FOUNDATION CHEMISTRY I

CHM092
CHAPTER 5:
THERMOCHEMISTRY
PREPARED BY
SYED ABDUL ILLAH ALYAHYA
Topic
CHAPTER 5

5.1 Introduction to Thermochemistry
5.2 System and Surroundings
5.3 Exothermic and Endothermic Reactions
5.4 Specific Heat Capacity
5.5 Enthalpy and Calorimetry
5.6 Enthalpy Changes for Chemical Reactions
5.7 Hesss Law
5.8 Lattice Energy and Born-Harber Cycle
Topic
5.1 Introduction to
Thermochemistry
All matter contains energy- whenever matter
undergoes a change, the quantity of energy that the
matter contains also changes
Example burning candle melts a piece of ice, both
chemical and physical changes
In chemical change- higher energy reactants (wax and O
2
form
lower energy products (CO
2
and H
2
O)
In physical change- heat is absorbed ice turns to water
Thermodynamics is the study of energy and its
transformations
Thermochemistrythe branch of thermodynamics
that deal with heat in chemical and physical changes
The Nature of Energy
5.1 Introduction to Thermochemistry
Manifestations of Energy
5.1 Introduction to Thermochemistry
Some Forms of Energy
Electrical
kinetic energy associated with the flow of electrical charge
Heat or Thermal Energy
kinetic energy associated with molecular motion
Light or Radiant Energy
kinetic energy associated with energy transitions in an atom
Nuclear
potential energy in the nucleus of atoms
Chemical
potential energy due to the structure of the atoms, the
attachment between atoms, the atoms positions relative to
each other in the molecule, or the molecules, relative
positions in the structure
5.1 Introduction to Thermochemistry
The amount of kinetic energy an object has is directly
proportional to its mass and velocity
KE = mv
2

Units of Energy
5.1 Introduction to Thermochemistry
Units of Energy
Joule (J) is the amount of energy needed to move a 1-
kg mass a distance of 1 meter
1 J = 1 Nm = 1 kgm
2
/s
2

Calorie (cal) is the amount of energy needed to raise the
temperature of one gram of water 1C
kcal = energy needed to raise 1000 g of water 1C
food Calories = kcals
Energy Conversion Factors
1 calorie (cal) = 4.184 joules (J) (exact)
1 Calorie (Cal) = 1000 cal = 1 kcal = 4184 J
1 kilowatt-hour (kWh) = 3.60 x 10
6
J
5.1 Introduction to Thermochemistry
Conservation of Energy
The Law of Conservation of
Energy states that energy
cannot be created nor destroyed
When energy is transferred
between objects, or converted
from one form to another, the
total amount of energy present
at the beginning must be
present at the end
5.1 Introduction to Thermochemistry
Temperature and Heat
The temperature of an object is a measure of its ability to
transfer energy as heat.
When two objects at different temperature are brought into
contact, energy will be transferred as heat from one at the
higher temperature to the one at the lower temperature.
Temperature determines the direction of thermal energy
transfer
The higher temperature of a given object, the greater the
thermal energy of its atoms, ion, or molecules (energy
associated with molecular motion)
Heating and cooling are processes by which energy
transferred as heat from high temperature to lower
temperature. Heat is not a substance
5.1 Introduction to Thermochemistry
Topic
5.2 System and
Surroundings
Definition
We define the system as the material or process within
which we are studying the energy changes within
We define the surroundings as everything else with which
the system can exchange energy with
What we study is the exchange of energy between the
system and the surroundings

Surroundings




System

Surroundings




System
5.2 System and Surroundings
Comparing the Amount of Energy in the
System and Surroundings During Transfer
Conservation of energy means that the amount of energy
gained or lost by the system has to be equal to the amount
of energy lost or gained by the surroundings
5.2 System and Surroundings
Energy Flow and
Conservation of Energy
Conservation of energy requires that the sum of the energy
changes in the system and the surroundings must be zero
Energy
universe
= 0 = Energy
system
+ Energy
surroundings

Is the symbol that is used to mean change
final amount initial amount
AE = E
final
- E
initial

5.2 System and Surroundings
Energy Flow
When energy flows out of a
system, it must all flow into the
surroundings
When energy flows out of a
system, E
system
is ve
When energy flows into the
surroundings, E
surroundings
is
+ve
Therefore:
E
system
= E
surroundings



Surroundings
AE +





System
AE

5.2 System and Surroundings
Energy Flow
When energy flows into a
system, it must all come from
the surroundings
When energy flows into a
system, E
system
is +ve
When energy flows out of the
surroundings,
E
surroundings
is ve
Therefore:
E
system
= E
surroundings



Surroundings
AE





System
AE +

5.2 System and Surroundings
Open systems both matter (mass) and energy can move into and out of an open system.
The earth, for example, is an open system. Energy comes in from the sun, and is re-radiated
back to space. Meteors strike the Earth, and cause parts of the Earth to be ejected into
space. We send satellites into interstellar space. These are difficult systems to study
scientifically because there are too many variables to track.
Closed systems matter cant be transferred from a closed system, but energy can. We study
these frequently, and a great example is the ubiquitous coffee cup calorimeter used in
many general chemistry laboratories. These are great ways to see how a system (some
chemical reaction) causes a change in temperature in the surroundings (the solvent, often
water) that is contained in the cup.
Isolated systems neither matter or energy can be transferred from these systems to the
surroundings
Types of System
5.2 System and Surroundings
Open systems both matter (mass) and energy can move into
and out of an open system. The earth, for example, is an open
system. Energy comes in from the sun, and is re-radiated back
to space.

Closed systems matter cant be transferred from a closed
system, but energy can. We study these frequently, and a great
example is the ubiquitous coffee cup calorimeter used in many
general chemistry laboratories. These are great ways to see
how a system (some chemical reaction) causes a change in
temperature in the surroundings (the solvent, often water) that
is contained in the cup.

Isolated systems neither matter or energy can be transferred
from these systems to the surroundings
Energy Flow in Chemical Reaction
5.2 System and Surroundings
Many chemical reactions are accompanied by the liberation
or absorption of heat.

Total heat absorbed or liberated in a chemical reaction is
called the heat of reaction

In chemical reaction, - systems are the reactants and
products. Surroundings is the vessel or container in which
the reaction take place and the air or other material in thermal
contact with the reaction system.
Internal Energy and Energy Exchange
5.2 System and Surroundings
The internal energy (U) in a chemical system is the sum of
the potential and kinetics energies of the atoms, molecules or
ions in the system.

