, -(23 x2) +
S(rhombic) = S(monoclinic) AH=+2.5 J -142 gm mole!
Therefore, the transformation of I mole of rhombic sulphur into
monoclinic sulphur is accompanied by absorption of 2.5 kJ of heat. 10
10 gm Na,SO,n mole
Example 15, Calculate heat of transition ofC (Diamond) to C (Graphite)
from following data 162x 142
(0) C (Diamond) +O, (g) -C0, (g): AH-39S.39 kJ Heat of solution of Na,SO, per mole 10
() c(Graphite) +O, (g)-Co, (g: AH--393.5| kJ --2300 J=- 2,300 kJ
 ×IS)-
Physical Ch Thermochemistry

H(Product) -H(Reactant)
SO,.1OH,0- 142 +(10 -322 gm mdle AH
weight of Na, bond lencrgy can be
calculated by heat of reaction.
Atomic this
way,
mole In it ofenergy required to dissociate i.c., break I mole
Theaverageamount.
1OH,0= equal toavogadro snumber, 6.023 x
10gmNa,SO, (ornunhber.ofbonds 10of any nonaly
in atycompound is s called bond energy of that bond. It is specified
SO,H,0permole
Na, resen
per mole. It is also known as enthalpy off formation of the
of
Heat ofsolution eented in kJ diatomic molecule .of chlorine gas. In this
bonds
molecule, the
$0.876 kJ eprenk about change accompanied in following
hond. Thi visequal tothe energy cl
+1580x 32s0876J = hadenergy
reaction
-

Cl, (g) =2CI(g); AH=242 60kJ

themochemical equation forr
questionthe reactions ae -20():
Similarly, O,(g)are also called
AH-495. 16kJ

0
As givenin
s0,
Na, (6)
(aq)}:
*a4 Na,SO,Na,SO,(aq ): AH-23 These
reactions
called heat
d
dissociation reactions and thc cnetyy
of dissociation. Thus, the bond energy of
diatomic
10H,0(9) +ag. dissolving Na,S0, in water p thisis heat. of dissociation. In case of polyatomic molecules
() Na,so,
in
change cqualto its
process of takes is becomes a much less definite quantity because the energy
It is assumed
thatthe olecu
bondenegy bond will depend to some extent on th¹
steps (s); hot break a given nature ot
in two following Na, So, 10H,0 weeary to
For example..the bond energy ofC-H bond is not afixed
he

Na, S0,(s) +10H.0()= e molecule.

compounds, it has different values. In fact,
Na,S0,(aq.); senainng
quantity
andfor. rdifferent organic
Na,SO,.10H,0(9) +sq. - AH=(x+50.876)Js caleulation of average
e value of heat of reaction for any bonddisis done by
(a4.): such compounds in which only that bond is present. This average
Na,S0, (s) *aq - Na, SO, the
Onaddition sp cific
bond is termed as representative bond energy of that
cquation(i)and (ii)
Coniparing =53.176kJ valuetor
any
compound, which has that bond. The representative bond
every
x+$0.876 -2.300orx for
bond considePred as the bond energy of that bond.
and
hydration for Na,SO,.10H,O from Na,S,.. energy is
So, the value of heat of Expe
perimentally, it is ieevidentthat the (heat)
formation
enthalpyfor ofe formation of isomeric
every CH, group in any
S3 176kI Enthalpy of
compounds i is same.
bond energies homologousseries. increases in the .almost same order. Thus, it is clear that
(i) Caleulation of specificctvpes of bond is an additive property.
energies fforrnation of
Bond enthalpies and bond broken in reate enthalpy of
chemical rezction occurs, some bonds are calculationnof different types of bond energies, first it is important
Whenevera Forthe
formed in product, For example e
knowledgeabout the heats ofdissociation of moiecules. These values
molecules and new bonds are To d
HBr(g) tohave determineddby spectrum method. For examrle- determinethe
H, (s) -Br, (g) -2 have already
YofC- Hbond in CH,. We know heats of
dissociation of carbon
Hg) + Br{g) = 2HBr(g) hond energy
nd hy drogen
H-*Br Hhr ) C(s)-C(g):
AH =+719.,6kJ
AH =+435.I J
(g):
() H, (g) -2H of methane, which is calculateed
hy it
Imolecule of H, and I molecule of Br, react
to form 2 molccules ofHBr Wemust know, heat of formation
whereas, tuo it is - 74.9 kJ. Hence,
Jn this reaction, one H-H and one Br -Br bond is dissociated dissociatior heat of combustion, and AH=-74.9 kJ
the bond
new H- Br bonds are formed. Energy is required information, This enere () C(s)+ 2H, (g) =CH,(g): and then add to cquation (0
while on other hand, energy is released in the bond 2
change is obtained in the forn of heat of
reaction. Now multiply equation (ii) by AH=1589.8 KJ
(g)-Cg) + 4H (g):
(v) C(s)+ 2H,
 Thermochemistry 101
100

