CHEMICAL

ENERGETICS

Learning Outcomes :
Students able to :
(a) explain that most chemical reactions
are
accompanied by enthalpy changes
(exothermic
or endothermic);
(b) define enthalpy change of reaction,
H, and
state the standard conditions;
(c) define enthalpy change of formation,
combustion, hydration, solution,

Energy Changes in Chemical Reactions

Heat is the transfer of thermal energy between two bodies that
are at different temperatures.
Temperature is a measure of the thermal energy.
Temperature = Thermal Energy

900C

400C
greater thermal energy

Thermochemistry is the study of heat change in chemical

reactions.
The system is the specific part of the universe that is of
interest in the study.
SURROUNDINGS
SYSTEM

open
Exchange:

mass & energy

closed

isolated

energy

nothing

Exothermic process is any process that release heat from the

system to the surroundings.
2H2 (g) + O2 (g)
H2O (g)

2H2O (l) + energy

H2O (l) + energy

Endothermic process is any process that absorb heat from the

surroundings to the system.
energy + 2HgO (s)
energy + H2O (s)

2Hg (l) + O2 (g)

H2O (l)

State Functions
Usually we have no way of knowing the
internal energy of a system; finding that
value is simply too complex a problem.

State Functions
However, we do know that the internal

energy of a system is independent of the

path by which the system achieved that
state.
In the system below, the water could have

reached room temperature from either

direction.

State Functions
Therefore, internal energy is a state

function.
It depends only on the present state of the
system, not on the path by which the
system arrived at that state.
And so, E depends only on Einitial and Efinal.

Enthalpy (H) is used to quantify the heat flow into or out of a

system in a process that occurs at constant pressure.

H = H (products) H (reactants)
H = heat given off or absorbed during a reaction at constant pressure

Hproducts < Hreactants

H < 0

Hproducts > Hreactants

H > 0

Thermochemical Equations
Is H negative or positive?
System absorbs heat
Endothermic
H > 0

6.01 kJ are absorbed for every 1 mole of ice that

melts at 00C and 1 atm.
H2O (s)

H2O (l)

H = +6.01 kJ

Thermochemical Equations
Is H negative or positive?
System releases heat
Exothermic
H < 0

890.4 kJ are released for every 1 mole of methane

that is combusted at 250C and 1 atm.
CH4 (g) + 2O2 (g)

CO2 (g) + 2H2O (l)

H = -890.4 kJ

Enthaply change of reaction, H

Change in heat energy always accompany
a chemical rx.
Enthaply change of reaction, H is defined
as heat change (released or absorbd) in a
chemical rx for the no of moles of rxts (or
pdts) shown in a balanced eqn.

Thermochemical Equations

The stoichiometric coefficients always refer to the number

of moles of a substance
H2O (s)

H = +6.01 kJ

If you reverse a reaction, the sign of H changes

H2O (l)

H2O (l)

H2O (s)

H = -6.01 kJ

If you multiply both sides of the equation by a factor n,

then H must change by the same factor n.
2H2O (s)

2H2O (l)

H = 2 x +6.01 = +12.0 kJ

Thermochemical Equations

The physical states of all reactants and products must be

specified in thermochemical equations.
H2O (s)

H2O (l)

H = +6.01 kJ

H2O (l)

H2O (g)

H = +44.0 kJ

To standardize enthalpy measurement,

following std condts are adopted :
T @ 25 C / 298 K
P @ 1 atm / 101 kPa
Aq soltn @ [1 moldm-3]
Most stable allotrope @ 25 C & 1 atm
Enthalpy change measured under such
condtns = std enthalpy change, H

Types of std enthalpies :

1. Std enthalpy change of formation, Hf
2. Std enthalpy change of combustion, Hc

hydration, Hhyd

4.

solution, Hsoln

5.

neutralisation, Hn

6.

atomisation, Ha

3.

7. Bond energy
8. Ionisation energy, IE
9. Electron affinity, EA

Std enthalpy change of formation

Enthalpy change when 1 mole of substance
is formed from its constituent elements under
standard conditions (298K, 1atm)

Std enthalpy change of combustion

Heat evolved when 1 mole of substance is
completely burnt in excess oxygen under
standard conditions (298K, 1atm). negative.

Standard enthalpy change of hydration

Heat evolved when 1 mole of gaseous ions is
surrounded by water molecules under standard
conditions (298K, 1atm). negative.

