Presentation Outline;

Define Origin of Heat of Reaction..

Exothermic Reaction..

Endothermic Reaction.

Graphical representation of Exothermic

and Endothermic reactions..

Different type of heat reactions & Hess’s

law.
 What is Thermochemistry ?

Thermochemistry is the study of the energy

and heat associated with chemical reactions
and/or physical transformations. A reaction
may release or absorb energy, and a phase
change may do the same, such as in melting
and boiling.
 First law of thermodynamics
• Law of conservation of energy, It states that :
• The total energy of an isolated system remains constant though it
may change from one form to another.
When a system is changed
from state A to state B, it
undergoes a change in the
internal energy from EA to
EB. Thus, we can write
ΔE = EB–EA

This energy change is brought about by the evolution or absorption of

heat and/or by work being done by the system. Because the total energy
of the system must remain constant,
• The mathematical statement of the First Law as :
• ΔE = q – w
where q = the amount of heat supplied to the system
• w = work done by the system

• First Law may also be stated as :

• The net energy change of a closed system is equal to the heat
transferred to the system minus the work done by the system.
• w = P×ΔV
• ΔE = q – P × ΔV
 ENTHALPY OF A SYSTEM

• The total heat content of a system at constant

pressure is equivalent to the internal energy E plus
the PV energy.

• This is called the Enthalpy (Greek en = in; thalpos =

heat) of the system and is represented by the
symbol H. Thus enthalpy is defined by the equation :
H = E + PV
Specific Heat Capacity
 Heat capacity:
Heat capacity of a system is defined as the amount of heat
required to raise the temperature of the system through 1°C .

If q is the amount of heat supplied to a system and as a result ,if

the temperature of the system rises from T1 and T2 ,then the heat
capacity of the system is given by

C = q / ( T2 -T1 ) C= q / Δ T
 Temperature vs. Heat

• Temperature is the measurement of the

avg. KE of the particles in matter.

• Heat energy that flows from a warmer

object to a cooler object.
 Learning Check

When you touch ice, heat is transferred from

1)your hand to the ice
2)the ice to your hand

When you drink a hot cup of coffee, heat is transferred from

1)your mouth to the coffee 4

2)the coffee to your mouth

Have you ever noticed that on a hot
summer day the pool is cooler than the
hot cement?

• OR maybe that the ocean is cooler

than the hot sand?
 Specific Heat Capacity
Specific Heat: The amount of heat required to raise the
temperature of 1 gram of a substance 1 degree Celsius.

1 calorie = 4.184 J
1,000 J = 1 KJ
4,184 J = 1 Kcal = 1 Calorie
 Substance Speci
fic
Heat
J/(g°
C)
Water 4.184
Ethanol 2.44
Aluminum 0.897
Granite 0.803
Learning Check
A. A substance with a large specific heat
1) heats up quickly 2) heats up slowly
B. When ocean water cools, the surrounding air
1) cools 2) warms 3) stays the same
C. Sand in the desert is hot in the day, and cool
at night. Sand must have a
1) high specific heat 2) low specific heat

LecturePLUS Timberlake 99 10
• Specific heat capacity , c, of a substance is defined as the amount of heat
required to raise the temperature of 1 gram of a substance through 1°C.

• Molar heat capacity of a substance is defined as the amount of heat required

to raise the temperature of 1 mole of a substance through 1° C.
Cm = C/n

The amount of heat , q , required to raise the temperature from T1 to T2 of

mass m grams of a sample and having specific heat capacity, c, can be
calculated as:

• q= m × c × ΔT
• q = C × ΔT
 Equation:

q = c x m x ΔT
AT = Tfinal – Tinitial

q = the heat absorbed or released

c = the specific heat of the substance
m = the mass of the sample in grams
AT = change in temperature
 Molar Heat Capacity at Constant
Volume
According to the first law of thermodynamics
dq = dE + PdV
Dividing both sides by dT, we have
!" !$%&!'
=
!# !#
At constant volume dV = 0, the equation reduces to
!$
𝐶𝑣 = ( ) v
!#

Thus the heat capacity at constant volume is defined as the

rate of change of internal energy with temperature at
constant volume.
Molar Heat Capacity at Constant Pressure

