ENERGETIC

CHEM 101
TOPIC 6
 Objectives
• State that chemical reactions take place through
energy changes (usually in the form of heat)
associated with the breaking and making of bonds.
• State that energy changes occur in chemical reactions
associated with the making and breaking of bonds.
• Explain the differences between exothermic and
endothermic reactions using energy profile diagrams.
• Explain the term ‘bond energy.
• Explain how bond energy data may be used to show
the relationship between strength of covalent bonds
and reactivity of covalent molecules.
 Objectives Cont’d
• Apply concepts associated with enthalpy
changes (Include enthalpy change of formation,
combustion, reaction, hydration, solution,
neutralisation, atomisation, ionisation energy,
electron affinity and lattice energy).
• Explain the effect of ionic charge and radius on
the magnitude of lattice energy;
• State Hess’ law of constant heat summation.
• Calculate enthalpy changes from appropriate
experimental data.
Energetics and Thermodynamics

​ nergetics is the branch of physical science that deals
E
primarily with energy and its transformations


Thermodynamics is the particular branch of
energetics which deals with heat energy and its
transformations


Enthalpy is the total energy associated with any
system (i.e. a sum of the internal energy and the energy
due to environmental factors such as pressure-volume
conditions)

http://www.sophia.org/define-enthalpy/define-enthalpy-tutorial
 Energy and Chemical Reactions
Chemical reactions take place through energy


changes (usually in the form of heat)

We use the term enthalpy (H) to describe the



energy possessed by a system


It is impossible to estimate the absolute enthalpy
of a system (instead we measure changes in
enthalpy)
http://www.sophia.org/define-enthalpy/define-enthalpy-tutorial
Conditions needed for a chemical reaction

1. Particles MUST collide

2. Particles must collide with the CORRECT
ORIENTATION
3. Particles must collide with a certain MINIMUM
AMOUNT OF ENERGY (ACTIVATION ENERGY)

• These three conditions are collectively called

EFFECTIVE COLLISIONS
Effective Collisions
Processes that occur in chemical reactions

1. Bonds are broken FIRST (energy is needed or

absorbed) i.e. bond breakage
2. Bonds are formed AFTERWARDS (energy is
released) i.e. bond formation

• Note BOTH processes ALWAYS OCCUR in a

chemical reaction!!!
 Chemical reactions
Summarizing
• Chemical reactions takes place through energy changes
(usually in the form of heat)

• Bond making is an exothermic process and as such its energy

values are negated (-ve)
• Bond breaking is an endothermic process and as such its
energy values are positive (+ve)
• When an energy change occurs at constant pressure, it is
called enthalpy change H
• The change in the amount of energy contained in a substance
between the beginning of a reaction and the end of a reaction
is called the change in energy / enthalpy and is given the
symbol ΔH
Energy/enthalpy profile diagram
• Exothermic Energy Profile
Diagram
• Key features:
• Energy of products is LESS
than energy of reactants
• Products are more stable
than reactants
• Energy is lost to the
surroundings in the form of
heat
• Enthalpy change = Energy of
products – Energy of
Reactants
• Enthalpy change is -ve
Energy/enthalpy profile diagram
• Endothermic Energy Profile
Diagram
• Key features:
• Energy of products is GREATER
than energy of reactants
• Products are less stable than
reactants
• Energy is absorbed from the
surroundings in the form of
heat
• Enthalpy change = Energy of
products – Energy of Reactants
• Enthalpy change is +ve
Exothermic Reactions

Most reactions are exothermic eg.
acid-base reactions, combustion
reactions and respiration

Temperature of the system increases

ΔH is negative (Energy of reactants is
higher than energy of products)

What is the activation Energy

(Ea)?
 Endothermic Reactions

Fewer reactions are endothermic eg.
Photosynthesis, thermal decomposition,
dissolving some salts in water


Temperature of the system decreases


ΔH is positive (Energy of reactants is
lower than energy of products)
http://www.gcsescience.com/rc25-exothermic-endothermic-reacti
on.htm
 Bond energy

• The term “bond energy” refers to the amount of

energy required to dissociate a molecule into its
respective atoms.