Change in internal energy (U) is a measure the energy
transferred as heat and work to or from the system.
AU = q + w
The sum of the energy transferred as heat between the
system and surrounding (q)
The energy transferred as work between the system and its
surroundings (w)
U is represent the internal energy, but some textbook use E, doesnt matter
Energy Diagrams
Energy diagrams are a graphical way of showing the
direction of energy flow during a chemical process
If the final condition has a larger
amount of internal energy than the initial
condition, the change in the internal
energy will be +ve

If the final condition has a smaller
amount of internal energy than the
initial condition, the change in the
internal energy will be ve

5.2 System and Surroundings
energy
released
AE
rxn
=
energy
absorbed
AE
rxn
= +
Energy Flow in a Chemical Reaction
The total amount of internal energy in
1mol of C(s) and 1 mole of O
2
(g) is
greater than the internal energy in 1 mole
of CO
2
(g)
at the same temperature and pressure
In the reaction C(s) + O
2
(g) CO
2
(g), there
will be a net release of energy into the
surroundings
E
reaction
= E
surroundings
In the reaction CO
2
(g) C(s) + O
2
(g), there
will be an absorption of energy from the
surroundings into the reaction
E
reaction
= E
surroundings

I
n
t
e
r
n
a
l

E
n
e
r
g
y

CO
2
(g)
C(s), O
2
(g)
Surroundings
System
C + O
2
CO
2
System
CO
2
C + O
2
5.2 System and Surroundings
Energy transferred as heat only (q) and does no work (w = 0)
E = q + 0 = q
The two cases where energy is transferred as heat only.
1. Heat flowing out from a system.
2. Heat flowing into a system
The system releases heat. q = -ve
The system absorbs heat. q = +ve
Energy Exchange in Chemical Reactions
5.2 System and Surroundings
Energy transferred as work only (w) and q = 0, E = 0 + w = w
1. Work done by a system = work done on the surroundings
The system does work on the surroundings. w = -ve
H
2
(g) + Zn
2+
(aq) + 2Cl
-
(aq)
Zn(s) + 2H
+
(aq) + 2Cl
-
(aq)
5.2 System and Surroundings
Energy Exchange in Chemical Reactions
2. Work done on a system = work done by a surroundings
The system has work done on it by the surroundings. w = +ve
5.2 System and Surroundings
Energy Exchange in Chemical Reactions
The values of q and w can have either a positive or negative
5.2 System and Surroundings
Energy Exchange in Chemical Reactions
q w
+ =
E
+
+
-
-
-
-
+
+
+
-
depends on sizes of q and w
depends on sizes of q and w
5.2 System and Surroundings
Energy Exchange in Chemical Reactions
Example 1
Determining the Change in Internal
Energy of a System
PROBLEM: When gasoline burns in a car engine, the heat released
causes the products CO
2
and H
2
O to expand, which
pushes the pistons outward. Excess heat is removed by
the cars radiator. If the expanding gases do 451 J of
work on the pistons and the system releases 325 J to the
surroundings as heat, calculate the change in energy
(E) in J, kJ, and kcal.
Define the system and surroundings and assign signs to q
and w correctly. Then E = q + w. The answer can then be
converted from J to kJ and to kcal.
PLAN:
SOLUTION:
Heat is given out by the system, so q = - 325 J
The gases expand to push the pistons, so the system does work on
the surroundings and w = - 451 J
E = q + w = -325 J + (-451 J) = -776 J
-776 J x
10
3
J
1 kJ
= -0.776 kJ -0.776 kJ x
4.184 kJ
1 kcal
= -0.185 kcal
Heat is given out by a chemical reaction, so it makes sense to define
the system as the reactants and products involved. The pistons, the
radiator and the rest of the car then comprise the surroundings.
Topic
5.3 Endothermic and Exothermic
Reactions
Endothermic & Exothermic Reactions
When E is , heat is being released by the system
Reactions that release heat are called exothermic reactions
When E is +, heat is being absorbed by the system
Reactions that absorb heat are called endothermic reactions
Chemical heat packs contain iron filings that are oxidized in an
exothermic reaction your hands get warm because the released heat
of the reaction is transferred to your hands
Chemical cold packs contain NH
4
NO
3
that dissolves in water in an
endothermic process your hands get cold because the pack is
absorbing your heat
For an exothermic reaction, the surroundings temperature
rises due to release of thermal energy by the reaction
This extra thermal energy comes from the conversion of
some of the chemical potential energy in the reactants into
kinetic energy in the form of heat
During the course of a reaction,old bonds are broken and
new bonds are made
The products of the reaction have less chemical potential
energy than the reactants
The difference in energy is released as heat
Molecular View of Exothermic Reactions
Molecular View of Endothermic Reactions
In an endothermic reaction, the surroundings temperature
drops due to absorption of some of its thermal energy by
the reaction
During the course of a reaction, old bonds are broken and
new bonds are made
The products of the reaction have more chemical potential
energy than the reactants
To acquire this extra energy, some of the thermal energy
of the surroundings is converted into chemical potential
energy stored in the products
Topic
5.4 Specific Heat Capacity
Heat Exchange
Heat is the exchange of thermal energy between the
system and surroundings
Heat exchange occurs when system and surroundings
have a difference in temperature
Temperature is the measure of the amount of thermal
energy within a sample of matter
Heat flows from matter with high temperature to matter with
low temperature until both objects reach the same
temperature - thermal equilibrium is achieved
After thermal equilibrium is attained, the object whose
temperature increased has gained thermal energy, and the
object whose temperature decreased has lost thermal
energy
5.4 Specific Heat Capacity
Quantity of Heat Energy Absorbed:
Heat Capacity
When a system absorbs heat, its temperature increases
The increase in temperature is directly proportional to the
amount of heat absorbed
The proportionality constant is called the heat capacity, C
units of C are J/C or J/K
q = C x T
The larger the heat capacity of the object being studied, the
smaller the temperature rise will be for a given amount of
heat

5.4 Specific Heat Capacity
Factors Affecting Heat Capacity
The heat capacity of an object depends on its amount of
matter
usually measured by its mass
200 g of water requires twice as much heat to raise its
temperature by 1C as does 100 g of water
The heat capacity of an object depends on the type of
material
1000 J of heat energy will raise the temperature of 100
g of sand 12 C, but only raise the temperature of 100 g
of water by 2.4 C

5.4 Specific Heat Capacity
Specific Heat Capacity
Measure of a substances intrinsic
ability to absorb heat
The specific heat capacity is the
amount of heat energy required to raise
the temperature of one gram of a
substance 1C
Symbol is C
s
units are J/(gC)
The molar heat capacity is the amount
of heat energy required to raise the
temperature of one mole of a substance
1C ( Molar heat capacity for water is
75.4 J/mol.
o
C)
5.4 Specific Heat Capacity
Specific Heat of Water
The rather high specific heat of water allows water to
absorb a lot of heat energy without a large increase in its
temperature
The large amount of water absorbing heat from the air
keeps beaches cool in the summer
without water, the Earths temperature would be about the same as
the moons temperature on the side that is facing the sun (average
107 C or 225 F)
Water is commonly used as a coolant because it can
absorb a lot of heat and remove it from the important
mechanical parts to keep them from overheating
or even melting
it can also be used to transfer the heat to something else
because it is a fluid
5.4 Specific Heat Capacity
Quantifying Heat Energy
The heat capacity of an object is proportional to its mass
and the specific heat of the material
So we can calculate the quantity of heat absorbed by an
object if we know the mass, the specific heat, and the
temperature change of the object
Heat = (mass) x (specific heat) x (temp. change)
q = (m) x (C
s
) x (T)
5.4 Specific Heat Capacity
Example 3: How much heat is absorbed by a copper
penny with mass 3.10 g whose temperature rises from
8.0 C to 37.0 C?