Equation (ii) above may be written as

!$ &!'
C= +
!# !#

We know, H=E+PV

Differentiating this equation w.r.t T at constant pressure, we get

!( !$ !'
( )P = ( )P+ P( )P
!# !# !#

comparing it with equation (iii) we have

!(
𝐶𝑃 = ( )P Thus heat capacity at constant pressure is defined as the
!#
rate
of change of enthalpy with temperature at constant pressure.
Relation Between Cp and Cv
From the definitions, it is clear that two heat capacities are not equal and Cp is greater than Cv by a factor w
related to the work done. The increase in temperature of the system would be lesser at constant pressure th
constant volume. Thus Cp is greater than Cv.

!" !$
𝐶𝑃 = and 𝐶𝑣 =
!# !#

By definition H=E+PV for 1 mole of an ideal gas

Or, H=E+RT

Differentiating w.r.t. temperature, T, we get

!" !$
= +R or,
!# !#
Cp=Cv+R or, Cp-Cv= R

Thus Cp is greater than Cv by a gas constant whose value is 1.987 cal K–1 mol–1 or 8.314 J K–1
mol–1 in S.I. units
Calculation of ΔE and ΔH

(A) ΔE : For one mole of an ideal gas, we have

C = dE /dT
v

or dE = C × dT
v

For a finite change, we have

ΔE = E – E = C (T – T ) and for n moles of an ideal gas,
2 1 v 2 1

we get, ΔE = E –E =n×C ×(T –T )

2 1 v 2 1
(B) ΔH : We know
ΔH = Δ (E + PV) = ΔE+Δ(PV)
= ΔE + Δ RT [PV = RT]
= ΔE + R ΔT
= Cv (T2 –T1)+R(T2 –T1)
= (Cv +R)(T2 –T1)
= Cp (T2 – T1) [Cp – Cv = R]

and for n moles of an ideal gas we get

ΔH= n x Cp x(T2-T1)
 H = n × Cp × (T2 – T1)

SOLVED PROBLEM 1. Calculate the value of E and H on heating 64.0 g of oxygen from 0ºC to
100ºC. Cv and Cp on an average are 5.0 and 7.0 cal mol–1 degree–1.
SOLUTION. We know
E = n × Cv × (T2 – T1) ...(i)
and H = n × Cp × (T2 – T1) ...(ii)
64
Here n = 4 moles; T2 = 100ºC = 373 K
16
T1 = 0º C = 273 K
On substitution we get
E = 4 × 5.0 × (373 – 273)
= 4 × 5.0 × 100 = 2000 cals
and H = 4 × 7.0 × (373 – 273)
= 4 × 7 × 100
= 2800 cals
 = 2800 cals

SOLVED PROBLEM 2. Calculate the amount of heat necessary to raise 213.5 g of water from 25º
to 100ºC. Molar heat capacity of water is 18 cal mol–1 K–1.
SOLUTION
By definition
q
C
T2 – T1
or q = C (T2 – T1) – for 1 mole
q = n C (T2 – T1) – for n moles ...(1)
In the present case
n = 213.5/18
C = 18 cal mol–1 K–1
T2 – T1 = (373 – 298)K
Substituting the value in (1)
213.5
q × 18 × (373 – 298)
18
= 16,012 cals = 16.012 kcals
 SOLVED PROBLEM 3. Three moles of an ideal gas (Cv = 5 cal deg–1 mol–1) at 10.0 atm and 0º are
converted to 2.0 atm at 50º. Find E and H for the change.
R = 2 cal mol–1 deg–1
SOLUTION.
(a) E = n CvdT
= 3 × 5 × (323 – 273)
= 750 cals
(b) H = n CpdT = n (Cv + R) dT
= 3 × (5 + 2) × (323 – 273)
= 1050 cals

JOULE-THOMSON EFFECT
Joule and Thomson (later Lord Kelvin) showed that when a compressed gas is forced through
calories or joules per degree per mol and is 1.987 cal (approximately 2 calories) or 8.314 joules.