cquation (iv)
Phyical Cheh Solution: Inorder determine bond energy of C Cbond, wehave to
changein thefollowing equation-
Subtracting cquation (ii) from cakulateeheat
c,H, (g) 2C (g) +4H (g):
CH, (g) =C(g) +41(g): dto brcak 4 mole c Multiplybotheequation (ii) and4(ii) by 2 and then by adding both these
Theretore, 1664.7 kJ heat is required eUuations,we gct
bond l664.7 Ce)+2H, (g)- 2C(g) + 4H ():
bond energy ofC- H AH23094kJ
methane. Thus the averaee 4I6).
4
cquation (i
of formation of C - Hbond. Simil.. subiracting
C,H, (g) 2C(g) + 4H (g):
cnthalpy On
mole. ofThis
energies
per is also
other bonds Jike C-CC-0, C=0, C- OH ectc. can bet use AH22S7. 14kJ
that 2257.14 kJ heat is uscd in breaking 4C - H
of formation of compounds having such
bond. equation shows
determine the enthaloy This CCbond. Thus
bonds are givcn in Table 2.4)
Cnergies of sone important holds and 4 x(C-H bond energy) + | (C--Cbond cnergy)==+2257. 14J
bonds at Z5C (Bond eher
Table 2.4 Enthalpy of formation of some mole) AL62)+ 1x (C- Cbond energy)-+ 2257.14 kJ
(hilo Joule per
Therefore CCbondcnerpy +2257,14- 1664.8-592.34 k
Enthalpv of formation Bond Enthalpy of formali Encreies
Bond
435.1
C-F 439.3 -liestions of Bond
I-H
C-ci 330.5
4pplt
Determination fenthalpies of reaction- The enthalpy of reaction
H-F 564.8 calculatedwiththe- helo of bond energies. It can be explained by taking
C- Br 276.1 be
H-CI 430.9 cm
followingexample.
N 292.9
368.2 to calculate the enthalpy of reaction for the given
H- Br 6I5.0 Suppose we want
299.0 C=N
H-I
878.6 teaction
0-0 138.1 C=N
C-S 2594 CH, - CH, ()+ H, (g) -H,C-CH; AH=
493.7 Ate reaction, 4 C-H bonds in C,H, remains unaffected only 1C-C
477.0 breaks. Onthe other hand in C,H. 1C-Chond
0-H 464.4 C=S IH-H bond ofH,
I54.8 ond and formed
C-H 416.2 F-F
and2C-H bonds ure
C|-CI 242.7 (AHc-ct2 x AHc-H)+(AHc.ctA)
C-0 3514 AH
Br- Br 192.5 energies from Table 2 4
C=0 711.3 On putting values of bond
C-C 347.3 AH (347.3+2 x 416.2) +(615.0+435. 1) =- 1296kJ
N-H 389, energies is auite
Thus. the valuc of Hcalculated with the help of bond
C=C 615.0
811.7 N-N I59,0 value of 133 kJ.
C=C
NN 418.4
cose to experimental
bond
() Calculation ofenthalpies of formation of compounds- The of
945.6 of cnthalpies of formation
enerzies can also be used for determination
N=N
enthalpy of formation of acetong.
Exam ple 17, Calculate the bond energy ofC C bond from follow ing CoupOunds. Suppose we want to calculate
data H