q = m C
s
AT
C
s
= 0.385 J/gC (Table 6.4)
the unit is correct, the sign is reasonable as
the penny must absorb heat to make its
temperature rise
T
1
= 8.0 C, T
2
= 37.0 C, m = 3.10 g
q,

J
Check: Check
Solution:
Follow the
conceptual
plan to
solve the
problem
Conceptual
Plan:


Relationships:
Strategize
Given:

Find:
Sort
Information
C
s
m, AT q
Exercise 2 Calculate the amount of heat released
when 7.40 g of water cools from 49 to 29 C
(waters specific heat is 4.18 J/gC)
Exercise 2 Calculate the amount of heat released
when 7.40 g of water cools from 49 to 29 C



q = m C
s
AT
C
s
= 4.18 J/gC (Table 6.4)
T
1
= 49 C, T
2
= 29 C, m = 7.40 g
q,

J
Check: Check
Solution:
Follow the
concept plan
to solve the
problem
Conceptual
Plan:


Relationships:
Strategize
Given:

Find:
Sort
Information
C
s
m, AT q
the unit is correct, the sign is reasonable as
the water must release heat to make its
temperature fall
Thermal Energy Transfer
When two objects at different temperatures are placed in
contact, heat flows from the material at the higher
temperature to the material at the lower temperature
Heat flows until both materials reach the same final
temperature
The amount of heat energy lost by the hot material equals
the amount of heat gained by the cold material
q
hot
= q
cold

m
hot
C
s,hot
AT
hot
= (m
cold
C
s,cold
AT
cold
)
5.4 Specific Heat Capacity
1. Heat lost by the metal > heat gained by water
2. Heat gained by water > heat lost by the metal
3. Heat lost by the metal > heat lost by the water
4. Heat lost by the metal = heat gained by water
5. More information is required


1. Heat lost by the metal > heat gained by water
2. Heat gained by water > heat lost by the metal
3. Heat lost by the metal > heat lost by the water
4. Heat lost by the metal = heat gained by water
5. More information is required


A piece of metal at 85 C is added to water at 25 C, the final
temperature of the both metal and water is 30 C. Which of
the following is true?



q = m C
s
AT
C
s, Al
= 0.903 J/gC, C
s, H2O
= 4.18 J/gC(Table 6.4)
Example 4: A 32.5-g cube of aluminum initially at 45.8 C is
submerged into 105.3 g of water at 15.4 C. What is the final
temperature of both substances at thermal equilibrium?
the unit is correct, the number is reasonable as the final
temperature should be between the two initial temperatures
m
Al
= 32.5 g, T
al
= 45.8 C, m
H20
= 105.3 g, T
H2O
= 15.4 C
T
final
,

C
Check:
Solution:
Conceptual
Plan:


Relationships:
Given:

Find:
C
s, Al
m
Al
, C
s, H2O
m
H2O

AT
Al
= kAT
H2O
q
Al
= q
H2O

T
final

Exercise 3 A hot piece of metal
weighing 350.0 g is heated to 100.0 C.
It is then placed into a coffee cup
calorimeter containing 160.0 g of water
at 22.4 C. The water warms and the
copper cools until the final temperature
is 35.2 C. Calculate the specific heat of
the metal and identify the metal.
Exercise 3 Calculate the specific heat and
identify the metal from the data
q = m x C
s
x AT; q
metal
= q
H2O

the units are correct, the number indicates
the metal is copper
metal: 350.0 g, T
1
= 100.0 C, T
2
= 35.2 C
H
2
O: 160.0 g, T
1
= 22.4 C, T
2
= 35.2C, C
s
= 4.18 J/g C
C
s ,
metal,

J/gC
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
m, C
s
, AT q
Additional Problems
5.4 Specific Heat Capacity
1. How much energy must be transferred to raise the temperature of a
cup of coffee (250mL) from 20.5
o
C to 95.6
o
C. (Assume that water
and coffee have the same density 1.00g/mL and specific heat
capacity 4.184 J/g.
o
C


2. A iron block whose temperature is 78.8
o
C is placed in a calorimeter
containing 244g of water at 18.8
o
C. After thermal equilibrium is
attained at 22
o
C. What is the mass of iron block? (Assume no energy
is lost to calorimeter and its surrounding)
Topic
5.5 Enthalpy and Calorimetry
Pressure Volume Work
PV work is work caused by a volume change against an
external pressure
When gases expand, V is +ve, but the system is doing
work on the surroundings, so w
gas
is ve
As long as the external pressure is kept constant
Work
gas
= External Pressure x Change in Volume
gas

w = PV
to convert the units to joules use 101.3 J = 1 atmL
5.5 Enthalpy and Calorimetry
Enthalpy
The enthalpy, H, of a system is the sum of the internal
energy of the system and the product of pressure and
volume
H is a state function
H = E + PV
The enthalpy change, H, of a reaction is the heat
evolved in a reaction at constant pressure
H
reaction
= q
reaction at constant pressure

Usually H and E are similar in value, the difference is
largest for reactions that produce or use large quantities of
gas
5.5 Enthalpy and Calorimetry
The Difference between H

and E
Lighters are usually fueled by butane (C
4
H
10
). When 1 mole
of butane burns at constant pressure, it produces 2658 kJ of
heat and does 3 kJ of work. What are the values of H and
E for the combustion of one mole butane?
Answer
H represents only the heat exchanged; therefore H = -
2658 kJ

But E represents the heat and work exchanged ; therefore
E = -2661 kJ
Notice that both are negative because heat and work are
flowing out of the system and into surroundings- same
magnitude

5.5 Enthalpy and Calorimetry
Enthalpy of Reaction
The enthalpy change in a chemical reaction is an extensive
property
the more reactants you use, the larger the enthalpy change
By convention, we calculate the enthalpy change for the
number of moles of reactants in the reaction as written
C
3
H
8
(g) + 5 O
2
(g) 3 CO
2
(g) + 4 H
2
O(g) H = 2044 kJ