SOLVED PROBLEM 1. The heat of combustion of ethylene at 17ºC and at constant volume is
– 332.19 kcals. Calculate the heat of combustion at constant pressure considering water to be in
liquid state. (R = 2 cal degree–1 mol–1)
SOLUTION
The chemical equation for the combustion of ethylene is
C2H4(g) + 3O2(g) 2CO2(g) + 2H2O(l)
1 mole 3 moles 2 moles negligible volume.
No. of moles of the products = 2
No. of moles of the reactants = 4
n = (2 – 4) = – 2
We know that H = E + n RT
Given that E = – 332.19 kcal
T = 273 + 17 = 290 K
R = 2 cals = 2 × 10– 3 kcals
H = – 332.19 + 2 × 10–3 × –2 × 290
= – 333.3 kcal
 SOLVED PROBLEM 2. The heat of combustion of carbon monoxide at constant volume and at
17ºC is – 283.3 kJ. Calculate its heat of combustion at constant pressure (R = 8.314 J degree–1 mol–1).
SOLUTION
1
CO(g) + 2
O2(g) CO2(g)
1
1 mole 2
mole 1 mole
No. of moles of products = 1
No. of moles of reactants = 1 12
n = No. of moles of products – No. of moles of reactants
1 1
1–1 –
2 2
Given that E = – 283.3 kJ
T = (273 + 17) = 290 K
and R = 8.314 J or 8.314 × 10–3 kJ
Substituting these values in the equation
H = E+ n × RT
 1 
we get H = – 283.3 +  – (8.314 10 –3 ) 290 
 2 
= – 283.3 – 1.20
= – 284.5 kJ
Heat of combustion of CO at constant pressure is – 284.5 kJ.
 SOLVED PROBLEM 3. The heat of formation of methane at 298 K at constant pressure is
– 17.890 kcal. Calculate its heat of formation at constant volume. (R = 1.987 cal degree–1 mol–1)
SOLUTION
The thermochemical equation for the heat of formation of methane at 298 K at constant pressure
is :
C(s) + 2H2(g) CH4(g) H = – 17.890 kcal
No. of moles of gaseous products =1
No. of moles of the gaseous reactants =2
Change in No. of moles, n = 1 – 2 = –1
Given that H = – 17.890 kcal; T = 25 + 273 = 298 K
and R = 1.987 cal = 1.987 × 10–3 kcal
Substituting these values in the equation
H = E + n × RT
E = – 17.89 + [– 1 × (1.987 × 10–3) × 298]
= – 18.482 kcal
The heat of formation of methane at constant volume is – 18.482 kcal.
 Origin of Heat of Reaction

In a chemical reaction, the amount of heat that

must be added or removed in order to keep all of
the substances present at the same temperature.
Some reactions will release energy and some
reactions will adsorb energy and the energy will
work here is Heat.
Whenever a chemical reaction will occur, it will
release heat or will adsorb heat.
So, We can get two different types of Heat of Reaction.

In a
Reaction

Heat Released Heat adsorbed

Exothermic Reaction
Many reactions release energy in the form of heat,
light, or sound. These are exothermic reactions.
In a chemical reaction, the amount of energy
required to break the old bonds of the reactants is
lower than amount of energy released for
formation of new bonds of the products and
thereby heat is transferred from system to
surrounding is referred to as Exothermic reaction.
 <
Energy required to Energy release for
break the old bonds formation of new
of reactants bonds of the
molecules products molecules

Heat transfer
System Surrounding
Endothermic Reaction
An endothermic reaction is any chemical
reaction that absorbs heat from its
environment.
In a chemical reaction, the amount of energy
required to break the old bonds of the reactants is
higher than amount of energy released for
formation of new bonds of the products and
thereby heat is penetrated from surrounding to
system is referred to as Exothermic reaction.
 >
Energy required to Energy release for
break the old bonds formation of new
of reactants bonds of the
molecules products molecules

Heat transfer
System Surrounding
Graphical representation of Exothermic
and Endothermic reactions

A graph is scatted out putting time or rate of reaction

or reaction coordination along x axis against energy or
heat along y axis. Let A and B two reactants produce
C and D two products by a reaction. If the reaction
release heat then it will be exothermic reaction and if
the reaction adsorb heat then it will be endothermic
reaction.
 EXAMPLES OF EXOTHERMIC AND ENDOTHERMIC PROCESSES

When trying to classify a process as exothermic or endothermic, watch how the temperature of the
surroundings changes. An exothermic process releases heat, and causes the temperature of the
immediate surroundings to rise. An endothermic process absorbs heat and cools the surroundings.

