Energetics

What is Energetics?
Enthalpy Changes Related to Breaking and
Forming of Bonds
Standard Enthalpy Changes
Experimental Determination of Enthalpy
Changes by Calorimetry
Hesss Law
Calculations involving Standard Enthalpy
Changes of Reactions
1

What is energetics?
Energetics is the study of energy changes
associated with chemical reactions.

Thermochemistry is the study of heat changes

associated with chemical reactions.
Some terms
Enthalpy(H) = heat content in a substance
Enthalpy change(H)
= heat content of products - heat content of
reactants
= Hp - Hr
2

Law of conservation of energy

The law of conservation of energy states that
energy can neither be created nor destroyed.

Exothermic and endothermic reactions

An exothermic reaction is a reaction that

releases heat energy to the surroundings.
(H = -ve)
4

Exothermic and endothermic reactions

An endothermic reaction is a reaction that

absorbs heat energy from the surroundings.
(H = +ve)
5

Energy Changes
Related to Breaking
and Forming of Bonds
6

Enthalpy changes related to breaking and

forming of bonds
e.g. CH4 + 2O2 CO2 + 2H2O

Enthalpy changes related to breaking and

forming of bonds
In an exothermic reaction, the energy required in
breaking the bonds in the reactants is less than
the energy released in forming the bonds in the
products (products contain stronger bonds).

Enthalpy changes related to breaking and

forming of bonds

Enthalpy changes related to breaking and

forming of bonds
In an endothermic reaction, the energy required
in breaking the bonds in the reactants is more
than the energy released in forming the bonds
in the products (reactants contain stronger
bonds).

10

Standard Enthalpy
Changes

11

Standard enthalpy changes

CH4(g) + 2O2(g) CO2(g) + 2H2O(g)
H = -802 kJ mol-1
CH4(g) + 2O2(g) CO2(g) + 2H2O(l)
H = -890 kJ mol-1

12

Standard enthalpy changes

As enthalpy changes depend on temperature
and pressure, it is necessary to define standard
states and conditions:
1.
2.
3.

elements or compounds in their normal

physical states;
a pressure of 1 atm (101325 Nm-2); and
a temperature of 25oC (298 K)

Enthalpy change under standard conditions denoted

by symbol: H
13

Standard enthalpy changes of

neutralization
Standard enthalpy change of neutralization
(Hneut) is the enthalpy change when one mole
of water is formed from the neutralization of an
acid by an alkali under standard conditions.
e.g. H+(aq) + OH-(aq) H2O(l)

Hneut = -57.3 kJ mol-1

14

Standard enthalpy changes of

neutralization
Acid
HCl
HCl
HCl
HF

Alkali
NaOH
KOH
NH3
NaOH

Hneu
-57.1
-57.2
-52.2
-68.6

H+(aq) + OH-(aq) H2O(l)

15

Standard enthalpy changes of

neutralization

Enthalpy level diagram for the neutralization of a

strong acid and a strong alkali
16

Standard enthalpy change of solution

Standard enthalpy change of solution (Hsoln)
is the enthalpy change when one mole of a
solute is completely dissolved in a sufficiently
large volume of solvent to form an infinitely
dilute solution under standard conditions.

17

Standard enthalpy change of solution

e.g. NaCl(s) + water Na+(aq)+Cl-(aq)

Hsoln= +3.9 kJ mol-1

Enthalpy level diagram

for the dissolution of
NaCl
18

Standard enthalpy change of solution

e.g. LiCl(s) + water Li+(aq) + Cl-(aq)
Hsoln= -37.2 kJ mol-1

Enthalpy level diagram

for the dissolution of
LiCl in water
19

Standard enthalpy change of solution

Salt
NaOH
NaCl
KOH
KBr

20

Hsoln(kJ mol-1)
-44.7
+3.9
-57.8
+20.0

Standard enthalpy change of

formation
Standard enthalpy change of formation (Hf )
is the enthalpy change of the reaction when
one mole of the compound in its standard
state is formed from its constituent elements
under standard conditions.

21

Standard enthalpy change of

formation
e.g.

2Na(s) + Cl2(g) 2NaCl(s)

H = -822 kJ mol-1

Na(s) + Cl2(g) NaCl(s)

Hf = -411 kJ mol-1
Standard enthalpy change of
formation of NaCl is -411 kJ mol-1.
22

Standard enthalpy change of

formation
What is Hf [N2(g)] ?
N2(g) N2(g)
Hf [N2(g)] = 0
The enthalpy change of formation of an
element is always zero.

23

Standard enthalpy change of combustion

e.g. C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)

H1 = -2220 kJ
2C3H8(g) + 10O2(g) 6CO2(g) + 8H2O(l)
H2 = -4440 kJ

It is more convenient to report enthalpy

changes per mole of the main reactant
reacted/product formed.
24

H2 = ?

Standard enthalpy change of combustion

Standard enthalpy change of combustion (Hc )
of a substance is the enthalpy change when one
mole of the substance burns completely in
excess oxygen under standard conditions.
e.g. C3H8(g) + 5O2(g) 3CO2(g) + 4H2O(l)
1 mole

Hc = -2220 kJ mol-1
25

Standard enthalpy change of combustion

26

Substance

Hc (kJ mol-1)

H2(g)
C (diamond)
C (graphite)
CO(g)
CH4(g)

-285.8
-395.4
-393.5
-283.0
-890.4

Experimental
Determination of
Enthalpy Changes
by Calorimetry
27

Experimental determination of enthalpy

changes by calorimetry
Calorimeter = a container used for measuring
the temperature change of solution

28

Types of calorimeter

Bomb calorimeter
Bomb calorimeter is a type of calorimeter used in measuring the
heat
of combustion of samples which can be burned in oxygen.
29

Four essential parts of bomb calorimeter

1. a bomb or vessel,

2. a bucket or container for

holding the bomb in a
measured quantity of
water, together with a
stirring mechanism,
3. an insulating jacket
4. a thermometer or other
sensor for measuring
temperature changes
within the bucket.
30

Types of calorimeter

Coffee-cup calorimeter is a constant-pressure calorimeter

measures the change in enthalpy of a reaction occurring in
solution during which the atmospheric pressure remains
constant.
31

Determination of enthalpy change of neutralization

m = mass of the solution ( m of acid + base )
C= specific heat capacity of water
T = temperature change (Tfinal T initial)
n = no. of moles of H2O formed

32

25.0 cm3 of 1.00 mol dm-3 HCl at 21.5 C were placed in a

polystyrene cup. 25.0 cm3 of 1.00 mol dm-3 NaOH at 21.5 C
were added. The mixture was stirred and the temperature of
the solution rose to 28.2 C.
Calculate the molar enthalpy change of neutralisation.
q
H
n
50.0 x 4.18 x6.7
H
56012 Jm0l 1
0.025 x1.00
H 56.0kJm0l 1
The Hn for strong acid + strong base is -57.8 kJ mol-1.
Explain why the experimental value obtained is less than the
actual value found in most of the references?
- The low experimental value indicates that the heat is lost to the
surroundings
33

Thermometric titration

34

The H is determined by
measuring the temperature
change as known volume
of NaOH (aq) is titrated
with HCl.

The temperature is
recorded at regular
intervals.

The maximum temperature

rise (T) is determined by
plotting the temperature of
the mixture against the
volume of HCl added.

ASSUMPTIONS to be taken when calculating

for Hn
1. Density of the mixture = density of H2O (1.0 g cm-3)

2. Specific heat capacity of ALL solution is 4.18 J g-1 C-1

3. Heat capacity of polystyrene cup is negligible.

35

Determination of enthalpy change of combustion

Hc is always
negative
Hc can be used to
give the energy
values of fuels and
foods

36

Determination of enthalpy change of combustion

The Hc is determined
by measuring the
temperature rise as a
known mass of water is
heated by burning a
known mass of
compound.

The temperature of
water is recorded at
regular time interval.

A simple apparatus used to determine the

enthalpy change of combustion of ethanol
37

The mass of the

compound is recorded
after the apparatus has
been cooled off.

DETERMINING THE ENTHALPY OF COMBUSTION

Hc = q/n
Where m = is the mass of water in the calorimeter,
c = is the specific heat capacity of the water,
T = is the temperature change of the
the water in the calorimeter
n = mass of the compound combusted

molecular mass

38

39

Determination of enthalpy change of solution

By measuring the temperature change when
a known mass of solute is added to a known
volume of solvent in a calorimeter
q= mcT
H = q/n
m = mass of water

n = no. of moles of the SOLID

40

Determination of enthalpy change of formation

The reaction is often theoretical and may not take place in
practice.
Hf of an element is ZERO.
Hf is often used to determine the stability of the compounds
relative to its constituent elements.
If Hf is < 0, the compound is energetically more stable than
its constituent elements.
If Hf is > 0, the compound is energetically less stable than its
constituent elements.
Example:
compound

HF (g)

HCl (g)

HBr (g)

HI (g)

Hf

-269

-92

-36

+27

41

Determination of enthalpy change of formation

The conversion of graphite to diamond has a small positive
value of H.
C(graphite) C(diamond) H = + 2.1 kJ/mol
The reaction is energetically feasible ( due to small positive
H), but it is kinetically VERY SLOW due to high activation
energy.

42

Determination of enthalpy change of formation

The enthalpy change of formation of a substance
can be quite high
Found out by applying Hesss law of constant
heat summation

43

Hesss Law

44

Hess Law
Route 1

H1
H2

H3

B
Route 2

H1 = H2 + H3

Hesss law of constant heat summation states

that the total enthalpy change accompanying
a chemical reaction is independent of the route
by which the chemical reaction takes place.
45

Hess Law
The enthalpy change in the chemical reaction is the same
whether the change is brought about in one stages or
through intermediate stages.
The enthalpy change is independent of its path as long
as the reactants and products are the same.
Route 1

H1
H3

H2

B
Route 2

H1 = H2 + H3

The
46 enthalpy change in the reaction A C is the same with ABC

Enthalpy level diagram

Relate substances together in terms of enthalpy
changes of reactions

Enthalpy level diagram

for the oxidation of
C(graphite) to CO2(g)

47

Enthalpy cycle (Energy cycle diagram)

Relate the various equations involved in a
reaction

Enthalpy cycle for the

oxidation of C(graphite)
to CO2(g)
48

Sample problem:
1. Calculate the standard enthalpy change of formation of CH4
given the following:
Hc of methane

-890.2 kJ/mol

Hc of hydrogen

-285.7 kJ/mol

Hc of graphite

-285.7 kJ/mol

2. Calculate the enthalpy change of the reaction:

CaF2 + H2SO4 2HF + CaSO4

given the enthalpy of formation of CaF2 , H2SO4 , HF

and CaSO4
are -1220, -814, -271, and -1434, in kJ/mol, respectively.
49

Importance of Hesss law

The enthalpy change of some chemical reactions
cannot be determined directly because:
the reactions cannot be performed in the
laboratory
the reaction rates are too slow
the reactions may involve the formation of side
products
But the enthalpy change of such reactions can be
determined indirectly by applying Hesss Law.
50

Enthalpy change of formation of CO(g)

Given: Hf [CO2(g)] = -393.5 kJ mol-1;

Hc [CO(g)] = -283.0 kJ mol-1

C(graphite) + O2(g)
+ O2(g)

Hf [CO(g)]

+ O2(g)
H1

CO2(g)

H2

Hf [CO(g)] + H2 = H1
Hf [CO(g)] = H1 - H2
= -393.5 - (-283.0 )
= -110.5 kJ mol-1
51

CO(g)

Enthalpy change of formation of CaCO3(s)

Ca(s) + C(graphite) + 3 O2
2

Hf [CaCO3(s)]

CaCO3(s)
H2

H1
CaO(s) + CO2(g)
Hf [CaCO3(s)] = H1 + H2

= -1028.5 kJ mol-1 + (-178.0) kJ mol-1

= -1206.5 kJ mol-1

52

Calculations involving
Standard Enthalpy
Changes of Reactions
53

Calculation of standard enthalpy change of

reaction from standard enthalpy changes
of formation

Hreaction = Hf [products] - Hf [reactants]

54

Calculation of standard enthalpy change of

formation from standard enthalpy changes
of combustion

Hf = Hc [products] - Hc [reactants]
55