5.5 Enthalpy and Calorimetry
Relationships Involving H
rxn

When reaction is multiplied by a factor, H
rxn
is
multiplied by that factor
because H
rxn
is extensive
C(s) + O
2
(g) CO
2
(g) H = 393.5 kJ
2 C(s) + 2 O
2
(g) 2 CO
2
(g) H = 2(393.5 kJ) = 787.0 kJ
If a reaction is reversed, then the sign of H is
changed
CO
2
(g) C(s) + O
2
(g) H = +393.5 kJ
5.5 Enthalpy and Calorimetry
Exchanging Energy Between
System and Surroundings
Exchange of heat energy
q = mass x specific heat x Temperature
Exchange of work
w = Pressure x Volume
E = m x Cs x T + (-PV)
5.5 Enthalpy and Calorimetry
Measuring E,
Calorimetry at Constant Volume
Because E = q + w, we can determine E by measuring q
and w
In practice, it is easiest to do a process in such a way that
there is no change in volume, so w = 0
at constant volume, E
system
= q
system

In practice, it is not possible to observe the temperature
changes of the individual chemicals involved in a reaction so
instead, we measure the temperature change in the
surroundings
use insulated, controlled surroundings
q
system
= q
surroundings

The surroundings is called a bomb calorimeter and is usually
made of a sealed, insulated container filled with water
q
surroundings
= q
calorimeter
= q
system
Bomb Calorimeter
Used to measure E
because it is a constant
volume system
The heat capacity of the
calorimeter is the amount of
heat absorbed by the
calorimeter for each degree
rise in temperature and is
called the calorimeter
constant C
cal
, kJ/C
q
cal
= C
cal
x T q
cal
= -q
rxn
Measuring H
Calorimetry at Constant Pressure
Reactions done in aqueous solution are
at constant pressure
open to the atmosphere
The calorimeter is often nested foam
cups containing the solution
q
reaction
= q
solution

= (mass
solution
x C
s, solution
x T)
H
reaction
= q
constant pressure
= q
reaction

to get H
reaction
per mol, divide by the
number of moles
Example 7: What is H
rxn/mol Mg
for the reaction
Mg(s) + 2 HCl(aq) MgCl
2
(aq) + H
2
(g) if 0.158 g Mg reacts in
100.0 mL of solution and changes the temperature from 25.6 C to 32.8
C?
the sign is correct and the value is reasonable because
the reaction is exothermic
0.158 g Mg, 100.0 mL, T
1
= 25.6 C, T
2
= 32.8 C,
assume d = 1.00 g/mL, C
s
= 4.18 J/gC
H,

kJ/mol
Check:
Solution:
Conceptual Plan:

Relationships:
Given:

Find:
q
rxn
, mol

AH

C
s
, AT, m q
soln

q
rxn
q
soln
= m x C
s, soln
x AT = q
rxn
, MM Mg= 24.31 g/mol
6.499 x 10
3
mol Mg, 1.00 x 10
2
g, AT = 7.2 C,,C
s
= 4.18 J/gC

AH,

kJ/mol
Exercise 6 What will be the final temperature of the solution
in a coffee cup calorimeter if a 50.00 mL sample of 0.250 M
HCl(aq) is added to a 50.00 mL sample of 0.250 NaOH(aq).
The initial temperature is 19.50 C and the AH
rxn
is 57.2
kJ/mol NaOH.
(assume the density of the solution is 1.00 g/mL and the
specific heat of the solution is 4.18 J/gC)
q
soln
= m x C
s, soln
x AT = q
rxn
, 0.250 mol NaOH = 1 L
Exercise 6 What will be the final temperature of the solution in a coffee cup
calorimeter if a 50.00 mL sample of 0.250 M HCl(aq) is added to a 50.00 mL
sample of 0.250 NaOH(aq). The initial temperature is 19.50 C.
the sign is correct and the value is reasonable, because the reaction is
exothermic we expect the final temperature to be higher than the initial
50.00 mL of 0.250 M HCl, 50.00 mL of 0.250 M NaOH T
1
= 19.50 C,
d = 1.00 g/mL, C
s
= 4.18 J/gC, A H = 57.2

kJ/mol
T
2
, C
Check:
Solution:
Conceptual
Plan:

Relationships:
Given:

Find:
s
n sol'
C m
T

= A
q
H mol
rxn
A = q
rxn n sol'
q q =
mol
rxn
q
H = A
1.25 x 10
2
mol NaOH, 1.00 x 10
2
g, T
1
= 19.50 C,
AH =57.2 kJ/mol, C
s
= 4.18 J/gC
T
2
, C
q
rxn
q
soln
AH

AT

C
s
, q
soln
, m
T
2
Example 8 Reaction involving limiting reactant
You place 50.0 mL of 0.500 M NaOH in a coffee-cup calorimeter at
25.00
0
C and carefully add 25.0 mL of 0.500 M HCl, also at 25.00
0
C. After
stirring, the final temperature is 27.21
0
C. Calculate q
soln
(in J) and H
rxn

(in kJ/mol). (Assume the total volume is the sum of the individual
volumes and that the final solution has the same density and specfic heat
capacity as water: d = 1.00 g/mL and s = 4.18 J/g*K). The heat capacity
of the calorimeter can be ignored.
Solution
We need to determine the limiting reactant from the net ionic equation.
The moles of NaOH and HCl as well as the total volume can be
calculated. From the volume, we use density to find the mass of the
water formed. At this point q
soln
can be calculated using the mass, Cs,
and DT. The heat divided by the moles of water will give us the heat per
mole of water formed.
For NaOH 0.500 M x 0.0500 L = 0.0250 mol OH
-

For HCl 0.500 M x 0.0250 L = 0.0125 mol H
+

HCl(aq) + NaOH(aq) NaCl(aq) + H
2
O(l)
H
+
(aq) + OH
-
(aq) H
2
O(l)
total volume after mixing = 75 mL
75 mL
x 1.00 g/mL = 75.0 g of water
q
reaction
= -(q
solution
)

= -(mass x specific heat x T)
= -[75.0 g x 4.18 J/g*
0
C x (27.21-25.00)
0
C]
= -693 J
(-693 J/0.0125 mol H
2
O)(kJ/10
3
J) = -55.4 kJ/ mol H
2
O formed
HCl is the limiting reactant.
0.0125 mol of H
2
O will form during the rxn.
Topic
5.6 Standard Enthalpy and
Enthalpy Changes of Chemical
Reactions
Standard Conditions
The standard state is the state of a material at a defined
set of conditions
pure gas at exactly 1 atm pressure
pure solid or liquid in its most stable form at exactly 1 atm pressure
and temperature of interest usually 25 C
substance in a solution with concentration 1 M
The standard enthalpy change, H, is the enthalpy
change when all reactants and products are in their
standard states
The standard enthalpy of formation, H
f
, is the enthalpy
change for the reaction forming 1 mole of a pure compound
from its constituent elements
the elements must be in their standard states
the H
f
for a pure element in its standard state = 0 kJ/mol
by definition
The Standard Enthalpy of Formation
The standard enthalpy of formation of a substance is the
enthalpy change that results when 1 mol of the substance in
its standard state is formed from its elements in their
standard states. The reference forms of the elements are
their most stable forms at 25 oC and 1 atm pressure

