Beruflich Dokumente
Kultur Dokumente
0 THERMOCHEMISTRY
( 4 HOURS)
9.1
9.2
9.3
9.4
Concept of enthalpy
Calorimetry
Hesss law
Born- Haber cycle
AHH
Learning outcomes
a) Explain endothermic and exothermic reactions using
the energy profile diagrams.
b) State standard conditions of reaction and define the
following term s;
i. Enthalpy
ii. Standard enthalpy
c) Define enthalpy of formation, combustion,
atomisation, neutralisation, hydration, and solution
(dissolution).
d) Write the thermochemical equation for each
enthalpy.
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What is
thermochemistry
Thermochemistry
A study of heat change in chemical reactions.
Almost all chemical reactions absorb or
released energy (in the form of heat)
Two types of chemical reactions:
Exothermic
Endothermic
9.1.0
Enthalpy, H
Enthalpy change, H
Example :
A+B
C+D
H = (H C + H D ) - (H A + H B )
PRODUCT
REACTANT
Standard Enthalpy, H
Exothermic reactions
H = ve
reactants
enthalpy
H = -ve
products
reaction pathway
Endothermic Reactions
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Thermochemical Equation
H = +6.01 kJ
Example:
2H2O(l) 2H2O(s)
H = 12.02 kJ
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Types of Enthalpies
Enthalpy of combustion
Enthalpy of atomisation
Enthalpy neutralisation
Enthalpy hydration
Enthalpy solution
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Enthalpy of Formation, Hf
Hf = 241.8 kJ mol1
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O2 (g) O2 (g)
Hf (O2 ) = 0
Hf (Cl2) = 0
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Hf = 285.8 kJ mol1
KMP-SK027-2008/2009
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Enthalpy of Combustion, Hc
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Enthalpy of Atomisation, Ha
Cl(g)
Ha = +123 kJ mol-1
The standard enthalpy of atomisationThe heat absorbed (energy required) when 1 mole of gaseous atoms is
formed from its element under standard conditions
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Enthalpy of Neutralization,
Hn
conditions
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Exercises
1. 2C(s) + H2(g) C2H2(g)
H= +226.6kJmol-1
(a)How much heat is absorbed when 1 gram
of ethyne gas is formed according to the
above equation?
(b)How much heat would be absorbed when 1
mole of carbon reacts according to the
above equation?
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2.
H= -575 kJ
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9.2 Calorimetry
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Learning outcomes
a) Define
i) heat capacity, C
ii) specific heat capacity, c
Calorimetry is the
experimental technique to
determine enthalpy of
reactions.
It will depend on
understanding of specific
heat and heat capacity.
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A simple calorimeter
A bomb calorimeter
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A bomb calorimeter
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Heat absorbed
by surroundings
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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
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q = mcT
Where:
q @ H
m
T
c
C
q = CT
q = mwcwT + mcccT
where
mc
= mass of calorimeter
mw = mass of water
cw
= specific heat of water
cc
= specific heat of calorimeter
T = temperature change
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Example 1:
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Solution
By using the equation:
q = mcT
=(466 g)(4.184 J/g.C)(74.60C8.50C)
= 1.29 x 105 J
= 129 kJ
Therefore the amount of heat absorbed by
the water is 129 kJ.
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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
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Solution
T = (27.8 -25.0 )C = 2.8C
Heat released
Heat absorbed by
water
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
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Example 3
Solution
Enthalpy of combustion
= mwcwT + mcccT
= 3.0 x 102 g x 4.184 Jg-1C-1 x 1.0C) + (1769 JC-1 x 1.0C)
= 3.0 x 103 J
Mol of Mg = 0.14 g
24.31 gmol-1
= 5.76 x 10-3 mol Mg
5.76 x 10-3 mol Mg released 3.0 x 103 J
1.0 mol Mg released :
3.0 x 103J
5.76 x 10-3 mol
= 5.2 x 105 J/mol
Thus, enthalpy of combustion is - 5.2 x 102 kJmol-1
Thermochemical equation is :
Mg(s) + O2(g)
MgO(s)
H = - 5.2 x 102 kJ
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9.3 Hesss
Law
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Learning outcomes
1. Define Hess Law
2. Apply Hesss law to calculate enthalpy
changes using the algebraic method and the
energy cycle.
