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CHAPTER 5:

THERMOCHEMISTRY
FOUNDATION CHEMISTRY I
CHM092 2015
Copyright The McGraw-Hill Companies, Inc. Permission required for reproduction or display.

Topic
CHAPTER 5

5.1
5.2
5.3
5.4
5.5
5.6
5.7

Introduction to Thermochemistry
System and Surroundings
Exothermic and Endothermic Reactions
Enthalpy, H
Specific Heat Capacity and Calorimetry
Standard Enthalpy
Enthalpy Changes of Chemical Reactions
Direct method and indirect method: Hesss Law

5.8

Lattice Energy and Born-Haber Cycle

Topic
5.1 Introduction to
Thermochemistry

5.1 Introduction to Thermochemistry


The Nature of Energy

Energy is defined as the capacity to do work


All matter contains energy- whenever matter undergoes a
change, the quantity of energy that the matter contains also
changes
Thermodynamics is the scientific study of the interconversion
of heat and other kinds of energy.
Thermochemistry is the study of heat change in chemical
reactions.
Kinetic energy is the energy of motion
Potential energy is the energy available by virtue of an
objects position
Chemical Energy is energy stored in the bonds of chemical
compounds (atoms and molecules). It is released in a
chemical reaction, often producing heat as a by product

5.1 Introduction to Thermochemistry


Energy changes in chemical
reactions:
Heat is the transfer of thermal energy
between two bodies that are at different
temperatures. Because thermal energy is
due to the movement of particles, it is a
type of kinetic energy, which is the energy
due to motion.
Thermal energy results in something having
an internal temperature, and that
temperature can be measured - for
example, in degrees Celsius or Fahrenheit
on a thermometer.

The faster the particles move within an


object or system, the higher the
temperature that is recorded.

Thermometer

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.

Checkpoint 1
Name two ways can an object possess energy?
How do these two ways differ form one another?

Topic
5.2 System and
Surroundings

5.2 System and Surroundings


Definition
System is the material or process that is being studied.
Surroundings is everything else that interact with the
system.
The interest of study is the exchange of energy between the
system and the surroundings

Surroundings

Surroundings

System

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
Energysystem + Energysurroundings

=0

Example:

C3H8 + 5O2
3CO2 + 4H2O
Exothermic chemical reaction!
Chemical energy lost by combustion = Energy gained by the surroundings
system
surroundings

5.2 System and Surroundings


Energy Flow
When energy flows out of a
system, it must all flow into the
surroundings :
Esystem is ve

Esurroundings is +ve
Therefore:
Esystem= Esurroundings

Surroundings
DE +

System
DE

5.2 System and Surroundings


Energy Flow
When energy flows into a
system, it must all come from
the surroundings:
Esystem is +ve

Esurroundings is ve
Therefore:
Esystem= Esurroundings

Surroundings
DE
System
DE +

Open systems both matter (mass) and energy can move into and
5.2 System and Surroundings
out of an open system. The earth, for example, is an open system.
Types
ofand
System
Energy comes in from
the sun,
is re-radiated back to space.
Meteors strike the Earth, and cause parts of the Earth to be
Open systems
cansend
exchange
and energy,
usually
ejected
into space.We
satellitesmass
into interstellar
space.
Thesein
formtoofstudy
heatscientifically
with its surroundings.
are difficultthe
systems
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
The
anan
open
system.
Energy
comes
in
The earth,
earth,for
forexample,
example,isis
open
system.
Energy
comes
from in
thefrom
sun,the
andsun,
is re-radiated
back to space.
and is re-radiated
back to space.
from these systems to the surroundings

5.2 System and Surroundings


Open systems both matter (mass) and energy can move into and
Types
of System
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.
the Earth,
andthe
cause
parts of
of energy
the Earth
to be
Meteors
Closedstrike
systems
allows
transfer
(heat)
ejected
butinto
not space.
mass 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
Matter can
not be
transferred
from
a closed
but
systems
neither
matter
or energy
cansystem,
be transferred
energy (heat)
Example:
coffee
cup calorimeter used in
fromcan.
these
systems to
the surroundings
many general chemistry laboratories.

5.2 System and Surroundings


Open systems both matter (mass) and energy can move into and
Types
of System
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
Isolated systems neither matter or energy can be
ejected into space. We send satellites into interstellar space. These
transferred from these systems to the surroundings.
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

5.2 System and Surroundings


Energy Flow in Chemical Reaction
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.