Example :
Ca (s) + C (s) + 3/2 O
2
(g) CaCO
3
(s) = -1207 kJ mol
-1

The standard heat of formation of CaCO
3
(s) is 1207 kJ mol
-1


The Standard heat of formation, H
f
, of a pure element in its most stable
form is zero, 0. 0

Examples :

for elements: Fe (s) , Na(s) , O
2
(g), Cl (g) and others = 0 kJmol-1.
Standard Enthalpies of Formation

Formation Reactions
Reactions of elements in their standard state to
form 1 mole of a pure compound
if you are not sure what the standard state of an element
is, find the form in Appendix IIB that has a H
f
= 0
because the definition requires 1 mole of compound be
made, the coefficients of the reactants may be fractions
Writing Formation Reactions
Write the Formation Reaction for CO(g)
The formation reaction is the reaction between the
elements in the compound, which are C and O
C + O CO(g)
The elements must be in their standard state
there are several forms of solid C, but the one with
AH
f
= 0 is graphite
oxygens standard state is the diatomic gas
C(s, graphite) + O
2
(g) CO(g)
The equation must be balanced, but the coefficient
of the product compound must be 1
use whatever coefficient in front of the reactants is
necessary to make the atoms on both sides equal
without changing the product coefficient
C(s, graphite) + O
2
(g) CO(g)

Example 9
Write the formation reactions for CO
2
(g) and Al
2
(SO
4
)
3
(S)
C(s, graphite) + O
2
(g) CO
2
(g)
2 Al(s) + 3/8 S
8
(s, rhombic) + 6 O
2
(g) Al
2
(SO
4
)
3
(s)
Exercise 7
Write balanced thermochemical equations to represent the
following standard enthalpies of formation.
NaHCO
3
(s) = - 948 kJ mol
-1

Fe
2
O
3
(s) = - 824 kJ mol
-1
Al
2
O
3
(s) = - 1590 kJ mol
-1
C
2
H
5
OH (l) = - 277 kJ mol
-1
NH
3
(g) = - 48.5 kJ mol
-1
H
2
O (l) = - 286 kJ mol
-1
o
f
AH
o
f
AH
o
f
AH
o
f
AH
o
f
AH
o
f
AH
Example 9: Write the formation reactions for the
following:
CO
2
(g)

Al
2
(SO
4
)
3
(s)

C(s, graphite) + O
2
(g) CO
2
(g)
2 Al(s) + 3/8 S
8
(s, rhombic) + 6 O
2
(g) Al
2
(SO
4
)
3
(s)
Standard Enthalpy of Combustion


The standard enthalpy (heat) of combustion of a substance is
the amount of heat released when 1 mole of the substance is
burnt completely in oxygen at standard state conditions.

Example 10

H
2
(g) + O
2
(g) H
2
O (l) = -286 kJ

The standard heat of combustion of hydrogen, H
2
(g) is 286 kJ mol
-1
.
o
c
AH
Example 10: How much heat is evolved in the complete
combustion of 13.2 kg of C
3
H
8
(g)?




1 kg = 1000 g, 1 mol C
3
H
8
= 2044 kJ, Molar Mass = 44.09 g/mol
the sign is correct and the number is reasonable
because the amount of C
3
H
8
is much more than 1 mole
13.2 kg C
3
H
8
,
q,

kJ/mol
Check:
Solution:
Conceptual
Plan:


Relationships:
Given:

Find:
mol kJ kg g
Exercise 9
How much heat is evolved when a 0.483 g diamond is burned?
(H
combustion
= 395.4 kJ/mol C)
{-15.9 kJ)
Exercise 8
Write balanced thermochemical equations which represent the standard
enthalpies of combustion for the following substances.
H
c
C
4
H
10
(g) = 2875 kJ mol
-1
H
c
Zn (s) = 350.6 kJ mol
-1
H
c
Al (s) = 795 kJ mol
-1
H
c
C
12
H
22
O
11
(s) = 5461 kJ mol
-1

Exercise 10
The amount of heat liberated by the complete combustion of 0.3 mol of
C
2
H
6
(g) is sufficient to boil a certain quantity of water with an initial
temperature of 30
o
C in a calorimeter. The enthalpy of combustion of C
2
H
6

(g) is 1560 kJ mol
-1
. Calculate the volume of water in the calorimeter
which was boiled by the heat released in the experiment. (The specific
heat capacity of water is 4.2 J g
-1
k
-1
; The density of water is1 g cm
-3
).
{ 1.6 dm
3
}
Standard Enthalpy of Neutralization (H
o
)
The standard enthalpy of neutralization is the enthalpy change when
one mole of H
+
(aq)

ions from an acid reacts with one mole of OH
-
(aq)

ions from an alkali to form one mole of water molecules, H
2
O (l) under
standard conditions.
H
+
(aq) + OH
-
(aq) H
2
O(l) H=std enthalpy of neutralization
Examples:
NaOH(aq) + HCl(aq) NaCl(aq) + H
2
O(l) H
o
= 57.3 kJ mol
1

Ca(OH)
2
(aq) + HNO
3
(aq) CaNO
3
(aq) + H
2
O(l) H
o
= 57.3 kJ mol
1

The above are neutralization reactions of strong acids and strong alkalis.
Strong acids and strong alkalis dissociate almost completely in aqueous solutions
to give H
+
(aq) and OH
-
(aq), standard enthalpy of neutralization of any strong
acid and strong alkali is almost constant at about -57.3 kJ mol
-1


That is , H
+
(aq) + OH
-
(aq) H
2
O(l) H = 57.3 kJ mol
1

If a weak acid or a weak base is used, the standard enthalpy change of
neutralization is always less than -57.3 kJ mol
-1
. This is because the weak acid
does not dissociate completely. Therefore, when the acid reacts, some of the heat
energy liberated during the neutralization reaction is absorbed to dissociate the
acid. For example,

KOH(aq) + HCN(aq) KCN(aq) + H
2
O(l) H
o
= 11.7 kJ mol
1

NaOH(aq) + CH
3
COOH(aq) CH
3
COONa(aq) + H
2
O(l) H
o
= 55.6 kJ mol
1

NH
4
OH(aq) + CH
3
COOH(aq) CH
3
COONH
4
(aq) + H
2
O(l) H
o
= 50.4 kJ mol
1

Standard enthalpy of neutralization of HF (weak acid) and a strong base is
higher than -57.3 kJ, i.e about -69 kJ because HF dissociates with liberation of
energy (exothermic). Similarly with H
2
SO
4
, it releases a lot of heat with dilution
when the aqueous alkali is added to it.