Standard enthalpy change of solution

Enthalpy change when 1 mole of the substance is
completely dissolved in a solvent to form an infinitely dilute
solution under standard conditions (298K, 1atm)

Hsol = +2258 - 1650 +

2(-364)

The Solution Process for NaCl

Hsoln = Step 1 + Step 2 = 788 784 = 4 kJ/mol

Standard enthalpy change of neutralization

Heat evolved when 1 mole of water is
formed in the neutralization between an
acid and a base under standard conditions
(298K, 1atm).

...
Standard enthalpy change of atomization
?
Enthaply change when 1 mole of gaseous
atoms is formed from its element under
standard conditions (298K, 1atm).
Mg (s) Mg (g) H = +147.7
kJ/mol
1 Cl2 (g) Cl (g)
H = +121.7
kJ/mol

Bond energy
Average energy required to break 1 mole of
covalent bond in the gaseous state.
positive.

Cl2 (g) 2Cl (g) H = +

kJ/mol
st

Ionisation energy (1 IE)

Min energy required to remove 1 mole of electrons
from one mole of gaseous atoms to form one mole of
the gaseous positive ions. positive.

Na (g) Na+ (g) + e H = +496

kJ/mol

Electron affinity (1st EA)

Enthalpy change when 1 mole of the
gaseous atom acquired 1 mole of
electrons to form one mole of gaseous
negative ions.
O (g) + e O- (g)
kJ/mol

H = -141.1

Learning Outcomes :
Students able to :
(d) calculate the heat energy
change from
experimental measurements
using the
relationship: heat change, q =
mcT
or q = mc ;
(e) calculate enthalpy changes
from experimental

Calorimetry
Since we cannot
know the exact
enthalpy of the
reactants and
products, we
measure H through
calorimetry, the
measurement of
heat flow.
Bomb Calorimeter

Bomb Calorimeter
Reactions can be
carried out in a sealed
bomb, such as this
one, and measure the
heat absorbed by the
water.

Bomb Calorimeter
Because the volume

in the bomb
calorimeter is
constant, what is
measured is really the
change in internal
energy, E, not H.
For most reactions,
the difference is very
small, E, consider as
H

Constant Pressure Calorimetry

By carrying out a
reaction in aqueous
solution in a simple
calorimeter such as this
one, one can indirectly
measure the heat
change for the system
by measuring the heat
change for the water in
the calorimeter.

Constant Pressure Calorimetry

Because the specific heat for water is well known

(4.184 J/molK), we can measure H for the
reaction with this equation:
q = m c T @
q=mc

q
m

Enthalpy change/heat change in Joule

Mass in gram
Specific heat capacity, c
The heat needed to the temperature of 1 g of a substance by 1 C. Symbol: c, units: J/
(gC).
T
Temperature change in C

Sample problem:
(must know water = 4.18 J/gC)
Q1. When 12 g of a food was burned
in a calorimeter, the 100 mL of water
in the calorimeter changed from 20C
to 33C. Calculate the heat released.
Soltn :
q=mcT
= 100 g x 4.18 J/(gC) x 13C
= 5.4 kJ

Q2 5 g of copper was heated from 20C to

80C. How much energy was used to heat
the Cu? [c Cu = 0.38 J/(gC)]
Q3 If a 3.1 g ring is heated using 10.0 J, its
temp. rises by 17.9C. Calculate the specific
heat capacity of the ring.

Q2 5 g of copper was heated from 20C to

80C. How much energy was used to
heat the Cu? [c Cu = 0.38 J/(gC)]
Soltn :
q=cmT
= 0.38 J/(gC) x 5 g x 60 C
= 114 J

Q3 If a 3.1 g ring is heated using 10.0 J,

its temp. rises by 17.9C. Calculate the
specific heat capacity of the ring.
Soltn :
q=cmT
c = q/mT
10.0 J
=
3.1 g x 17.9C
= 0.18 J/(gC)

Q4:
3.00 g of octane was burned in a calorimeter
with excess oxygen, the 1000 mL of water in
the calorimeter rose from 23.0C to 57.6C.
Write the thermochemical equation for octane,
representing the enthalpy change of
combustion.
Soltn :
S1 => q = mcT
= 1000 x 4.18 x 34.6
= 144 628 J

S2 => Octane (C8H18) has a molar

mass of 114.26 g/mol
n = 3.00 = 0.0263 mol
114.26
J
S3 => H = mol
144 628 J
=
0.0263 mol
= 5508 kJ/mol
C8H18(l) + 25O2 (g)
2

8CO2 (g) + 9H2O(l) H0C = -5508 kJ

Learning Outcomes :
Students able to :
(a) state Hess law, and its use to
find enthalpy
changes that cannot be
determined directly,
e.g. an enthalpy change of
formation from
enthalpy changes of
combustion;
(b) construct energy level

Hess Law
Hesss Law: When reactants are converted
to products, the change in enthalpy is the
same whether the reaction takes place in
one step or in a series of steps.
(Enthalpy is a state function. It doesnt
matter how you get there, only where you
start and end.)