Exothermic processes Endothermic processes

Making ice cubes Melting ice cubes

Formation of snow in clouds Conversion of frost to water vapour
Condensation of rain from water vapour Evaporation of water
Mixing sodium sulfite and bleach Baking bread
Rusting iron Cooking an egg
Burning sugar Producing sugar by photosynthesis
Forming ion pairs Separating ion pairs
Mixing water and strong acids Mixing water and ammonium nitrate
Mixing water with an anhydrous salt Making an anhydrous salt from a hydrate
Crystallizing liquid salts (as in sodium acetate Melting solid salts
in chemical handwarmers)
Nuclear fission Reaction of barium hydroxide octahydrate
crystals with dry ammonium chloride
mixing water with calcium chloride Reaction of thionyl chloride (SOCl2)
with cobalt(II) sulfate heptahydrate

Such reactions which are accompanied by absorption of heat are called Endothermic reactions.
 by Hº.
VARIATION OF HEAT (OR ENTHALPY) OF REACTION WITH TEMPERATURE
The heat of reaction changes with change in temperature of a gas due to variation in its specific
heat. The equations representing the variation of heat change of reaction with temperature are known
as Kirchoff’s equations.
At constant volume, the heat of reaction, E, is given by the relation
E = E2 – E1
where E1 and E2 are the internal energies of the reactants THERMOCHEMISTRY
and products. 279
Differentiating this equation with respect to temperature at constant volume, we get

 d ( E)   dE2   dE1 
 dT    –  ...(1)
v  dT v  dT v
we have already seen that

 dE 
  Cv
 But we have already seen that
    –  
 dT v  dT  v  dT  v
 d (dEE )seen
But we have already  that
 dE2   dE1 
–
 v Cv  dT  v
    
  dT    dT  v
 dT v  dE 
But we have already seen that  Cv
 dT v
dE 
d ( EdT
)  Cv
=dv(C( v)E
2 –) (C=v)1(C
= Cv ...(2)
dT v)2 – (Cv)1 = Cv
d ( E ) dT
= (Cv)2 – (Cv)1 = Cv
where (Cv)2(C
where andv)(C )
and
2 v 1
are
(Cheat
)
v 1
capacities
are dT of the products
heat capacities of and
thereactants
products respectively. Or, change
and reactants in heat
respectively.
whereof(C v)2 at
and (C atv)constant
1 are heat volume
capacities of degree
the products andinreactants respectively. Or,tochan
of reaction
reaction constant volume per degree change
per in temperature
change is equal to the
temperature
of reaction at constant volume per degree change in temperature is equal to the differen
difference in
is equal heat
th
capacities
capacities
capacities at
at constant
at constant
constant volume
volume
volume
of ofand
products
of products
products and reactants.
reactants.
and reactants.
Integrating
Integrating the above
the above equation
equation between between temperatures
temperatures T1 and T T21, and T2, we have
we have
Integrating the above equation between temperatures T1 and T2, we have
T2 T2
E2 – EE ∫E1 Cv ∫dT Cv dT
2 T2–
1
T 1
T1
or E2E– –E1 E C dT
∫ = vC [T – T ]
2 1 v 2 1
where Eor
2 and E1 are heats ofEreaction
2 T–
1
E1at=temperatures
Cv [T2 – T1T]2 and T1 respectively.
where E2atand
Similarly, E1 are
constant heats of
pressure thereaction at temperatures
heat of reaction T2 and
H is given T1reaction
by the respectively.
 or E2 – E1 = Cv [T2 – T1]
where E2 and E1 are heats of reaction at temperatures T2 and T1 respectively.
Similarly, at constant pressure the heat of reaction H is given by the reaction
H = H2 – H1
where H2 is the heat content (enthalpy) of the products and H1 being that of the reactants.
Differentiating with respect to temperature at constant pressure, we have