The total amount of internal energy in


1mol of C(s) and 1 mole of O2(g) is
greater than the internal energy in 1 mole
of CO2(g)
at the same temperature and pressure

In the reaction C(s) + O2(g) CO2(g), there


will be a net release of energy into the
surroundings

Internal Energy

5.2 System and Surroundings


Energy Flow in a Chemical Reaction
energy
C(s), O2(g) absorbed
DErxn = +
energy
released
CO2(g)
DErxn =
Surroundings

Ereaction = Esurroundings

In the reaction CO2(g) C(s) + O2(g), there


will be an absorption of energy from the
surroundings into the reaction
Ereaction = Esurroundings

System
CO
O22
C
+ 2OC
2 +CO

5.2 System and Surroundings


Energy Exchange in Chemical Reactions
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

5.2 System and Surroundings


Energy Exchange in Chemical Reactions
Energy transferred as work only (w) and q = 0, E = 0 + w = w
1. Work done by a system = work done on the surroundings

Zn(s) + 2H+(aq) +
2Cl-(aq)
H2(g) + Zn2+(aq) + 2Cl-(aq)

The system does work on the surroundings. w = -ve

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


Internal Energy and Energy Exchange
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.

DU = 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

5.2 System and Surroundings


Units of Energy
Joule (J) is the SI unit for energy.
The amount of energy possessed by a 1-kg mass moving at
a speed of 1 m/s.
1 kJ = 1000 J

23

5.2 System and Surroundings


Chemistry In Action: Fuel Values of Foods
and Other Substances

Calorie (cal) - commonly used on food labels.


1 cal 4.184 J
1000 cal = 1 Cal = 1 kcal
Food calories (Cal) are really 1000 calories (cal)
1 Cal = 1000 cal = 4184 J
C6H12O6 (s) + 6O2 (g)

6CO2 (g) + 6H2O (l) DH = -2801 kJ/mol

Substance

DHcombustion (kJ/g)

Apple

-2

Beef

-8

Beer

-1.5

Gasoline

-34

5.2 System and Surroundings


State Function
Thermodynamics is the scientific study of the interconversion
of heat and other kinds of energy.

State functions are properties that are determined by the


state of the system, regardless of how that condition was
achieved.

DU = Ufinal - Uinitial
DP = Pfinal - Pinitial
DV = Vfinal - Vinitial
DT = Tfinal - Tinitial
Potential energy of hiker 1 and hiker 2 is the
same even though they took different paths.

Topic
5.3 Exothermic and Endothermic
Reactions

5.3 Exothermic and Endothermic


Reactions
Exothermic process is any process that released or gives off
heat transfers thermal energy from the system to the
surroundings.
2H2 (g) + O2 (g)
2H2O (l) + energy
H2O (g)

H2O (l) + energy

Endothermic process is any process in which heat has to be


supplied to the system from the surroundings.

energy + 2HgO (s)


energy + H2O (s)

2Hg (l) + O2 (g)


H2O (l)

27

Schematic of Exothermic and Endothermic Processes


Enthalpy (H) is used to quantify the heat flow into or out of a system in a
process that occurs at constant pressure.

DH = H (products) H (reactants)

DH = heat given off or absorbed during a reaction at constant pressure


EXOTHERMIC

ENDOTHERMIC

reactants

products

Hproducts < Hreactants


DH < 0

Hproducts > Hreactants


DH > 0

28

Energy Profile Diagram for Endothermic reaction


Is DH negative or
positive?
System absorbs
heat

H2O (l)

Endothermic

DH > 0
H2O (s)

6.01 kJ are absorbed for every 1 mole of ice that


melts at 00C and 1 atm.

H2O (s)

H2O (l)

DH = 6.01 kJ/mol
29

Energy Profile Diagram for Exothermic reaction


Is DH negative or
positive?
System gives off
heat
Exothermic

CH4 + 2O2

DH < 0
CO2 + 2 H2O

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) DH = -890.4 kJ/mol


30

Examples of endothermic & exothermic


Endothermic absorbed the heat/energy
For example : the decomposition of CaCO3 need
heat and supplied to the system, thus heat as a
reactant
CaCO3(s) + heat CaO(s) + CO2(g)
Exothermic released the heat/energy
For example : the combustion of iron always
gives off heat, thus heat as a product after
the reaction
4Fe(s) + 3O2 (g) 2Fe2O3(s) + heat

Examples of endothermic and exothermic

Endothermic

Exothermic

32

Topic
5.4 Enthalpy

5.4 Enthalpy
Standard Enthalpy/ Heat of Reaction, H
Enthalpy (H) is the amount of heat energy measured at
constant pressure of a chemical reaction.
Standard enthalpy change/heat of reaction, H, is the
enthalpy change when all reactants and products are in
their standard states
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 1M

5.4 Enthalpy
Standard Enthalpy/ Heat of Reaction, H
There are 3 basic rules to apply when we use
thermochemical equations for calculation.
i.

The standard heat of reaction released or absorbed


depends very much on the amount of reactants that
reacted completely to give the products or it depends on
the amount of products actually formed. Therefore, it
can be calculated by using the stoichiometric
coefficients of the equation for the reaction.

5.4 Enthalpy
Standard Enthalpy/ Heat of Reaction, H
ii. If any of the equations above are reversed, the enthalpy
change, H, will have the same numerical value but with
an opposite sign. That is, the reverse of an endothermic
reaction is exothermic and vice versa.

5.4 Enthalpy and Calorimetry


Standard Enthalpy/ Heat of Reaction, H
iii. The physical state of each substance (reactant or
product) involved in the chemical reaction has to be
specified in the thermochemical equation because the
value of H varies with the physical state of the reactants
or the products in the reaction.

Examples of thermochemical reactions

The stoichiometric coefficients always refer to the number


of moles of a substance
H2O (s)

DH = 6.01 kJ/mol

If you reverse a reaction, the sign of DH changes


H2O (l)

H2O (l)

H2O (s)

DH = -6.01 kJ/mol

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


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

2H2O (l)

DH = 2 x 6.01 = 12.0 kJ

38

Examples of thermochemical reactions

The physical states of all reactants and products must be


specified in thermochemical equations.
H2O (s)

H2O (l)

DH = 6.01 kJ/mol

H2O (l)

H2O (g)

DH = 44.0 kJ/mol

39

Checkpoint 2

Topic
5.5 Specific Heat Capacity and
Calorimetry

5.5 Specific Heat Capacity and Calorimetry


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.
The heat capacity (C) of a substance is the amount
of heat (q) required to raise the temperature of a
given mass (m) of the substance by 1C.
units are J/C or J/Kelvin

q = C x T
The unit of temperature must be consistent either C or K.
The temperature difference is the measurement of the
relative amount of internal energy between two bodies.

5.5 Specific Heat Capacity and Calorimetry


Quantity of Heat Energy Absorbed:
Heat Capacity
The larger the heat capacity of the object being studied, the
smaller the temperature rise will be for a given amount of
heat.
The molar heat capacity is the amount of heat energy
required to raise the temperature of 1 mole of a substance
by 1C.

5.5

Specific Heat Capacity and Calorimetry

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

5.5

Specific Heat Capacity and Calorimetry


Quantifying Heat Energy:
Specific Heat Capacity

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
The specific heat capacity (s) of a substance is the
amount of heat (q) required to raise the
temperature of 1 gram of the substance by 1C.
- units are J/(gC)

Heat = (mass) x (specific heat) x (temp. change)

q = m x s x T

To calculate heat (q) absorbed or released:


q = m x s x DT

heat capacity, C = m x s
q = C x DT
where DT= Tfinal - Tinitial

5.5

Specific Heat Capacity and Calorimetry


Specific Heat Capacity of Water

Water has a high specific heat value. This 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

Checkpoint 3
Which substance in Table below will
undergo the greatest temperature
change when the same mass of each
substance absorbs the same quantity of
heat?

5.5

Specific Heat Capacity and Calorimetry


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

qhot = qcold
mhotCs,hotDThot = (mcoldCs,coldDTcold)

5.5

Specific Heat Capacity and Calorimetry

Example 5.2:
A 466-g sample of water is heated from 8.50C to 74.60C.

Calculate the amount of heat absorbed (in kilojoules) by the


water.
Note:The unit of temperature must be
consistent either C or K. The
temperature difference is the
measurement of the relative amount of
internal energy between two bodies.

5.5

Specific Heat Capacity and Calorimetry

Example 5.2:
Strategy We know the quantity of water and the specific heat of water.
With this information and the temperature rise, we can calculate the amount
of heat absorbed (q).
Solution Using Equation (6.12), we write

Check The units g and C cancel, and we are left with the desired unit kJ.
Because heat is absorbed by the water from the surroundings, it has a
positive sign.

5.5

Specific Heat Capacity and Calorimetry

Example 5.3:

Calculate the amount of energy required to heat 95.0 grams of


water from 22.5C to 95.5C.
Solution
DT = Tfinal Tinitial = 95.5 C 22.5 C
DT = 73.0 C
q = (95.0 g) (4.184 J/g C) (73.0 C)
q = 2.90 x 104 J or 29.0 kJ

Checkpoint 4
How much heat (in kJ) is required to warm 2.5 kg of sand
from 25.0C to 100C
(specific heat of sand =0.84 J/g.C)

53

Checkpoint 5
The specific heat of ethylene glycol is 2.42 J/g.K. How
many of J of heat are needed to raise the temperature
of 62.0 g of ethylene glycol from 131.1C to 40.5C?

5.5

Specific Heat Capacity and Calorimetry

Constant-Volume Calorimetry:
Bomb Calorimeter
Calorimetry is the measurement of
heat changes.
Constant-volume calorimetry
Isolated system
Measures DU
Typical procedure used in a bomb
calorimeter.
Known amount of sample placed in steel
container and then filled with oxygen gas.
Steel chamber submerged in known
amount of water.
Sample ignited electrically.
Temperature increase of water is
determined.

No heat enters or leaves!

5.5

Specific Heat Capacity and Calorimetry

Constant-Volume Calorimetry:
Bomb Calorimeter
qsys = qwater + qbomb + qrxn

qsys = 0
qrxn = - (qwater + qbomb)
qwater = m x s x Dt
qbomb = Cbomb x Dt
Reaction at Constant V
DH = qrxn

DH ~ qrxn
No heat enters or leaves!

56

5.5

Specific Heat Capacity and Calorimetry

Example 5.4:

A quantity of 1.435 g of naphthalene (C10H8),


a pungent-smelling substance used in moth
repellents, was burned in a constant-volume
bomb calorimeter.
Consequently, the temperature of the water
rose from 20.28C to 25.95C.
If the heat capacity of the bomb plus water
was 10.17 kJ/C, calculate the heat of
combustion of naphthalene on a molar basis;
that is, find the molar heat of combustion.

5.5

Specific Heat Capacity and Calorimetry

Example 5.3:
Strategy
Knowing the heat capacity and the temperature rise, how do we calculate
the heat absorbed by the calorimeter?

What is the heat generated by the combustion of 1.435 g of naphthalene?


What is the conversion factor between grams and moles of
naphthalene?

5.5 Specific Heat Capacity


Example 5.3:
Solution The heat absorbed by the bomb and water is equal to the product
of the heat capacity and the temperature change.
From Equation (6.16), assuming no heat is lost to the surroundings, we write

Because qsys = qcal + qrxn = 0, qcal = qrxn. The heat change of the reaction is
57.66 kJ. This is the heat released by the combustion of 1.435 g of C10H8;
therefore, we can write the conversion factor as

5.5

Specific Heat Capacity and Calorimetry

Example 5.3:

The molar mass of naphthalene is 128.2 g, so the heat of combustion of 1


mole of naphthalene is

Check Knowing that the combustion reaction is exothermic and that the
molar mass of naphthalene is much greater than 1.4 g, is the answer
reasonable? Under the reaction conditions, can the heat change (257.66 kJ)
be equated to the enthalpy change of the reaction?

Checkpoint 6
A quantity of 1.922 g of methanol (CH3OH) was
burned in a constant-volume bomb calorimeter.
Consequently, the temperature of the water rose by
4.20C. If the quantity of water surrounding the
calorimeter was 2000g and the heat capacity of the
calorimeter was 2.02 kJ/C, calculate the molar heat
combustion of methanol.

61

Sample Problem 5.4


PROBLEM:

PLAN:

Calculating the Heat of Combustion

A manufacturer claims that its new dietetic dessert has


fewer than 10 Calories per serving. To test the claim, a
chemist at the Department of Consumer Affairs places one
serving in a bomb calorimeter and burns it in O2 (the heat
capacity of the calorimeter = 8.151 kJ/K). The temperature
increases 4.937oC. Is the manufacturers claim correct?

- q sample = qcalorimeter

SOLUTION: qcalorimeter

40.24 kJ

= heat capacity x DT
= 8.151 kJ/K x 4.937 K
= 40.24 kJ

kcal

= 9.63 kcal or Calories

4.184 kJ
The manufacturers claim is true.

5.5

Specific Heat Capacity and Calorimetry

Constant-Pressure Calorimetry
System: reactants and products
Surroundings: water
Used to measure:
Specific heats
DH values
qsys = qwater + qcal + qrxn
qsys = 0
qrxn = - (qwater + qcal)

qwater = m x s x Dt
qcal = Ccal x Dt
Reaction at Constant P
DH = qrxn

No heat enters or leaves!


63

5.5

Specific Heat Capacity and Calorimetry

Example 5.5:
A lead (Pb) pellet having a mass of
26.47 g at 89.98C was placed in a
constant-pressure calorimeter of
negligible heat capacity containing
100.0 mL of water.
The water temperature rose from
22.50C to 23.17C.
What is the specific heat of the lead
pellet?

5.5

Specific Heat Capacity and Calorimetry

Example 5.5:
Strategy A sketch of the initial and final situation is as follows:

We know the masses of water and the lead pellet as well as the initial and
final temperatures. Assuming no heat is lost to the surroundings, we can
equate the heat lost by the lead pellet to the heat gained by the water.
Knowing the specific heat of water, we can then calculate the specific heat of
lead.

5.5

Specific Heat Capacity and Calorimetry

Example 5.5:
Solution Treating the calorimeter as an isolated system (no heat lost to the
surroundings), we write

or

The heat gained by the water is given by

where m and s are the mass and specific heat and


DT = Tfinal Tinitial

5.5

Specific Heat Capacity and Calorimetry

Example 5.5:
Therefore,

Because the heat lost by the lead pellet is equal to the heat gained by the
water, qPb = 280.3 J. Solving for the specific heat of Pb, we write

68

Checkpoint 7
A quantity of 1.00 x 102 mL of 0.500 M HCl is mixed with
1.0 x 102 mL of 0.50 M Ba(OH)2 in a constant-pressure
calorimeter having a heat capacity of 335 J/C. The initial
temperature of both solutions is the same at 22.50C. The
final temperature of the solution is 24.90C. Calculate the
heat change for the neutralization reaction.
NaOH (aq) + HCl (aq) NaCl (aq) + H2O (l)
Assume that the densities and specific heats of the solutions are the
same as for water (1.00 g/mL and 4.184 J/C, respectively)

69

Topic
5.6 Standard Enthalpy

5.6 Standard Enthalpy


Because there is no way to measure the absolute value of the
enthalpy of a substance, must I measure the enthalpy change for
every reaction of interest?
Establish an arbitrary scale with the standard enthalpy of
f
formation (DH0f) as a reference point for all enthalpy expressions.

Standard enthalpy of formation (DH0f) 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 25C
and 1 atm pressure. The standard enthalpy of formation of any element in
its most stable form is zero.

DH0f (O2) = 0
DH0

(O3) = 142 kJ/mol

DH0f (C, graphite) = 0

DH0f (C, diamond) = 1.90 kJ/mol

72

5.6 Standard Enthalpy


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
Hf = 0 is graphite
oxygens standard state is the diatomic gas
C(s, graphite) + O2(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) + O2(g) CO(g)

5.6 Standard Enthalpy


Types of Enthalpy Change

The Standard Enthalpy of Formation , Hf


Example :
Ca (s) + C (s) + 3/2 O2 (g) CaCO3 (s)

= -1207 kJ mol-1

The standard heat of formation of CaCO3 (s) is 1207


kJ mol-1
The Standard heat of formation, Hf , of a pure element
in its most stable form is zero, 0. 0

Checkpoint 8
a) Write a thermochemical equation for the formation of
ethanol, C2H5OH (l) under standard conditions. The Hf of
C2H5OH (l) = -287 kJ/mol
b) Write the formation reactions for C7H12O(l) and Al2(SO4)3 (S)

5.6 Standard Enthalpy


Types of Enthalpy Change

The Standard Enthalpy of Combustion , Hc


The amount of heat released when 1 mole of the
substance is burnt completely in oxygen at standard
state conditions.
Example
H2 (g)

O2 (g)

H2O (l)

D oc = -286 kJ

The standard heat of combustion of hydrogen, H2 (g)


is
286 kJ mol-1.

Writing Combustion Reactions


Write the Combustion Reaction for CH3OH(l)
The combustion reaction is the reaction between the
CH3OH and gas oxygen (g)
CH3OH(l) + 3/2O2(g) CO2(g) + 2H2O(g)
The compounds/substance must be in 1 mole
The equation must be balanced, but the coefficient of
the oxygen gas and product doesnt matter
use whatever coefficient in front of the oxygen and products
are necessary to make the atoms on both sides equal without
changing the reactant coefficient

CH3OH(l) + 3/2O2(g) CO2(g) + 2H2O(g) DH = -ve

Example 5.6.1: How much heat is evolved in the complete


combustion of 13.2 kg of C3H8(g)? Given 1 mol C3H8 = 2044 kJ

Given:
Find:
Conceptual
Plan:
Relationships:

13.2 kg C3H8, 1 mol C3H8 = 2044 kJ

q, kJ/mol

kg

mol

kJ

1 kg = 1000 g,, Molar Mass = 44.09 g/mol

Solution:

Check:

the sign is correct and the number is reasonable because


the amount of C3H8 is much more than 1 mole

5.6 Standard Enthalpy


Example 5.6.2

How much heat is evolved when a 0.483 g


diamond is burned?
(DHcombustion = 395.4 kJ/mol C)

Example 5.6.2 How much heat is evolved when a 0.483 g


diamond is burned? Given 1 mol C3H8, DH = 395.4 kJ/mol C
Given:

0.483 g C, DH = 395.4 kJ/mol C

q, kJ/mol

Find:
Concept Plan:

Relationships:

mol

kJ

1 mol C = 395.4 kJ, Molar Mass = 12.01 g/mol

Solution:

Check:

the sign is correct and the number is reasonable because


the amount of diamond is less than 1 mole

Checkpoint 9
According to thermochemical equation for the combustion
of acetone:
C H O(l) 4O (g) 3CO (g) 3H O(g)
3 6
2
2
2

Ho 1790kJ

If the reaction contains 177 mL of acetone, how much heat is


released by its complete combustion? The density acetone is
0.788 g/mL.

81

5.6 Standard Enthalpy


Types of Enthalpy Change

The Standard Enthalpy of Neutralization , Hn

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, H2O (l)
under standard conditions.
H+(aq) + OH-(aq) H2O(l) H = std enthalpy of neutralization

5.6 Standard Enthalpy


The Standard Enthalpy of Neutralization , H
Examples:
NaOH(aq) + HCl(aq) NaCl(aq) + H2O(l)

Ho = 57.3 kJ

mol1

Ca(OH)2(aq) + HNO3(aq) CaNO3(aq) + H2O(l) Ho = 57.3 kJ

mol1

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) H2O(l)

H = 57.3 kJ mol1

The Standard Enthalpy of Neutralization , H


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) + H2O(l) Ho = 11.7 kJ mol1
NaOH(aq) + CH3COOH(aq) CH3COONa(aq) + H2O(l) Ho = 55.6 kJ mol1

NH4OH(aq) + CH3COOH(aq) CH3COONH4(aq) + H2O(l) Ho = 50.4 kJ mol1

The Standard Enthalpy of Neutralization , H


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 H2SO4, it
releases a lot of heat with dilution when the aqueous alkali is
added to it.
NaOH(aq) + HF(aq) NaF(aq) + H2O(l)

Ho = 69.0 kJ mol1

KOH(aq) + H2SO4(aq) K2SO4(aq) + H2O(l) Ho = 66.0 kJ mol1

85

Topic
5.7 Enthalpy Changes of
Chemical Reactions

5.7 Enthalpy Changes of Chemical


Reactions
Method of Determining Enthalpy
Change, H

DIRECT METHOD
Hreaction= nHf(products) nHf(reactants)

INDIRECT METHOD

HESSS LAW

Calculating Standard Enthalpy Change using


direct Method
The standard enthalpy of reaction (DH0rxn) is the enthalpy change that
occurs in a system when one mole of matter is transformed by a
chemical reaction under standard conditions.
The standard enthalpy of reaction Hrxn is related to the standard
enthalpy of formation Hf of the reactants and products by the
following equation:

aA + bB

cC + dD
DH0rxn = [cDH0f (C) + dDH0f (D) ] - [ aDH0f (A) + bDH0f (B) ]
DH0rxn = S nDH0f (products) - S nDH0f (reactants)
Where means sum and n is the coefficient of the reaction

Any reaction can be written as the sum of formation


reactions (or the reverse of formation reactions) for the
reactants and products.
88
This method for is called the direct method.

Figure 6.12

Elements

-DHof

formation

Reactants

decomposition

Enthalpy, H

The general process for determining DHorxn from DHof values.

DHof
Hinitial

DHorxn
Products

Hfinal
DHorxn = S nDHof(products) - S nDHof(reactants)

Example 5.7.1: Calculate the enthalpy change in


the reaction
2 C2H2(g) + 5 O2(g) 4 CO2(g) + 2 H2O(l)
1. Write formation reactions for each compound and
determine the DHf for each
2 C(s, gr) + H2(g) C2H2(g)

DHf = +227.4 kJ/mol

C(s, gr) + O2(g) CO2(g)

DHf = 393.5 kJ/mol

H2(g) + O2(g) H2O(l)

DHf = 285.8 kJ/mol

Example 5.7.1: Calculate the enthalpy change in


the reaction
2 C2H2(g) + 5 O2(g) 4 CO2(g) + 2 H2O(l)
DHreaction = S n DHf(products) S n DHf(reactants)
DHrxn = *(4DHCO2 + 2DHH2O) (2DHC2H2 + 5DHO2)]
DHrxn = *(4(393.5) + 2(285.8)) (2(+227.4) + 5(0))+
DHrxn = 2600.4 kJ

Checkpoint 10
Calculate the DH
rxn for decomposing 10.0 g of
limestone, CaCO3, under standard conditions.
CaCO3(s) CaO(s) + O2(g)

5.7 Enthalpy Changes of Chemical


Reactions
Calculating Standard Enthalpy Change using
Indirect Method- Hesss 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.)

Calculating the Enthalpy Change


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

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

Given:

Eq 1 : CO (g) + O2 (g) CO2 (g)


Ho1 = -283.0 kJ/mol
Eq 2 : C (graphite) + O2 (g) CO2 (g) Ho2 = -393.5 kJ/mol
Calculate the enthalpy change of reaction for the above
reaction.

Solution
- H for the forming CO (g) from C (graphite) and O2 (g) can be
determined indirectly, as long as H for other reactions is
already measured.

Calculating the Enthalpy Change


Because DH 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 ) + O2 (g) CO (g)
Horxn = ?
Eq 1 : CO (g) + O2 (g) CO2 (g)
Ho1 = -283.0 kJ/mol
Eq 2 : C (graphite) + O2 (g) CO2 (g) Ho2 = -393.5 kJ/mol
Thus , Horxn = Ho1 + Ho2
Eq 1 in reversed form so Ho1 is +ve
CO2 (g) CO (g) + O2 (g)
+
C (graphite) + O2 (g) CO2 (g)
C (graphite ) + O2 (g) CO (g)

Ho1 = +283.0 kJ/mol


Ho2 = -393.5 kJ/mol
Horxn = -110.5 kJ/mol

Example 5.7.2: Calculate the enthalpy change in


the reaction by using direct and indirect method
2 C2H2(g) + 5 O2(g) 4 CO2(g) + 2 H2O(l)
Hesss Law (Indirect Method)
Arrange equations so they add up to desired reaction
2 C2H2(g) 4 C(s) + 2 H2(g)

4 C(s) + 4 O2(g) 4CO2(g)


2 H2(g) + O2(g) 2 H2O(l)

DH = 2(227.4) kJ

DH = 4(393.5) kJ
DH = 2(285.8) kJ

2 C2H2(g) + 5 O2(g) 4 CO2(g) + 2 H2O(l)

DH = 2600.4 kJ

Example 5.7.2: Calculate the enthalpy change in


the reaction by using direct and indirect method
2 C2H2(g) + 5 O2(g) 4 CO2(g) + 2 H2O(l)
Direct Method
DHreaction = S n DHf(products) S n DHf(reactants)

DHrxn = *(4DHCO2 + 2DHH2O) (2DHC2H2 + 5DHO2)]


DHrxn = *(4(393.5) + 2(285.8)) (2(+227.4) + 5(0))+
DHrxn = 2600.4 kJ

Checkpoint 11
Use Hesss Law to calculate the standard enthalpy of formation
of acetylene (C2H2) from its elements:

The equations for each step and the corresponding enthalpy


changes are

Topic
5.8 Lattice Energy & Born-Haber
Cycle

5.8 Lattice Energy & 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

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 under standard condition.
Provide a measure of strength of ionic bond between
ions in the crystal lattice.
always exothermic
hard to measure directly, but can be calculated from
knowledge of other processes

Example: Na+(g) + Cl-(g) Na+Cl-(s)

Copyright 2011 Pearson Education, Inc.

5.8 Lattice Energy & Born-Haber Cycle


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

Copyright 2011 Pearson Education, Inc.

5.8 Lattice Energy & Born-Haber Cycle


The BornHaber Cycle
We can determine lattice energy indirectly, by
assuming that the formation of an ionic compound
takes place in a series of steps.
This procedure, known as the Born-Haber cycle,
relates lattice energies of ionic compounds to
ionization energies, electron affinities and other
atomic and molecular properties.
It is based on Hesss law.
Developed by Max Born and Fritz Haber, the BornHaber cycle defines the various step that precede the
formation of an ionic solid.

Copyright 2011 Pearson Education, Inc.

5.8 Lattice Energy & Born-Haber Cycle


The BornHaber Cycle
Beside standard enthalpy of lattice energy, there are
other general common enthalpy changes such as:
1.
2.
3.
4.

The standard enthalpy of atomization


The standard enthalpy of ionization
The standard bond dissociation enthalpy
Electron Affinity

5.8 Lattice energy & Born-Haber Cycle


1. The 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.
Enthalpy involved in converting a solid/liquid/aqueous
material to gas and the process is endothermic.
Example
H2 (g)
Na(s)

H (g)
Na(g)

H = +216 kJ
H = +109 kJ

NOTE: Dissociation of diatomic gaseous elements:


Diatomic gas as example Cl2, Hoat is equal to half the bond energy
(enthalpy).
Cl2(g) Cl(g)
Hoat = E (Cl-Cl)
Hoat = (+242 )
Hoat = +121 kJmol-1

Copyright 2011 Pearson Education, Inc.

5.8 The Born-Haber Cycle


2. The Standard Enthalpy of Ionization
The standard enthalpy of ionization is the enthalpy change for
one mole of a gaseous element or cation to lose electrons to
form a mole of positively charged gaseous ions.The process
is endothermic.
1st ionization energy (1st IE)
The amount of energy required to remove the first valence electron from
a gaseous atom is called the first ionization energy.
2nd ionization energy (2nd IE)
The amount of energy 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 M2+(g) H = Second ionization energy

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5.8 Lattice energy & Born-Haber Cycle


3. 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

H2 (g)

2H (g)

H = +432 kJ mol-1

The standard bond dissociation enthalpy of the


H-H bond in H2 molecule is +432 kJ mol-1

Copyright 2011 Pearson Education, Inc.

5.8 Lattice Energy & Born-Haber Cycle


4. 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 A2-(g)
H =Second electron affinity

Copyright 2011 Pearson Education, Inc.

Example 1: The BornHaber Cycle


Consider the following reaction:

Li (s) + F2(g) LiF(s) H=


-594.1 kJ
f
The standard enthalpy change for this reaction is -594.1 kJ (same with
standard enthalpy of formation for LiF)
STEP 1: Standard enthalpy of Atomization: Convert solid lithium to
lithium vapor
of solid
to ato
gas
is also
We will illustrate
the(direct
use ofconversion
Born-Haber
cycle
find
theknown
lattice
as sublimation)
energy of lithium fluoride.

H=
155.2
Li(g)
Consider Li
the(s)
reaction
between
lithium
andkJ
fluorine
1

The energy of atomization is 155.2 kJ


STEP 2: Dissociate mole of F2 gas into separate gaseous F atoms.

F2 (g) F (g)

H=
75.3 kJ
2

109

The energy needed to break the bonds in 1 mole of F2 molecules


is 150.6 kJ. Here we are breaking the bonds in half a mole of F2, so the
enthalpy change is 150.6/2 or 75.3 kJ

Copyright 2011 Pearson Education, Inc.

STEP 3: Ionize 1 mole of gaseous Li atoms


Li (g) Li+(g) + e-

H=
520 kJ
3

This process corresponds to the first ionization of Li.


STEP 4: Add 1 mole of electrons to 1 mole of gaseous F
atoms. The energy change for this process is just the
opposite of electron affinity.
F(g) + e- F-(g)

H=
-328kJ
4

STEP 5: Combine 1 mole of gaseous Li+ and 1 mole of F- to


form 1 mole of solid LiF.

Li+(g) + F-(g) LiF (s)

H=
?
5

The reverse of step 5 defines the lattice energy of


LiF.
110
Thus the lattice energy must have the same
magnitude as H 5 but an opposite sign.

Copyright 2011 Pearson Education, Inc.

Although we cannot determine H5 directly, we can calculate


its value by the following procedure.
Li (s) Li(g)

H=
155.2 kJ
1

F2 (g) F (g)

H=
75.3 kJ
2

Li (g) Li+(g) + e-

H=
520 kJ
3

F(g) + e- F-(g)

H=
4 -328kJ

f (s) H= ?
Li+(g) + F-(g) LiF
5

Li (s) + F2(g) LiF(s) H

overall

= -594.1 kJ

According to Hesss Law, we can write


H
Overall= H
1 + H
5
3 + H
2 + H
4 + H

111

-594.1 kJ = 155.2 kJ + 75.3 kJ + 520 kJ -328 kJ + H


5
H=
-1017 kJ
5

Copyright 2011 Pearson Education, Inc.

5.8 Lattice Energy & Born-Haber Cycle


Example 2: The BornHaber Cycle
kJ mol-1
> Na(g)

Enthalpy of atomization of sodium

Na(s)

Enthalpy of atomisation of chlorine

Cl2(g) > Cl(g)

+ 121

1st Ionisation Energy of sodium

Na(g) > Na+(g) + e

+ 500

Electron Affinity of chlorine

Cl(g) + e > Cl(g)

364

Lattice Enthalpy of NaCl

Enthalpy of formation of NaCl

Hoverall

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

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

+ 108

?
411

= H
1 + H
5
3 + H
2 + H
4 + H

H=
?
5

Copyright 2011 Pearson Education, Inc.

Born-Haber Cycle - NaCl


1

Enthalpy of formation of NaCl

Na(s) + Cl2(g) >


2

Na+(g) + Cl(g)

Enthalpy of sublimation of sodium

Na(s)
3

NaCl(s)

>

Na(g)

Enthalpy of atomisation of chlorine

Cl2(g) >

Na+(g) + Cl(g)

Cl(g)
Na(g) + Cl(g)

Ist Ionisation Energy of sodium

Na(g) > Na+(g) + e


5

Electron Affinity of chlorine

Cl(g) + e
6

>

3
Na(g) + Cl2(g)

Cl(g)

Lattice Enthalpy of NaCl

2
Na(s) + Cl2(g)

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


Lattice Enthalpy is exothermic.
Oppositely charged ions are
attracted to each other.

1
NaCl(s)

Born-Haber Cycle - NaCl


CALCULATING THE LATTICE ENTHALPY

Na+(g) + Cl(g)

Apply Hesss Law


6

5=

-4

-3

-2

-1

The minus shows you are going in the


opposite direction to the definition
= - (-364) - (+500) - (+121) - (+108) + (-411)
= - 776 kJ mol-1
2
3
4

5
6
1

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

Na+(g) + Cl(g)
Na(g) + Cl(g)

+108 kJ
+(121 kJ)
+500kJ Na(s)
364 kJ
DH (NaCl

411 kJ

Na(g) + Cl2(g)

+ Cl2(g)

1
NaCl(s)

Born-Haber Cycle - NaCl


CALCULATING THE LATTICE ENTHALPY

Na+(g) + Cl(g)

Apply Hesss Law


5

OR
4

Ignore the signs and just use the values;


If you go up you add, if you come down
you subtract the value

Na+(g) + Cl(g)
Na(g) + Cl(g)

-1 3

= (364) - (500) - (121) - (108) - (411)


= - 776 kJ mol-1

Na(g) + Cl2(g)

Na(s) + Cl2(g)

1
NaCl(s)

Checkpoint 12: The BornHaber Cycle


Given the information below, determine the
lattice energy of MgCl2
Mg(s) Mg(g)
Cl2(g) Cl(g)
Mg(g) Mg+(g)
Mg+(g) Mg2+(g)
Cl(g) Cl(g)
Mg(s) + Cl2(g) MgCl2(s)

DH1f = +147.1 kJ/mol


DH2f = +122 kJ/mol
DH3f = +738 kJ/mol
DH4f = +1450 kJ/mol
DH5f = 349 kJ/mol
DH6f = 641 kJ/mol

Answer
DHlattice energy = -2522 kJ/mol

End of Chapter 5

Good Luck for Your Final Exams!!