Hesss Law
Because H is a
state function, the
total
enthalpy
change depends
only on the initial
state
of
the
reactants and the
final state of the
products.

Calculate the standard enthalpy of formation of CS2 (l)

given that:
C(s) + O2 (g)
CO2 (g) H0 = -393.5 kJ

(g
)

(g
)

3O

2O

(g

SO

CO

Energy cycle :

CO2 (g) + 2SO2 (g)

(g
)

CS2(l) + 3O2 (g)

H0 = -296.1 kJ

SO2 (g)

S(s) + O2 (g)

C(s) + 2S(s)

CS2(l)

H0 = -1072 kJ

Calculate the standard enthalpy of formation of CS2 (l)

given that:
C(s) + O2 (g)
CO2 (g) H0 = -393.5 kJ
S(s) + O2 (g)

SO2 (g)

CS2(l) + 3O2 (g)

H0 = -296.1 kJ

CO2 (g) + 2SO2 (g)

H0 = -1072 kJ

1. Write the enthalpy of formation reaction for CS 2

C(s) + 2S(s)

CS2 (l)

2. Add the given rxns so that the result is the desired rxn.
C(s) + O2 (g)
2S(s) + 2O2 (g)
+

CO2(g) + 2SO2 (g)

C(s) + 2S(s)

H0 = -393.5 kJ
H0 = -296.1x2 kJ

CO2 (g)
2SO2 (g)

CS2 (l) + 3O2 (g) H0 = +1072 kJ

CS 2 (l)

H0 = -393.5 + (2x-296.1) + 1072 = +86.3 kJ

Benzene (C6H6) burns in air to produce carbon

dioxide and liquid water. Calculate the std
enthalpy change of combustion of benzene. The
standard enthalpies of formation of benzene is
-49.04 kJ/mol, water is -187.90 kJ/mol & carbon
dioxide is -393.50 kJ/mol.

C6H6 (l) + 15/2O2 (g)

6CO2 (g) + 3H2O (l

= - 2875.66 kJ/mol

Learning Outcomes :
Students able to :
(a) define lattice energy for simple
ionic crystals
in terms of the change from
gaseous ions to
solid lattice;
(b) explain qualitatively the effects
of ionic charge
and ionic radius on the
numerical magnitude

Born Haber Cycle

Lattice Energy, Hlatt: heat change
when 1 mole of solid ionic compound is
formed from its constituent gaseous
ions.
Na+(g) + Cl-(g) NaCl(s)
H = -771
latt

kJ/mol

Lattice dissociation energy, - Hlatt

energy needed to break down lattice of 1 mole ionic
crystalline solid to forms its gaseous ions

NaCl(s) Na+(g) + Cl-(g)

kJ/mol

-Hlatt = +771

Magnitude of lattice energy :

Increases when ionic charges

increases
Increases when ionic radii
decreases
# strong attraction between small
ions & highly charged ions
=> Hlatt > negative

Hlatt MgO is more tive than

Hlatt Na2O
=> Hlatt MgO > Hlatt Na2O
because ?

Mg2+ is smaller in
size &
has bigger charge
than Na+

Born Haber Cycle

Thermochemical cycle used to

determine Hlattice
eg : the lattice energy of NaCl

cannot be determine directly

from the reaction :
Na+(g) + Cl-(g) NaCl(s)

Born-Haber Cycles for NaCl

enthalpy H

Na+ (g) + e- + Cl (g)

H

first ionisation energy

Na (g) + Cl (g)
H

first electron affinity

Na+ (g) + Cl- (g)

atomisation

Na (g) + Cl2 (g)

H atomisation
Na (s) + Cl2 (g)
H

formation

NaCl (s)

H lattice
enthalpy

Born-Haber Cycles : applying Hesss Law

There are two routes from elements to ionic compound
enthalpy H

Na+ (g) + e- + Cl (g)

H

first ionisation energy

Na (g) + Cl (g)
H

first electron affinity

Na+ (g) + Cl- (g)

atomisation

Na (g) + Cl2 (g)

Apply
Hesss
Law:

H atomisation
Na (s) + Cl2 (g)
H

formation

lattice

NaCl (s)

HatmNa + HatmCl + H1st IE + H1st EA + Hlattice =

Hformation

Born-Haber Cycles: applying Hesss Law

HatmNa + HatmCl + H1st IE + H1st EA + Hlattice = Hformation
Rearrange to find the lattice energy:

Hlattice = Hformation - (HatmNa + HatmCl + H1st IE + H1st EA)

Constructing Born Haber cycle to calculate

lattice energy of LiF
H3 = BE / Hatomization
H4 = EA1
H2 = IE1

H1 = Hatomization

H5 = Lattice Energy

Born-Haber cycle for the formation of magnesium

chloride
2+
E
Mg (g) +2e +
2Cl(g)

second
ionisation energy of
H4 = +1460
kJ
H5 = -697.4
2 kJ
x electron affinity of chlorin
magnesium

Mg+(g) +e+2Cl(g)

H3= +744kJ
first ionisation energy of magnesium

Mg2+(g) + 2Cl(g)

Mg(g) +
2Cl(g) H2= +243 kJ

bond energy of chlorine

Mg(g) +
Cl2(g)
H1 = +147
kJ
enthalpy
of atomisation of magnesium
Mg(s) +
Cl2(g)

H6

lattice enthalpy of
magnesium chloride

enthalpy of formation of
Hformation = -429.4 kJ
magnesium chloride

MgCl2(s)

Hformation= H1 + H2 + H3 + H4 + H5 +
H
H66 = Hformation - (H1 + H2 + H3 + H4

Hformation= H1 + H2 + H3 + H4 +
H
H65 +=H
H6formation - (H1 + H2 + H3 + H4
+ H5)

= - 429.4 (147 + 243 + 744 +1460 +

H
=
2326.0
lattice
(-697.4))

kJmol-1

Learning Outcomes :
Students able to :
(a) construct energy cycles for the
formation of
aqueous solutions of ionic
compounds;
(b) explain qualitatively the
influence on
solubility of the relationship
between
enthalpy change of solution,

Solubility of Solid in Liquids

Enthalpy of Solution is the enthalpy
change that takes place when
1 mole of a solute dissolves in a
solvent to form
an infinitely dilute solution.
NaCl(s) + aq NaCl(aq)
+5 kJ mol-1

Hsol =

Enthalpy of Solution
The sum of two imaginary steps
reverse of the Lattice Enthalpy
the Hydration Enthalpy

(of the cations and anions)

HLattice
Hhyd

- Lattice Enthalpy
- Hydration Enthalpy

Energy cycle for solution

Ionic lattice +
solvent

Hsolution

- HLatt

solution
Hhyd (cation)
+ Hhyd (anion)

Gaseous ions +
solvent

Hsolution = Hhyd (cation) + Hhyd (anion) - HLattice

Enthalpy Diagram of enthalpy of

solutionNa
of+(g)
NaCl
+ Cl-(g)
-HLattice =
+776 kJ mol-1

Hhyd =
-771 kJ mol-1

Na+(aq) + Cl-(aq)
-1
NaCl(s) + aq Hsol = +5 kJ mol

Hsol = -HLatt + (Hhyd(cation) + Hhyd(anion

= - (-776) + -771

+ 5 kJ mol-1

ha separate the
Energy is absorbed to
td
ec ]
ions in the lattice [ - HLattice
id
es
so
lu
bi
Energy is released by hydration
litof
y?

the ions

If more energy is released than

absorbed, Hsolution will be negative

and the solute is more likely to
The more negative the value for
dissolve.
Hsolution
the more likely the solute is to
dissolve.

e
Is H
nEndothermic
t or exothermic
?
h
H
Solute +
a
solvent
l
H
p
yH

Gaseous
ions

solution

Hhyd(cat)

Latt

Hhyd(an)

solution

solution

-HLE

Solutio
n

+ Hhyd(cat)

+
Hhyd(an)

e
n
t
h
a
l
p
y

Gaseous
ions
Hhyd(cat)
HLatt

Solutio
n
Hsolution

Solute +
solvent

Hsolution =

Hhyd(an)

HLE

+
Hhyd(cat)

Is Hsolution
exothermic
or
endotherm
ic?

+
Hhyd(an)

Ag+(g)
Cl-(g)
Ag+
(aq)
Cl-(aq)
AgCl(s
)

Hsoln = +81kJ/mol

AgCl.

Which solute / substance dissolve

in water?
NaOH
Ans :

END OF CHAPTER!!!