 d( H)   dH 2   dH1 
    –  
 dT  P  dT  P  dT  P
According to the equation, Chapter 7, we have

 dH 
  CP
 dT  P

 d( H) 
  = (CP)2 – (CP)1 = CP
 dT  P
where (CP)2 and (CP)1 are the heat capacities of products and reactants respectively.
or d ( H) = CP × dT
Change in heat of reaction at constant pressure per degree change of temperature is eq
difference in heat capacities of products and reactants at constant pressure.
Integrating the equation between temperature T1 and T2, we have
  d( H) 
= capacities
where (CP)2 and (CP)1aredTthe heat (CP)2 – (CP)of
1 =products
CP and reactants respectively. ...(5)
P
or where (C ) and (C d) (areH)the=heatCcapacities
P × dT of products and reactants respectively.
P2 P1
Change or in heat of reactiondat constant
( H) = CP pressure
× dT per degree change of temperature is equal to
differenceChange
in heatincapacities of products
heat of reaction andpressure
at constant reactantsperatdegree
constant pressure.
change of temperature is equal to
difference in
Integrating theheat capacities
equation of products
between and reactants
temperature at constant
T1 and pressure.
T2, we have
T temperature T1 and T2, we have
Integrating the equation between
2
T2
H 2 – H1 ∫ C p dT
H2 – H1 ∫ C p dT
T1
T1
or or H2 H– –H1H= = CCp [T[T2 –– TT1]] ...(6) ...(6)
2 1 p 2 1
The relations (2), (3),
The relations (5) (5)
(2), (3), andand
(6)(6)were
werefirst
firstderived byKirchoff
derived by Kirchoffandand
areare called
called Kirchoff’s
Kirchoff’s equations.
equations.
These These
equations maymay
equations be used forfor
be used calculating
calculatingheat reactionatata given
heat of reaction a given temperature
temperature whenwhen it is known
it is known
at someat other
some other temperature
temperature andand whenthetheheat
when heatcapacities
capacities ofofproducts
productsandand
reactants are known.
reactants are known.
280 8 PHYSICAL CHEMISTRY

SOLVED PROBLEM 1. The heat of reaction 12 H2 + 12 Cl2 HCl at 27ºC is – 22.1 kcal. Calculate the
heat of reaction at 77ºC. The molar heat capacities at constant pressure at 27ºC for hydrogen,
chlorine and HCl are 6.82, 7.70 and 6.80 cal mol–1 respectively.
SOLUTION
Here,
1 1
H2 Cl 2 HCl H = – 22.1 kcal
2 2
CP = Heat capacities of products – Heat capacities of reactants

1 1 
= 6.80 –  (6.82) (7.70) 
2 2 
= 6.80 – 7.26 = – 0.46 cal = – 0.46 × 10–3 kcal
T2 = 273 + 77 = 350 K; T1 = 273 + 27 = 300 K
T2 – T1 = (350 – 300) K = 50 K
Substituting these values in Kirchoff’s equation, we have
H2 – H1 = Cp (T2 – T1)
= – 22.1 + (–0.46 × 10–3) × 50
= – 22.1 + (–0.023)
= – 22.123 kcal
Heat of reaction at 77ºC is – 22.123 kcal
 SOLVED PROBLEM 2. The heat of reaction N2 + 3H2 2NH3 at 27ºC was found to be –21.976 kcal.
What will be the heat of reaction at 50ºC ?
The molar heat capacities at constant pressure and at 27ºC for nitrogen, hydrogen and ammonia
are 6.8, 6.77 and 8.86 cal mol–1 degree–1.
SOLUTION
Here, H = – 21.976 kcal
T2 = 273 + 50 = 323 K
T1 = 273 + 27 = 300 K
[T2 – T1] = (323 – 300) K = 23 K
Cp = Heat capacities of products – Heat capacities of reactants
= (2 × 8.86) – [6.8 + (3 × 6.77)]
= 17.72 – (6.8 + 20.31) = – 9.39 cal
= – 9.39 × 10–3 kcal
Substituting these values in Kirchoff’s equation, we have
H2 = H1 + (T2 – T1) Cp
= – 21.976 + [23 × (– 9.39 × 10–3)]
= – 21.976 + (– 0.216) = – 22.192 kcal
Heat of reaction at 50ºC is = 22.192 kcal
Different type of heat reactions
There are four different types of heat reactions.
Heat of Formation
The heat of formation of a
compound may be defined as the
quality of heat change during the
formation of one mole of a
substance from this constituent
elements.
 6.6 Standard Enthalpy of Formation and Reaction 253

conditions (1 atm), and For

the subscript
example, “f” stands for formation.
the standard By convention,
enthalpy of the stan-
dard enthalpy of formation of any element in its most stable form is zero. Take the element
formation of carbon dioxide would be the
oxygen as an example. Molecular oxygen (O2) is more stable than the other allotropic
form of oxygen, ozoneenthalpy
(O3), at 1ofatm
theandfollowing
25°C. Thus,reaction under
we can write the
DH°f (O 2) 5 0, but
DH°f (O3) 5 142.2 kJ/mol. Similarly, conditions
graphite is above:
a more stable allotropic form of
carbon than diamond at 1 atm and 25°C, so we have DH°f (C, graphite) 5 0 and
DH°f (C, diamond)C5(s,graphite)
1.90 kJ/mol.
+ O2(g) Based
‹ CO on 2(g)
this; OH
reference for elements, we can now
f = -393.5 kJ/mol
define the standard enthalpy of formation of a compound as the heat change that
results when 1 moleHere
of theall elements
compound are from
is formed written in their
its elements at astandard
pressure of 1 atm.
Table 6.4 lists thestates,
standardandenthalpies
one mole of formation
of product for aisnumber
formed.of elements
This and
compounds. (For a more complete list of DH°f values, see Appendix 2.) Note that
is true for all enthalpies of formation.
although the standard state does not specify a temperature, we will always use DH°f
values measured at 25°C for our discussion because most of the thermodynamic data
are collected at this temperature.
The importance of the standard enthalpies of formation is that once we know
The standard enthalpy
their values, of any calculate
we can readily substances at its most
the standard stableofform
enthalpy is zero
reaction, DH8rxn ,
defined as the enthalpy of a reaction carried out at 1 atm. For example, consider the
Graphite (top) and diamond (bottom).
hypothetical reaction

aA 1 bB ¡ cC 1 dD

TABLE 6.4 Standard Enthalpies of Formation of Some Inorganic

Substances at 25°C
 aA 1 bB ¡ cC 1 d D

TABLE 6.4 Standard Enthalpies of Formation of Some Inorganic

Substances at 25°C

Substance DH°
f (kJ/mol) Substance DH°
f (kJ/mol)

Ag(s) 0 H2O2(l ) 2187.6

AgCl(s) 2127.0 Hg(l ) 0
Al(s) 0 I2(s) 0
Al2O3(s) 21669.8 HI(g) 25.9
Br2(l ) 0 Mg(s) 0
HBr(g) 236.2 MgO(s) 2601.8
C(graphite) 0 MgCO3(s) 21112.9
C(diamond) 1.90 N2(g) 0
CO(g) 2110.5 NH3(g) 246.3
CO2(g) 2393.5 NO(g) 90.4
Ca(s) 0 NO2(g) 33.85
CaO(s) 2635.6 N2O(g) 81.56
CaCO3(s) 21206.9 N2O4(g) 9.66
Cl2(g) 0 O(g) 249.4
HCl(g) 292.3 O2(g) 0
Cu(s) 0 O3(g) 142.2
CuO(s) 2155.2 S(rhombic) 0
F2(g) 0 S(monoclinic) 0.30
HF(g) 2271.6 SO2(g) 2296.1
H(g) 218.2 SO3(g) 2395.2
H2(g) 0 H2S(g) 220.15
H2O(g) 2241.8 Zn(s) 0
H2O(l) 2285.8 ZnO(s) 2348.0
 values measured at 25°C for our discussion because most of the thermodynamic data
are collected at this temperature.
The importance of the standard enthalpies of formation is that once we know
their values, we can readily calculate the standard enthalpy of reaction, DH8rxn ,
defined as the enthalpy of a reaction carried out at 1 atm. For example, consider the
Graphite (top) a
hypothetical reaction
Thermochemistry

aA 1 bB ¡ cC 1 dD
where a, b, c, and d are stoichiometric coefficients. For this reaction DH°rxn is given by