• Bond energy, E is defined as the amount of energy

needed to break one mole of a particular bond in one
mole of gaseous molecule (also called bond dissociation
energy)

• Bond energy is directly related to the strength of the

covalent bond and is indirectly related to its reactivity.
 Bond energy

• It has a positive value since it is an

endothermic reaction
• It applies to gaseous compounds only
• Its unit is kJmol-1
• It is very difficult to measure directly
• It indicates the strength of a covalent bond
and possible reactivity of the molecule
 Factors affecting bond energy

• 1. Bond length (See atomic radii of F, Cl, Br, I

and compare to bond energies).
• 2. Number of covalent bonds (See C-O and
C=O)
• 3. The degree of polarity (See HF, HCl, HBr and
HI)

***The three factors are related***

 Bond length
• Look at the trend between bond length and
bond energy.
Number of covalent bonds/bond order

A triple bond is stronger than a double

bond and a double bond is stronger than a
single bond.
The degree of polarity
 Bond Energy and Reactivity

If bonds can be broken easily, the reaction would
occur quickly


If the bonds cannot be broken easily, the reaction
would occur slowly

Which is more reactive?

N2 B.E = 945 kJ mol-1
OR
O2 B.E = 498 kJ mol-1
 Bond Energy and Chemical Stability

The energy required to break:
O-H in H2O(g) is 463 kJ mol-1
O-O bond in H2O2 (g) is 139 kJ mol-1

 H2O2 is less stable than water because it contains

the O-O bond which is easier to break than the O-H
bond in H2O


Hydrogen peroxide will be more chemically
reactive than water
 Calculating enthalpy changes using bond
energies
• The balance sheet method • CH4 + 2O2 → CO2 + 2H2O
used in the study guide pg Bonds broken Bonds formed
63 (endothermic +)/KJmol-1 (exothermic -)/KJmol-1
• 1. Set up a table with two
columns
• Identify the bonds broken
4 x E((C-H) = 4x 410 =1640 2x E(C=O) = 2 x 740 =-1480
and formed as well as the 2 x E(O=O) =2x 496 =992 4 x E(O-H) = -1840
number of bonds.
• Look up the values of bond TOTAL = + 2632KJ TOTAL = -3320KJ
energies in the data
booklet.
• Calculate difference in
energy associated with the
two processes. • Overall enthalpy change =
+ 2632 – 3320 = -688KJmol-1
 Calculating ΔH from Bond Energies

This equation can also be used.

ΔHrxn = ΣΔHbonds broken– ΣΔHbonds formed

eg. Calculate the enthalpy of the following reaction:

CH4 + Cl2 → CH3Cl + HCl

http://www.ausetute.com.au/heatbond.html
 Checkpoint
Use Bond enthalpies (in data booklet) to
estimate the enthalpy change in the
following reaction:
 Calculating enthalpy changes using bond
energies
CHECK POINT
Calculate the enthalpy change for the following
reactions, hence state if the reactions are
exothermic or endothermic:
• H2(g) + I2(g) → 2 HI(g)
• nitrogen + hydrogen → ammonia
• ethene + steam → ethanol
 Enthalpy changes
• Enthalpy change is the name given to the amount of
heat evolved or absorbed in a reaction carried out
at constant pressure. It is given the symbol ΔH.
• Standard enthalpy changes refer to reactions done
under standard conditions, and with everything
present in their standard states. Standard states are
sometimes referred to as "reference states".
• The symbol for a standard enthalpy change is ΔH Ɵ
 Standard enthalpy changes
Standard conditions are:
• 298 K (25°C)
• a pressure of 1 bar (100 kPa).
• where solutions are involved, a concentration of 1 mol dm -3