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Hesss Law
Algebraic
Method
Energy Cycle
Method
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Example 1
= -1560 kJmol-1
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2.
3.
Example
Write the chemical equations for the given
enthalpy change.
a.
H= -393kJ
b.
c.
H= -286 kJ
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H = +1560 kJ
2C(s)
H = 2(-393) kJ
2O2(g)
2CO2(g)
H = 3(-286) kJ
= +1560-786-858
= -84 kJ
Energy Cycle
H Of
2 C (s )
3 H 2 (g )
H
H O1
2 O 2 (g )
O
2
C 2 H 6 (g )
= 3 (-2 8 6 )
3 /2 O 2 ( g )
= 2 (-3 9 3 )
7 /2 O 2 ( g )
H O3 = - ( - 1 5 6 0 )
2 C O 2 (g ) + 3 H 2O (l )
Hf = 2( H1 ) + 3( H2 ) + H
3
2(-393) 3(-286) 1560
- 84 kJ
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Example 2
Let us consider the formation of tin(IV) chloride,
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Algebraic Method
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KMP-SK027-2008/2009
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Learning outcomes
a. Define lattice energy and electron affinity.
b. Explain the following effects on the magnitude
of lattice energy.
i. ionic charges
ii. Ionic radii
c. Explain the dissolution process of ionic solids.
d. Construct Born-Haber cycle for simple ionic
solids using energy cycle diagram.
e. Calculate the enthalpy changes using BornHaber cycles.
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Na+(g) + Cl-(g)
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Exercises
1.
b) Considering NaF
and CaO, which has
the lower melting
point???
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Answer: 1 (a)
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Answer: 1 (b)
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Answer: 2
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Ionisation Energy, IE
energy required to remove 1 mole of electron
from 1 mole of atom in gaseous state.
Mg (g) Mg+ (g) + e
IE1 = +740 kJmol1
(First ionization energy of Mg)
Mg+ (g) Mg2+ (g) + e
Electron Affinity, EA
the heat change when 1 mole of gaseous atoms
gains 1 mole of electrons to form 1 mole of gaseous
ions.
O (g) + e O (g)
EA1 = 142 kJmol1
(First electron affinity of O)
O (g) + e O2( (g)
EA2 = +844 kJ mol-1
(Second electron affinity of O)
Na+ and Cl- ions in the solid crystal are separated from
each other and converted to the gaseous state (Hlattice)
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ic
t
t
La
r
e
n
E
e
He
at
of
Hy
d ra
tio
gy
Heat of Solution
Na+ and Cl- ion in
the solid state
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Born-Haber Cycle
Born-Haber Cycle is an energy cycle for ionic
compound. It connects enthalpy of formation,
which can be determined experimentally.
It is often used to calculate the lattice energy
of an ionic compound which cannot be
determined experimentally.
The Born-Haber Cycle contains enthalpy of
sublimation, enthalpy of atomisation, IE, EA
and lattice energy.
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Solution
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Example 2 :
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
?
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NOTE!
In this Born-Haber cycle
*energy diagram:
positive (+ve)values are
denoted as going
upwards(),
negative(-ve) values as
Lattice energy going downwards().
Ionisation
Electron Affinity of
Energy of
Cl
Na
Na+
+ Cl- (g)
Na(g) + Cl(g)
(g)
HaCl
+ve
Na(g) + Cl2(g)
HaNa
Na(s) +
E=0 Cl2(g)
-ve
Hf
Hf NaCl
NaCl(s)
NaCl
Solution :
H0f HS IE Ha(Cl) EA Hlattice
Hlattice H0f HS IE Ha(Cl) EA
Hlattice 411
kJ 108kJ 500kJ 122kJ 364kJ
Hlattice 777kJ
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Answer: Exercise 1
KMP-SK027-2008/2009
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Exercise 2
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Answer: Exercise 2
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Exercise 3:
i.
ii.
iii.
iv.
v.
vi.