¢H°rxn 5 [c¢H°f (C) 1 d¢H°f (D)] 2 [a¢H°f (A) 1 b¢H°f (B)] (6.17)

Standard
We can generalize
TABLE 6.4 Enthalpies
Equation of
(6.17) as Formation of Some Inorganic
Substances at 25°C
¢H°rxn 5 ©n¢H°f (products) 2 ©m¢H°f (reactants) (6.18)

Substance
where DH°fstoichiometric
m and n denote the (kJ/mol) Substance
coeffi DH°fand
cients for the reactants (kJ/mol)
products,
and © (sigma) means “the sum of.” Note that in calculations, the stoichiometric coef-
Ag(s) are just numbers without
ficients 0 units. H2O2(l ) 2187.6
To use Equation (6.18) to calculate DH°rxn, we must know the DH°f values of the
AgCl(
compounds s) that take part in2127.0
the reaction. TheseHg( l ) can be determined by
values 0 applying
theAl( s) method or the indirect
direct 0 method. I2(s) 0
Al2ODirect
The 3(s) Method 21669.8 HI(g) 25.9
 Heat of
Decomposition
The amount of heat required to
decompose 1 mole of a substance to its
constituent elements is called Heat of
Decomposition.

H2O (l) = ½ O2 (g) + ½ H2 (g) ;

OH = +285.5 kJ/mol
 Heat of
Combustion
The heat of combustion of a compound or
an element is defined as the amount of heat
evolved, when 1 mole of a substance is
burnt completely in oxygen at a given
temperature at 1 atm. Pressure.

kJ
CH4 (g) + 2O2 (g) CO2 (g) =2H2O (l) ; OH = -890 noS
 Enthalpy or Heat of
Neutralisation
Heat of Neutralisation is defined as the
change of heat or enthalpy during the
formation of one mole of water by the
neutralisation reaction of required
amounts of an acid and a base.
kJ
HCl (aq) + NaOH (aq) = NaCl (aq) = H 2O (l) ; OH = -57.34 n oS
 Hess’s Law
If a reaction can take place by more then one routes
the overall change in enthalpy is the same
whichever route is followed.
Illustration of Hess’s Law
Let us assume that a reactant A gives product
D directly by a single step and its change of
enthalpy is OH1.
OH1
A D
Now the same reactant A produce D into
two steps. First A is converted into B
with an enthalpy change OH2 and in the
2nd step intermediate product B is
converted in to D with enthalpy change
OH3.
OH2 OH3
A B B D
According to the Hess’s law, we get

OH1 = OH2 + OH3

It follows also that the standard enthalpy change
for the reaction D€A is -OH and for A€D is+
OH.
 The Direct Method
This This
method of measuring
method DH°fDworks
of measuring for for
H°f works compounds
compounds thatthat
cancan
be be
readily synthesized
readily synthesized
fromfrom
their their
elements. Suppose
elements. we we
Suppose wantwantto know
to know thethe
enthalpy
enthalpyof of
formation
formationofofcarbon
carbon
dioxide. We must
dioxide. measure
We must the the
measure enthalpy of the
enthalpy reaction
of the when
reaction whencarbon
carbon(graphite)
(graphite)and and
molecular
molecular oxygen
oxygen in their
in their standard
standard states
states are are converted
converted to carbon
to carbon dioxide
dioxide in initsitsstan-
stan-
dard dard
state:state:
C(graphite) 1 O2 (g) ¡ CO2 (g) ¢H°rxn 5 2393.5 kJ/mol
C(graphite) 1 O2 (g) ¡ CO2 (g) ¢H°rxn 5 2393.5 kJ/mol
We know from experience that this combustion easily goes to completion. Thus, from
We know from(6.18)
Equation experience
we canthat this combustion easily goes to completion. Thus, from
write
Equation (6.18) we can write
¢H°rxn 5 ¢H°f (CO2, g) 2 [¢H°f (C, graphite) 1 ¢H°f (O2, g)]
5 2393.5 kJ/mol
¢H°rxn 5 ¢H°f (CO2, g) 2 [¢H°f (C, graphite) 1 ¢H°f (O2, g)]
Because both graphite
5 2393.5andkJ/mol
O2 are stable allotropic forms of the elements, it follows
that DH°f (C, graphite) and DH°f (O2, g) are zero. Therefore,
Because both graphite and O2 are stable allotropic forms of the elements, it follows
¢H° 5 ¢H°f (CO2, g) 5 2393.5 kJ/mol
that DH°f (C, graphite) and DHrxn
°f (O2, g) are zero. Therefore,
or ¢H°f (CO2, g) 5 2393.5 kJ/mol
¢H°rxn 5 ¢H°f (CO2, g) 5 2393.5 kJ/mol
Note that arbitrarily assigning zero DH°f for each element in its most stable form
 coeffi cients.

EXAMPLE 6.9
Calculate the standard enthalpy of formation of acetylene (C2H2) from its elements:

2C ( graphite ) 1 H2 ( g ) ¡ C2 H 2 ( g )

The equations for each step and the corresponding enthalpy changes are

(a) C ( graphite ) 1 O2 ( g ) ¡ CO2 ( g ) ¢ H°

rxn 5 2393.5 kJ/ mol
(b) H2 ( g ) 1 1
2 O2 ( g ) ¡ H2O ( l ) ¢ H°
rxn 5 2285.8 kJ/ mol
(c) 2C2H2 ( g ) 1 5O2 ( g ) ¡ 4CO2 ( g ) 1 2H2O ( l ) ¢ H°
rxn 5 22598.8 kJ/ mol

Strategy Our goal here is to calculate the enthalpy change for the formation of C2H2
from its elements C and H2. The reaction does not occur directly, however, so we must
use an indirect route using the information given by Equations (a), (b), and (c).
Solution Looking at the synthesis of C2H2, we need 2 moles of graphite as reactant.
So we multiply Equation (a) by 2 to get

(d) 2C ( graphite ) 1 2O2 ( g ) ¡ 2CO2 ( g ) ¢ H°

rxn 5 2 ( 2393.5 kJ/ mol )
5 2787.0 kJ/ mol

Next, we need 1 mole of H2 as a reactant and this is provided by Equation (b). Last, we
need 1 mole of C2H2 as a product. Equation (c) has 2 moles of C2H2 as a reactant so
ame
we need to reverse the equation and divide it by 2:
o weld
5 1
(e) 2CO2 ( g ) 1 H2O ( l ) ¡ C2 H 2 ( g ) 1 2 O2 ( g ) ¢ H°
rxn 5 2 ( 2598.8 kJ/ mol )
5 1299.4 kJ/ mol

Adding Equations (d), (b), and (e) together, we get

2C ( graphite ) 1 2O2 ( g ) ¡ 2CO2 ( g ) ¢ H°

rxn 5 2787.0 kJ/ mol
H2 ( g ) 1 1
2 O2 ( g ) ¡ H2O ( l ) ¢ H°
rxn 5 2285.8 kJ/ mol
5
2CO2 ( g ) 1 H2O ( l ) ¡ C2 H 2 ( g ) 1 2 O2 ( g ) ¢ H°
rxn 5 1299.4 kJ/ mol

2C ( graphite ) 1 H2 ( g ) ¡ C2 H 2 ( g ) ¢ H°
rxn 5 226.6 kJ/ mol

Therefore, DH°f 5 DH° rxn 5 226.6 kJ/mol. The DH°f value means that when 1 mole of
C2H2 is synthesized from 2 moles of C(graphite) and 1 mole of H2, 226.6 kJ of heat are
absorbed by the reacting system from the surroundings. Thus, this is an endothermic
process.
Practice Exercise Calculate the standard enthalpy of formation of carbon disulfide
(CS2) from its elements, given that

C ( graphite ) 1 O2 ( g ) ¡ CO2 ( g ) ¢ H°
rxn 5 2393.5 kJ/ mol
S ( rhombic ) 1 O ( g ) ¡ SO ( g ) ¢ H° 5 2296.4 kJ/ mol