Standard states
• This is the physical and chemical state that you would expect
to find reactants in under standard conditions.
• That means that the standard state for water, for example, is
liquid water, H2O(l) - not steam or water vapour or ice.
• Oxygen's standard state is the gas, O2(g) - not liquid oxygen or
oxygen atoms.
Types of standard enthalpy change
• Standard enthalpy change of reaction, ΔH rƟ
• Standard enthalpy change of neutralisation, ΔH nƟ
• Standard enthalpy change of solution, ΔH solƟ
• Standard enthalpy change of combustion, ΔH cƟ
• standard enthalpy change of formation, ΔH fƟ
• standard enthalpy change of atomisation, ΔH atƟ

• standard enthalpy change of hydration, ΔH fƟ

 Standard enthalpy change of formation, ΔH fƟ
• The standard enthalpy change of formation of a compound is the
enthalpy change which occurs when one mole of the compound is
formed from its elements under standard conditions, and with
everything in its standard state.
Example:

• The standard enthalpy change of formation of an element in

its standard state is zero. Why?
 Standard enthalpy change of reaction, ΔHrƟ

• The standard enthalpy change of a reaction is

the enthalpy change which occurs when
equation quantities of materials react under
standard conditions, and with everything in its
standard state.
Example:
 Calculating enthalpy change of reaction, ΔHrƟ

Enthalpy of a reaction = sum of the enthalpies of

formation for the products – sum of enthalpies of
formation for the reactants
∆Hreaction = Σ∆Hf (products) - Σ∆Hf (reactants)
Example:
Standard enthalpies of formation are:
C2H5OH(l) -228, CO2 -394, and H2O(l) -286 kJ/mol.
Calculate the enthalpy of the reaction,
C2H5OH + 3 O2 → 2 CO2 + 3 H2O
Standard enthalpy change of combustion, ΔHcƟ
• The standard enthalpy change of combustion of a compound is
the enthalpy change which occurs when one mole of the
compound is burned completely in oxygen under standard
conditions, and with everything in its standard state.
• The enthalpy change of combustion will always have a negative
value, because burning always releases heat.
Example:

Why is the enthalpy change of combustion of hydrogen the

same as that for the formation of water?
Standard enthalpy change of combustion,
ΔHcƟ
Measurements required:
Mass of water in the calorimeter (g)
Temperature rise of the water (K)
Loss in mass of the fuel (g)
E = mcΔT
c = specific heat capacity of water
(4.2Jg-1K-1)
Calculate the enthalpy change of
combustion of propanol given the
following information:
Mass of water = 100g
Temperature rise = 21.5K
Loss in mass of propanol fuel = 0.28g
Molar mass of propanol = 60.1g/mol
The value given from a data book is
-2010 kJ/mol, suggest a reason for this?
 Standard enthalpy change of neutralization,
ΔHnƟ
• The standard enthalpy change of neutralization is the
enthalpy change when solutions of an acid and an
alkali react together under standard conditions to
produce 1 mole of water.
• Enthalpy changes of neutralization are always negative
Example:
Measuring enthalpy change of neutralization,
ΔHnƟ
Measurements required:
• Total mass of solutions in the calorimeter (g)
• Change in temperature (K)
• E = mcΔT
• c = specific heat capacity of water (4.2Jg-1K-1)
Calculate the enthalpy change of neutralisation
given the following information:
Volume of HCl used = 50ml of 1M solutions
Volume of NaOH used = 50 ml of 1M solutions
Temperature rise = 6.2 K
The value given for this reaction from a data book was -57.1 kJ/mol,
suggest a reason for the difference between the 2 values.
Standard enthalpy change of solution, ΔHsolƟ

• The enthalpy change of solution is the

enthalpy change when 1 mole of an ionic
substance dissolves in water to give a solution
of infinite dilution or 1 M.
Example:
NH4NO3 (s) → NH4+ (aq) + NO3- (aq)
Measuring enthalpy change of solution, ΔHsolƟ