(Ö 2C(s) +2H, (g) -C,H, (g} AH=+52.26 J

H-C-C-C-H
() C(s) C(g): AH=+719.6kJ 3C (g) + 6ll (g) + O(g) =
(ii) H,(g) 2H (g): AH=+435.IkI HO H
If bond energy of C-H bond is 4 162 kJ.
 103

102 changes.
Physical Chem Thermoc
achemistry
the calculated value. This clearly shows that
the
actual
two Imorethan mnore stable than the Kekule's structure. Thc actual
reaction involves benzenc is
The above H-H(g)bonds to
give six atoms ofH. of anunce hybrid of the two Kekule's structure and may be
() Breaking
of three
sublimation .
of three
brelkim structure
tructureisthe
aeresentedas follows.

give onc atom of Oand reort

0-0e) bond to
ofC(g)
three atoms 2C-Chonds. 6C. Hbond and
C(S)to give
(i) In
acetone
formation, 1C-0M the resonance cnergy of benzene.
are forned. of acetonc is given
bv
ce of 151 kJ gives
The difference
of formation Calculate thhe heat of formation of Nil, (g) fromthe following
Thus, the enthalpy Example 18.

data
Bonds enthalpy
Bonds
+AHcao 945.5 kJ
-2xAHc-c t6x AHc-H NeN
389.1 kJ
N-H
in Table 2.4
Incorporating the data given I|-H 435.I kJ

489.5 +3 719.6)-(2 x347.3 +6x 4162 4iu. Solution: The

formationn of a NH, molecule can be represented as
AH,-(3x435.1
7I1.3)
=(|305.3-244,75 +
2158.8)-(694.6+ 24972 +
N,()H,(g)-NM, g)
-194.25 kJ per mole
there is simitarn
Determination of resonance cnergy- Generally, energies a
(ii) as calculated from bond
between the enthalcpies of formation exhibits resonung
NN); (H-H)- H-N-H
nined experimentally. However, ifa compound
values and this differenre
those determi
considerable difference hetween the two formation of ammonis is
there
energy, For exarmple- consider the dissociarin Thus. the heat of
is the measurc of the resonance
fbenzene
cH, ()= 6C (g) +óH (g)

Assuming benzene has Kekule's structure i., consists of thre

is (472.75 + 652.65)-(4167.3)
single and three double bonds, then heat of dissqciation of benzene
AH, -3(AH-)+ 3(4H-Jt(H-) --41,9 kJ
=3 347,3 +3 *615.0+6 x41I62 given reaction at 25°C
Example 19, Calculate AH° for the
- $384.1 kJ mof-! 2H,0()
CH,-CH, (g) +30,(g) -2C0, (g) + 414, 499,
The experimental value of heat of dissociation of benzene is known to te
515.1kl rmol.So the actual energy requircd for the dissociation ofbenzene
ofC-1,0 =0,C=0,0-H and C--Care
The bond cenergies
724, 460 and 619 kJ mol, respectively.
 can 104
data
Hence, or or be
Solution:
calculated Example AH° Solution
O-H- for
Allo-# 2xAHo-H
=920.18 H
-2413-|1315+937-x
aHo1) AH as The 0, H,
20. AH°= this H
(g) (g)
460.09
=aHynAto.o-(2x
aHo-) heat =
-3772-4736
Calculate
=
=-964 kJ =(4 reaction C=c
920.18 20(g):2H(g): (4 H
kJ 2 of 414 x ×
formation is (g)
bond +619+3 H-Ht
460,09kJ
energy
+30=0(g)=20=C
ofreaction
AHc=Ct3
499)-(4
x
(Since
of
H, -0
H,O (g)+ bond
H AHç-ot4*-(4x
aHxAHÍ=0)
x.
724
-O(g)+2H-0 =
has at +4
2 0,(g) AH=-241.81
AH=+493.3 25°C
460) x
AH=+431S, Physicalth
0-H
=H,o by
band fol