NaOH(aq) + HF(aq) NaF(aq) + H
2
O(l) H
o
= 69.0 kJ mol
1

KOH(aq) + H
2
SO
4
(aq) K
2
SO
4
(aq) + H
2
O(l) H
o
= 66.0 kJ mol
1

Calculating Standard Enthalpy Change
for a Chemical Reaction
Any reaction can be written as the sum of formation
reactions (or the reverse of formation reactions) for
the reactants and products
The H for the reaction is then the sum of the H
f

for the component reactions
H
reaction
= n H
f

(products)
n H
f

(reactants)
means sum
n is the coefficient of the reaction
CH
4
(g) C(s, graphite) + 2 H
2
(g) A H = + 74.6 kJ

2 H
2
(g) + O
2
(g) 2 H
2
O(g) AH = 483.6 kJ
CH
4
(g)+ 2 O
2
(g) CO
2
(g) + H
2
O(g)
C(s, graphite) + 2 H
2
(g) CH
4
(g) AH
f
= 74.6 kJ/mol CH
4
C(s, graphite) + O
2
(g) CO
2
(g) AH
f
= 393.5 kJ/mol CO
2
H
2
(g) + O
2
(g) H
2
O(g) AH
f
= 241.8 kJ/mol H
2
O
CH
4
(g) + 2 O
2
(g) CO
2
(g) + 2 H
2
O(g) AH = 802.5 kJ
AH = [((393.5 kJ)+ 2(241.8 kJ) ((74.6 kJ)+ 2(0 kJ))]
= 802.5 kJ
AH = [(AH
f
CO
2
(g) + 2AH
f
H
2
O(g)) (AH
f
CH
4
(g) + 2AH
f
O
2
(g))]
Example 11: Calculate the enthalpy change in the
reaction
2 C
2
H
2
(g) + 5 O
2
(g) 4 CO
2
(g) + 2 H
2
O(l)
1. Write formation reactions for each compound
and determine the AH
f
for each
2 C(s, gr) + H
2
(g) C
2
H
2
(g) AH
f
= +227.4 kJ/mol
C(s, gr) + O
2
(g) CO
2
(g) AH
f
= 393.5 kJ/mol
H
2
(g) + O
2
(g) H
2
O(l) AH
f
= 285.8 kJ/mol
2 C
2
H
2
(g) 4 C(s) + 2 H
2
(g) AH = 2(227.4) kJ
4 C(s) + 4 O
2
(g) 4CO
2
(g) AH = 4(393.5) kJ
2 H
2
(g) + O
2
(g) 2 H
2
O(l) AH = 2(285.8) kJ
2. Arrange equations so they add up to desired reaction
2 C
2
H
2
(g) + 5 O
2
(g) 4 CO
2
(g) + 2 H
2
O(l) AH = 2600.4 kJ
Example 11: Calculate the enthalpy change in the
reaction
2 C
2
H
2
(g) + 5 O
2
(g) 4 CO
2
(g) + 2 H
2
O(l)
AH
reaction
= E n AH
f
(products) E n AH
f
(reactants)

AH
rxn
= [(4AH
CO2
+ 2AH
H2O
) (2AH
C2H2
+ 5AH
O2
)]

AH
rxn
= [(4(393.5) + 2(285.8)) (2(+227.4) + 5(0))]

AH
rxn
= 2600.4 kJ
Example 11: Calculate the enthalpy change in the
reaction
2 C
2
H
2
(g) + 5 O
2
(g) 4 CO
2
(g) + 2 H
2
O(l)
Exercise 11 Calculate the AH for decomposing
10.0 g of limestone, CaCO
3
, under standard
conditions.
CaCO
3
(s) CaO(s) + O
2
(g)
Copyright 2011 Pearson Education, Inc.
Exercise 11 Calculate the AH for decomposing 10.0 g of
limestone, CaCO
3
(s) CaO(s) + O
2
(g)




MM
limestone
= 100.09 g/mol,

the units and sign are correct
10.0 g CaCO
3

AH, kJ
Check:
Solution:
Conceptual
Plan:



Relationships:
Given:
Find:
AH
f
s AH
rxn
per mol CaCO
3

g CaCO
3
mol CaCO
3
kJ

from
above
CaCO
3
(s) CaO(s) + O
2
(g)
AH
rxn
= +572.7 kJ
83
Exercise 12
Given the chemical equation below :
SO
3
(g) + H
2
O (l) H
2
SO
4
(aq)
56.5 kJ of heat is released, when a certain quantity
of SO
3
(g) gas is dissolved in water to give 24.5 g of H
2
SO
4
in
the solution.
(a)Calculate the heat of reaction, H, for the formation of
H
2
SO
4
represented by the above thermochemical equation.
(b)Draw the enthalpy diagram for the above reaction.
{Ans: -226kJ}
Stoichiometric Calculations involve AH
Exercise 13 How much heat is evolved when a
0.483 g diamond is burned?




1 mol C = 395.4 kJ, Molar Mass = 12.01 g/mol
the sign is correct and the number is reasonable
because the amount of diamond is less than 1 mole
0.483 g C, AH = 395.4 kJ/mol C
q,

kJ/mol
Check:
Solution:
Concept Plan:



Relationships:
Given:

Find:
mol kJ g
Exercise 14
(a) 2NO (g) + O
2
(g) 2NO
2
(g)
57 kJ of heat energy is released for each mole of NO
2
molecule formed
in the above reaction. Calculate the enthalpy change, H, for the above
reaction.
(-114 kJ)
(b)
Using the answer from (a) above, determine the enthalpy change, H,
for the reactions represented by the following equations :
i) NO (g) + O
2
(g) NO
2
(g) (-57 kJ)
ii) NO
2
(g) NO (g) + O
2
(g) (+57 kJ)
iii) 2/3 NO (g) + 1/3 O
2
(g) 2/3 NO
2
(g) {-38 kJ}

Topic
5.7 Hesss Law
AH is well known for many reactions, and it is inconvenient
to measure AH for every reaction in which we are
interested.
Since H is a state function, the AH in going from some
initial state to some final state is independent of the
pathway.
This means that in going from a particular set of reactants
to a particular set of products, the AH is the same whether
the reaction takes place in one step or in a series of steps.
We can estimate AH using published values and the
properties of enthalpy- Thus, it is not necessary to make
calorimetric measurements for all reactions- This principle
is known as Hesss Law


5.7 Hesss Law
5.7 Hesss Law
Consider the oxidation of carbon to form carbon monoxide.

C (graphite ) + O
2
(g) CO (g) H = ?

Problems
-Even if a deficiency of oxygen is used, the primary product
of the reaction of carbon and oxygen is CO
2
.
-Even if a CO is formed, it reacts with O
2
to form CO
2.
Thus
the reaction cannot be carried out in a way that allows CO to
be sole product- impossible to measure H for this reaction
by calorimetry.

Solution
- H for the forming CO (g) from C (graphite) and O
2
(g) can be
determined indirectly, as long as H for other reactions is
already measured.
5.7 Hesss Law
Because AH is a state function, the total enthalpy change
depends only on the initial state of the reactants and the
final state of the products.
C (graphite ) + O
2
(g) CO (g) H
o
rxn
= ?
Eq 1 : CO (g) + O
2
(g) CO
2
(g) H
o
1
= -283.0 kJ/mol
Eq 2 : C (graphite) + O
2
(g) CO
2
(g) H
o
2
= -393.5 kJ/mol





Thus , H
o
rxn
= H
o
1
+ H
o
2


Eq 1 in reversed form so H
o
1
is +ve

CO
2
(g) CO (g) + O
2
(g) H
o
1
= +283.0 kJ/mol
+
C (graphite) + O
2
(g) CO
2
(g) H
o
2
= -393.5 kJ/mol

C (graphite ) + O
2
(g) CO (g) H
o
rxn
= -110.5 kJ/mol
Hesss law states that if a reaction is carried out in a
series of steps, AH for the overall reaction will be equal to
the sum of the enthalpy changes for the individual steps.
Definition
5.7 Hesss Law
[3 NO
2
(g) 3 NO(g) + 1.5 O
2
(g)] AH = (+174 kJ)
[1 N
2
(g) + 2.5 O
2
(g) + 1 H
2
O(l) 2 HNO
3
(aq)] AH = (128 kJ)
[2 NO(g) N
2
(g) + O
2
(g)] AH = (183 kJ)
3 NO
2
(g) + H
2
O(l) 2 HNO
3
(aq) + NO(g) AH = 137 kJ

Example 14: Hesss Law
Given the following information:
2 NO(g) + O
2
(g) 2 NO
2
(g) AH = 116 kJ
2 N
2
(g) + 5 O
2
(g) + 2 H
2
O(l) 4 HNO
3
(aq) AH = 256 kJ
N
2
(g) + O
2
(g) 2 NO(g) AH = +183 kJ
Calculate the AH for the reaction below:
3 NO
2
(g) + H
2
O(l) 2 HNO
3
(aq) + NO(g) AH = ?

[2 NO
2
(g) 2 NO(g) + O
2
(g)] x 1.5 AH = 1.5(+116 kJ)
[2 N
2
(g) + 5 O
2
(g) + 2 H
2
O(l) 4 HNO
3
(aq)] x 0.5 AH = 0.5(256 kJ)
[2 NO(g) N
2
(g) + O
2
(g)] AH = 183 kJ

Exercise 15 Hesss Law
Given the following information:
Cu(s) + Cl
2
(g) CuCl
2
(s) AH = 206 kJ
2 Cu(s) + Cl
2
(g) 2 CuCl(s) AH = 36 kJ
Calculate the AH for the reaction below:
Cu(s) + CuCl
2
(s) 2 CuCl(s) AH = ? kJ

Exercise 15 Hesss Law
Given the following information:
Cu(s) + Cl
2
(g) CuCl
2
(s) AH = 206 kJ
2 Cu(s) + Cl
2
(g) 2 CuCl(s) AH = 36 kJ
Calculate the AH for the reaction below:
Cu(s) + CuCl
2
(s) 2 CuCl(s) AH = ? kJ

CuCl
2
(s) Cu(s) + Cl
2
(g) AH = +206 kJ
2 Cu(s) + Cl
2
(g) 2 CuCl(s) AH = 36 kJ
Cu(s) + CuCl
2
(s) 2 CuCl(s) AH = +170. kJ

Extra Practice Hesss Law
Use Hesss Law to calculate the enthalpy change for
the formation of CS
2

(l)
from C
(s)
and S
(s)
from the
following enthalpy values

C
(s)
+ O
2

(g)
CO
2

(g)
H
o
f
= -393.5 kJ/mol

S
(s)
+ O
2

(g)
SO
2

(g)
H
o
f
= -295.8 kJ/mol

CS
2

(s)
+3O
2

(g)
2SO
2

(g)
+CO
2

(g)
H
o
f
= -1103.9
kJ/mol




Topic
5.8 Lattice Energy and
The Born-Haber Cycle
Energetics of Ionic Bond Formation
The ionization energy of the metal is endothermic
Na(s) Na
+
(g) + 1 e

H = +496 kJ/mol
The electron affinity of the nonmetal is exothermic
Cl
2
(g) + 1 e

Cl

(g)

H = 244 kJ/mol
Generally, the ionization energy of the metal is larger than
the electron affinity of the nonmetal, therefore the formation
of the ionic compound should be endothermic
But the heat of formation of most ionic compounds is
exothermic and generally large. Why?
Na(s) + Cl
2
(g) NaCl(s) H
f
= 411 kJ/mol
5.8 Lattice Energy & The Born-Haber Cycle
The Crystal Lattice
The extra energy that is released comes from the formation
of a structure in which every cation is surrounded by anions,
and vice versa
This structure is called a crystal lattice
The crystal lattice is held together by the electrostatic
attraction of the cations for all the surrounding anions
The crystal lattice maximizes the attractions between
cations and anions, leading to the most stable arrangement

5.8 Lattice Energy & The Born-Haber Cycle
The Crystal Lattice
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
Lattice Energy
The extra stability that accompanies the formation of the
crystal lattice is measured as the lattice energy
The lattice energy is the energy released when the solid
crystal forms from separate ions in the gas state
always exothermic
hard to measure directly, but can be calculated from
knowledge of other processes
Lattice energy depends directly on size of charges and
inversely on distance between ions
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
The Standard Lattice Enthalpy

The standard lattice enthalpy of an ionic compound is the
heat released when 1 mole of the ionic crystal is formed from
its gaseous ions. The value is negative because the
process is exothermic.
Example
Na
+
(g) + Cl
-
(g) NaCl (s) H = -770 kJ
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.

The BornHaber Cycle

The BornHaber Cycle is a hypothetical series of
reactions that represents the formation of an ionic
compound from its constituent elements

The reactions are chosen so that the change in enthalpy of
each reaction is known except for the last one, which is the
lattice energy
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
BornHaber Cycle
Use Hesss Law to add up enthalpy changes of other
reactions to determine the lattice energy
H
f
(salt) = H
f
(metal atoms, g) + H
f
(nonmetal atoms, g) +
H
f
(cations, g) + H
f
(anions, g) + H(crystal lattice)
H(crystal lattice) = Lattice Energy
for metal atom(g) cation(g), H
f
= 1
st
ionization energy
dont forget to add together all the ionization energies to
get to the desired cation
M
2+
= 1
st
IE + 2
nd
IE
for nonmetal atoms (g) anions (g), H
f
= electron affinity
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
The Standard Enthalpy of Ionization

The standard enthalpy of ionization is the enthalpy
required to remove 1 mole of electrons from 1 mole of
gaseous metallic atom to form a positive ion. The process is
endothermic because energy is absorbed to release an
electron from an atom.

The amount of energy required to remove the first valence
electron from a gaseous atom is called the first ionization
energy while that required to remove the second electron
from the gaseous positive ion is called the second ionization
energy.
Example
M(g) - e M
+
(g) H = First ionization energy
M
+
(g) - e M
2+
(g) H = Second ionization energy
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
Electron Affinity

The electron affinity is the enthalpy liberated / released when
1 mole of gaseous atoms accept 1 mole of electrons to
become negative ions. It has a negative value, showing that
this reaction is exothermic.

Example
A(g) + e A
-
(g) H = First electron affinity
A
-
(g)+ e A
2-
(g) H =Second electron affinity
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
The Standard Bond Formation Enthalpy

The standard bond formation enthalpy is the energy that is
released when 1 covalent bond is formed between 2 free
gaseous atoms. This proses is exothermic.

Example
2H (g) H
2
(g) H = - 432 kJ mol
-1

The standard bond formation enthalpy of the H-H bond in H
2
molecule is 432 kJ mol
-1
.
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
Standard Bond Enthalpy (Bond Energy)
The standard bond dissociation enthalpy is the energy
that must be absorbed to separate the two atoms in a
covalent bond. This process is endothermic

Example

H
2
(g) 2H (g) H = +432 kJ mol
-1


The standard bond dissociation enthalpy of the H-H bond in
H
2
molecule is +432 kJ mol
-1
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
Standard Enthalpy of Atomization

The standard enthalpy of atomization is the heat absorbed
when 1 mole of free gaseous atom is formed from its element
in the standard state. The process is endothermic as heat is
absorbed.

Example
H
2
(g) H (g) H = +216 kJ
Na(s) Na(g) H = +109 kJ
5.8 Lattice Energy & The Born-Haber Cycle
Copyright 2011 Pearson Education, Inc.
Copyright 2011 Pearson Education, Inc.
BornHaber Cycle for NaCl
AH
f
(NaCl, s) = AH
f
(Na atoms,g) +
AH
f
(Cl atoms,g) + AH
f
(Na
+
,g) +
AH
f
(Cl

,g) + AH(NaCl lattice)

AH
f
(NaCl, s) = AH
f
(Na atoms,g) +
AH
f
(ClCl bond energy) + Na 1
st

Ionization Energy + Cl Electron
Affinity + NaCl Lattice Energy
Na(s) Na(g) AH
f
(Na,g)
Cl
2
(g) Cl(g) AH
f
(Cl,g)
Na(g) Na
+
(g) AH
f
(Na
+
,g)
Cl

(g) Cl

(g) AH
f
(Cl

,g)
Na
+
(g) + Cl

(g) NaCl(s) AH (NaCl lattice)

Na(s) + Cl
2
(g) NaCl(s) AH
f
(NaCl, s)
Na(s) Na(g) AH
f
(Na,g)
Cl
2
(g) Cl(g) AH
f
(Cl,g)
Na(g) Na
+
(g) AH
f
(Na
+
,g)
Cl

(g) Cl

(g) AH
f
(Cl

,g)
Na
+
(g) + Cl

(g) NaCl(s) AH (NaCl lattice)

Na(s) Na(g) +108 kJ
Cl
2
(g) Cl(g) +(244 kJ)
Na(g) Na
+
(g) +496 kJ
Cl

(g) Cl

(g) 349 kJ
Na
+
(g) + Cl

(g) NaCl(s) AH (NaCl lattice)

Na(s) + Cl
2
(g) NaCl(s) 411 kJ
NaCl Lattice Energy = AH
f
(NaCl, s)
[AH
f
(Na atoms,g) + AH
f
(ClCl
bond energy) + Na 1
st
Ionization
Energy + Cl Electron Affinity ]
NaCl Lattice Energy = (411 kJ)
[(+108 kJ) + (+122 kJ) + (+496 kJ) +
(349 kJ) ]
= 788 kJ
Exercise 16 Given the information below,
determine the lattice energy of MgCl
2
Mg(s) Mg(g) AH
1

f
= +147.1 kJ/mol
Cl
2
(g) Cl(g) AH
2

f
= +122 kJ/mol
Mg(g) Mg
+
(g) AH
3

f
= +738 kJ/mol
Mg
+
(g) Mg
2+
(g) AH
4

f
= +1450 kJ/mol
Cl(g) Cl

(g) AH
5

f
= 349 kJ/mol
Mg(s) + Cl
2
(g) MgCl
2
(s) AH
6

f
= 641 kJ/mol

Exercise 16 Given the information below,
determine the lattice energy of MgCl
2
Mg(s) Mg(g) AH
1

f
= +147.1 kJ/mol
2{ Cl
2
(g) Cl(g)} 2-AH
2

f
= 2(+122 kJ/mol)
Mg(g) Mg
+
(g) AH
3

f
= +738 kJ/mol
Mg
+
(g) Mg
2+
(g) AH
4

f
= +1450 kJ/mol
2{Cl(g) Cl

(g)} 2-AH
5

f
= 2(349 kJ/mol)
Mg
2+
(g) + 2 Cl

(g) MgCl
2
(s) AH
lattice energy
= ? kJ/mol
Mg(s) + Cl
2
(g) MgCl
2
(s) AH
6

f
= 641 kJ/mol

Copyright 2011 Pearson Education, Inc.
Exercise17

Given the following data :
The Standard heat of formation of BaCl
2
(s) H
1
= -860 kJ mol
-1
The Standard heat of atomization of barium, Ba(g) H
2
= +175 kJ mol
-1
The first ionization energy of Ba(s) H
3
= +500 kJ mol
-1
The second ionization energy of Ba(s) H
4
= +1000 kJ mol
-1
The Standard enthalpy of atomization of Cl
2
(g) H
5
= +121 kJ mol
-1

The first electron affinity of Cl
2
(g) H
6
= -364 kJ mol
-1
(a) Write the thermochemical equations to represent all the above
reactions
(b) Construct a Born-Haber cycle for the formation of solid barium
chloride BaCl
2
(s) and calculate the standard lattice enthalpy of
BaCl
2
(s) .
{ -2049 kJ }
Copyright 2011 Pearson Education, Inc.
Exercise 18
The thermochemical equations given below represent all the reactions involved in a
Born-Haber cycle for the formation of solid sodium fluoride, NaF(s) , from its
elements in their standard states.
I) Na (s) + F2 (g) NaF(s) H = x kJ
II) Na (s) Na+(g) H = +610 kJ
III) F2 (g) F-(g) H = -271 kJ
IV) Na+(g) + F-(g) NaF(s) H = -915 KJ

(a) Use the above equations, construct a Born-Haber cycle for the
formation of sodium fluoride.
(b)(i) Name the enthalpy change for the reactions represented by
equations I, and IV.
(ii) calculate the value of x.
(c) Equations (II) and (III) are formed by the combination of 2
consecutive steps of reactions . Write equations for the 2
consecutive steps in each of the equations (II) and (III) . Name the
enthalpy change for each reaction step in the two equations.