Measurements required:
• Total mass of water added to the calorimeter (g)
• Change in temperature (K)
• E = mcΔT
• c = specific heat capacity of water (4.2Jg-1K-1)
Calculate the enthalpy of solution of NaOH given the following
information:
Mass of water = 100g
Mass of NaOH = 6.2 g
Temperature rise = 16 K
Molar mass of NaOH = 40 g
 Enthalpy changes by experiment
• Some standard enthalpy change can be
calculated from the results of experiments
involving a calorimeter.
• A calorimeter is used to minimize heat
exchange with the surroundings.
• See study guide page 64 & 65 for procedure
used to measure enthalpy changes. (This skill
will be further developed in the labs on
enthalpy change)
 Hess’s Law
• Hess’s Law states that the total enthalpy
change for a chemical reaction is independent
of the route by which the reaction takes place,
provided the initial and final conditions are
the same.
• ∆H1 = ∆H2+ ∆H3
 Hess’s Law
• Calculations using enthalpy diagrams or Hess’s cycle
Step 1
• Write down the balanced equation for the enthalpy
change you wish to find, including state symbols (write ∆H
over the top of the arrow)
Step 2
• Given enthalpy change complete a cycle that you can
apply Hess’s law
Step 3
• Apply Hess’s Law. Find two routes within the diagram that
do not go against the flow of any arrows. (If you must go
against the flow of an arrow then change the sign of ∆H)
• Example
Given
• C + O2  CO2 (g) ΔH1 = -394 kJ mol-1 eqn 1
• CO + ½O2  CO2 ΔH2 = -283 kJ mol-1 eqn 2

Find the ΔHf of: C(s) + ½O2 (g) → CO(g)

• Rearrange the equations in order to get the equation in question

• C + O2  CO2 (g)
CO2  CO + ½O2

• If you remove the compounds on either side, the result is the equation in
question  C(s) + ½O2 (g) → CO(g)

• Then the enthalpy of formation is sum of values

 -394 + 283 = -110.5 kJ mol-1
• This question can also
be done using a Hess’s
Law cycle shown here.
• ∆H1 = ∆H + ∆H2
• ∆H = ∆H1 - ∆H2

• ∆H = -394 + 283 = -
110.5 kJ mol-1
 Other examples using Hess’s Law to
calculate enthalpy changes
• Look at examples from the Study guide
• Examples from Calculations in AS/A level Chemistry
• Types of questions
Calculate enthalpy change:
1. given standard enthalpy change of combustion
data.
2. Given standard enthalpy change of formation
data.
3. Given bond enthalpy data
Standard enthalpy change of hydration
• The hydration enthalpy is the enthalpy change when 1
mole of gaseous ions dissolve in sufficient water to give
an infinitely dilute solution.
• An infinitely dilute solution is one where there is a
sufficiently large excess of water that adding any more
doesn't cause any further heat to be absorbed or
evolved.
• Hydration enthalpies are always negative.
Example:
Al3+(g) + aq Al3+(aq) ΔH°hyd, 298 = -4613 kJ mol-1
 Lattice enthalpy, ΔH Ɵ
latt
• The lattice dissociation enthalpy is the enthalpy
change needed to convert 1 mole of solid
crystal into its scattered gaseous ions. Lattice
dissociation enthalpies are always positive.
• The lattice formation enthalpy is the enthalpy
change when 1 mole of solid crystal is formed
from its scattered gaseous ions. Lattice
formation enthalpies are always negative.
• Generally when the term lattice energy is used
it is in reference to lattice formation enthalpy.
 Lattice enthalpy
• Lattice energy cannot be determined
experimentally
• We can calculate the lattice enthalpy of an
ionic compound using a Born-Haber cycle.
• The lattice enthalpy ