9.
0 THERMOCHEMISTRY
Concept of Enthalpy
Important Terms
Heat is energy transferred between two bodies of
different temperatures
System is any specific part of the universe
Surroundings is everything that lies outside the
system
Open system is a system that can exchange
mass and energy with its surroundings
Closed system is a system that allows the
exchange of energy with its surroundings
Isolated system is a system that does not allow
the exchange of either mass or energy with its
surroundings
Energy is the ability to do work
SI unit of energy is kg m2 s-2 or Joule (J)
Non SI unit of energy is calorie (Cal)
1 Cal = 4.184 J
Thermochemistry
A study of heat change in chemical reactions.
Two types of chemical reactions:
Exothermic
Endothermic
Exothermic reactions
Enthalpy of products < Enthalpy of reactants, H is
negative.
Energy is released from the system to the
surroundings.
Consider the following reaction:
A (g) + B (g) C (g) H = ve
(reactants)
(product)
reactants
enthalpy
H = -ve
products
reaction pathway
Energy profile diagram for exothermic reaction
Endothermic Reactions
Enthalpy of products > enthalpy of reactants, H is
positive
Energy is absorbed by the system from the surrounding
Consider the following reaction
A (g) + B (g) C(g)
H = + ve
(reactants)
(product)
Energy profile of diagram endothermic reactions
Enthalpy, H
The heat content of a system or total energy in the
system
Enthalpy, H of a system cannot be measured when
there is a change in the system.
Example: system undergoes combustion or ionisation.
Enthalpy of Reaction, H and
Standard Condition
Enthalpy of reaction:
The enthalpy change associated with a chemical
reaction.
Standard enthalpy, H
The enthalpy change for a particular reaction that
occurs at 298K and 1 atm (standard state)
Thermochemical Equation
The thermochemical equation shows the enthalpy changes.
Example : H2O(s)
H2O(l)
H = +6.01 kJ
1 mole of H2O(l) is formed from 1 mole of H2O(s) at 0C,
H = +6.01 kJ
However, when 1 mole of H2O(s) is formed from 1 mole of
H2O(l), the magnitude of H remains the same with the
opposite sign of it.
H2O(l) H2O(s) H = 6.01 kJ
Types of Enthalpies
There are many kind of enthalpies such as:
Enthalpy of formation
Enthalpy of combustion
Enthalpy of atomisation
Enthalpy neutralisation
Enthalpy hydration
Enthalpy solution
Enthalpy of Formation, Hf
The change of heat when 1 mole of a compound is
formed from its elements at their standard states.
H2 (g) + O2(g) H2O (l)
Hf = 286 kJ mol1
The standard enthalpy of formation of any element in
its most stable state form is ZERO.
H (O2 ) = 0
H (Cl2) = 0
Enthalpy of Combustion, Hc
The heat released when 1 mole of substance is
burned completely in excess oxygen.
C(s) + O2(g) CO2(g)
Hc = 393 kJ mol1
Enthalpy of Atomisation, Ha
The heat change when 1 mole of gaseous atoms is formed
from its element
Ha is always positive because it involves only breaking of
bonds
e.g:
Na(s)
Cl2(g)
Na(g)
Cl(g)
Ha = +109 kJ mol-1
Ha = +123 kJ mol-1
Enthalpy of Neutralization, Hn
The heat change when 1 mole of water, H2O is formed from the
neutralization of acid and base .
HCl(aq)+ NaOH(aq) NaCl(aq) +H2O(aq)
Hn = 58 kJ mol1
Enthalpy of Hydration, Hhyd
The heat change when 1 mole of gaseous ions is
hydrated in water.
e.g:
Na+(g) Na+(aq) Hhyd = 406 kJ mol-1
Cl-(g)
Cl-(aq)
Hhyd = 363 kJ mol-1
Enthalpy of Solution, Hsoln
The heat change when 1 mole of a substance is
dissolves in water.
e.g:
KCl(s) K+(aq) + Cl(aq) Hsoln = +690 kJ mol-1
Enthalpy of Sublimation, Hsubl
The heat change when one mole of a substance
sublimes (solid into gas).
H subl
I2 (s)
I2(g)
Hsubl =
+106 kJ mol1
Calorimetry
A method used in the laboratory to measure the
heat change of a reaction.
Apparatus used is known as the calorimeter
Examples of calorimeter
Simple calorimeter
Bomb calorimeter
Simple calorimeter
The outer Styrofoam cup
insulate the reaction
mixture from the
surroundings (it is
assumed that no heat is
lost to the surroundings)
Heat release by the
reaction is absorbed by
solution and the
calorimeter
A bomb calorimeter
Important Terms in Calorimeter
Specific heat capacity, c
Specific heat capacity, c of a substance is the amount of
heat required to raise the temperature of one gram of the
substance by one degree Celsius (Jg 1C1).
Heat capacity, C
Heat capacity,C is the amount of heat required to raise
the temperature of a given quantity of the substance by
one degree Celsius (JC1)
Heat released by
substance
Heat absorbed
by calorimeter
q = mcT
q = heat released by substance
m= mass of substance
C= specific heat capacity
T = temperature change
Basic Principle in Calorimeter
Heat released
by a reaction
Heat absorbed
by surroundings
Surroundings may refer to
the:
i. Calorimeter itself or;
ii. The water and calorimeter
qreaction= mcT or CT
Example 1
In an experiment, 0.100 g of H2 and excess of O2 were compressed
into a 1.00 L bomb and placed into a calorimeter with heat capacity
of 9.08 x 104 J0C1. The initial temperature of the calorimeter was
25.0000C and finally it increased to 25.155 0C. Calculate the
amount of heat released in the reaction to form H2O, expressed in kJ
per mole.
Solution
Heat released = Heat absorbed by the
calorimeter
q
= CT
= (9.08 X 104 J0C-1) X (0.1550C)
= 1.41 X 104 J
= 14.1 kJ
H2(g) + O2(g) H2O(c)
mole of H2 = 0.100
2.016
= 0.0496 mol
moles of H2O
mole of H2
0.0496 mol of H2O released 14.1 kJ energy
1 mol H2O released
14.1
= 0.0496
Heat of reaction, H
= 284 kJ
= - 284 kJ mol1
kJ
Example 2
1. Calculate the amount of heat released in a reaction in
an aluminum calorimeter with a mass of 3087.0 g and
contains 1700.0 mL of water. The initial temperature of
the calorimeter is 25.0C and it increased to 27.8C.
Given:
Specific heat capacity of aluminum = 0.553Jg-1 C-1
Specific heat capacity of water
= 4.18 Jg-1 C-1
Water density = 1.0 g mL-1
T = (27.8 -25.0 )C = 2.8C
Solution
Heat released
Heat absorbed by
aluminium
calorimeter
q = mwcwT + mcccT
= (1700.0 g)(4.18 Jg-1 C-1)(2.8 C) +
(3087.0 g)(0.553 Jg-1 C-1)(2.8C)
= 24676.71 J
= 24.7 kJ
+ Heat absorbed by
water
HESSS LAW
Hess Law
Hesss Law states that when reactants are converted to
products, the change in enthalpy is the same whether the
reaction takes place in one step or in the series of steps.
The enthalpy change depends only on the nature of the
reactants and products and is independent of the route
taken.
H1
A
H 2
H 3
H1 H2 H3
Algebraic Method
Step 1
i. List all the thermochemical equations involved
i.C
O
CO
(S)
2( g )
2( g )
1 O
H O
2
2( g )
2( g )
2 ( g)
iii .C H
7 O
2CO
3H O
2
2 6( g )
2( g )
2( g )
2 ( g)
ii.H
H - 393kJmol- 1
H -286kJmol- 1
H -1560kJmol
-1
ii. Write the enthalpy of formation reaction for C2H6
H ?
f
C 3H
C H
( s)
2( g )
2 6( g )
iii. Add the given reactions so that the result is the desired
reaction.
(i ) 2
2C( S ) 2O2( g ) 2CO2( g )
H1 2 -393 kJ
(ii ) 3
3 H 2( g ) 3 O2( g ) 3 H 2O( g )
2
H 2 3 -286kJ
reverse (iii) 2CO 2(g) 3 H 2O( g ) C 2 H 6( g ) 7 O2( g ) H3 1560kJ
2
_______________________________________________________________
H f ?
2C( s ) 3 H 2( g ) C 2 H 6( g )
- 84kJ
H f H1 H 2 H3
-84kJ
Energy Cycle Method
Draw the energy cycle and apply Hesss Law to calculate the
unknown value.
HOf
2C (s )
3H2 (g)
C2H6 (g)
H O2 = 3(-286)
HO1
2O2 (g)
3/2 O2 (g)
= 2(-393)
2CO2 (g) + 3H2O (g)
7/2 O2 (g)
HO3 = - (-1560)
H f = 2( H1 ) + 3( H 2 ) + H3
-786 - 858 1560
1
-84 kJmol
Example 1
The thermochemical equation of combustion
of carbon monoxide is shownHas below.
C(s) + O2(g) CO(g)
=?
H
H
given :
C(s) + O2(g) CO2(g)
H= -394 kJ mol-1
CO(s) + O2(g) CO2(g) H= -283 kJ mol-1
Calculate the enthalpy change of the combustion
of carbon to carbon monoxide.
Example 2
Calculate the standard enthalpy of
formation
of methane if the enthalpy of
H c
combustion
of
carbon,
hydrogen
and
H c
methane
are as follows:
H c
H [C(s)]
= -393 kJ mol-1
H [H2(s)]
= -293 kJ mol-1
H [CH4(s)]
= -753 kJ mol-1
Example 3
Standard enthalpy of formation of
ammonia, hydrogen chloride and
ammonium chloride is -46.1 kJ mol-1,
-92.3 kJ mol-1, 314.4 kJ mol-1
respectively. Write the thermochemical
equation for the formation of each
substance and calculate the enthalpy
change for the following reaction.
NH3(g) + HCl (g) NH4Cl(s)
Exercise
1.Calculate the enthalpy of formation of
benzene
if :
H f
-1
H
(CO
)
=
-393.3
kJ
mol
2(g)
H
f
H f
H (H2O(l) ) = -285.5 kJ mol-1
H (C6H6(l) ) = -3265.3 kJ mol-1
BornHaber
Cycle
Lattice Energy, Hlattice
is the energy required to completely separate one mole of a
solid (ionic compound) into gaseous ions
e.g:
NaCl(s) Na+(g) + Cl-(g)
(lattice dissociation)
Na+(g) + Cl-(g)
Hlattice = +771 kJ mol-1
NaCl(s) Hlattice = -771 kJ mol-1
(lattice formation)
The magnitude of lattice energy increases as
the ionic charges increase
the ionic radii decrease
There
is a strong attraction between small
ions and highly charged ions so the H is
more negative.
for MgO is more negative than H
for Na2O because Mg2+ is smaller in size
and has bigger charge than Na+, therefore
Hlattice (MgO) > Hlattice (Na2O)
Hydration Process of Ionic
Solid
Na+ and Cl- ions in the solid crystal are
separated from each other and converted
to the gaseous state (Hlattice)
The electrostatic forces between gaseous
ions and polar water molecules cause
the ions to be surrounded by water
molecules (Hhydr)
Hsoln = Hlattice + Hhdyr
Na+ and Cl- ion in
the gaseous state
e
c
i
t
t
a
En
y
g
er
He
at
of
Hy
dra
tio
n
Heat of Solution
Na+ and Cl- ion in
the solid state
Hydrated Na+ and Cl- ion
Born-Haber Cycle
The process of ionic bond formation occurs in a
few stages. At each stage the enthalpy changes are
considered.
The Born Haber cycle is often used to calculate
the lattice energy of an ionic compound.
In the Born-Haber cycle energy diagram, by
convention, positive values are denoted as going
upwards, negative values as going downwards.
Consider the enthalpy changes in the formation of
sodium chloride.
Example :
i.
ii.
iii.
iv.
v.
vi.
Given;
Enthalpy of formation NaCl
Enthalpy of sublimation of Na
First ionization energy of Na
Enthalpy of atomization of Cl
Electron affinity of Cl
=
Lattice energy of NaCl
=
=
- 411 kJmol-1
=
+ 108 kJmol-1
=
+ 500 kJmol-1
=
+ 122 kJmol-1
- 364 kJmol-1
?
Example: A Born-Haber cycle for NaCl
energy
Na+(g) + e
+ Cl(g)
Ionisation
Electron Affinity of
Energy of
Cl
Na
Na+(g) + Cl- (g)
Na(g) + Cl(g)
HaCl
Na(g) +
+ve
Cl2(g)
Lattice energy
HaNa
E=
0
-ve
Na(s) + Cl2(g)
From Hesss Law:
Hf
Hf NaCl
NaCl(s)
NaCl
= HaNa + HaCl +IENa +
EACl + Lattice Energy
Na(s)
NaCl(s)
H
Cl2(g)
= 411 kJ mol-
Ho2= +108 kJ mol-
Ho4= +122 kJ mol-1
Na(g)
H 3= + 500 kJ mol
o
Cl(g)
-
Ho5= 364 kJ mol-1
Na+(g)
Ho6=?
Cl(g)
Calculation:
H0f HS IE Ha(Cl) EA Hlattice
Hlattice H0f HS IE Ha(Cl) EA
Hlattice 411
kJ 108kJ 500kJ 122kJ 364kJ
Hlattice 777kJ
Example:
Construct a Born-Haber Cycle to calculate the lattice
energy of KBr based on the following data;
Standard enthalpy of formation of KBr = - 392 kJ mol-1
Enthalpy of sublimation of K = + 90 kJ mol-1
Ionisation energy of K
= + 420 kJ mol-1
Enthalpy of atomization of Br2 = + 112 kJ mol-1
Electron affinity of Br
= - 342 kJ mol-1
Exercise:
Construct a Born-Haber cycle to explain why ionic
compound NaCl2 cannot form under standard conditions.
Use the data below:
i.
Enthalpy of sublimation of sodium
= +108 kJmol-1
First ionization energy of sodium
= +500 kJmol-1
Second ionization energy of sodium = +4562 kJmol-1
Enthalpy of atomization of chlorine
= +121kJmol-1
Electron affinity of chlorine
= -364 kJmol-1
Lattice energy of NaCl2
= -2489 kJmol-1
ii.
iii.
iv.
v.
vi.
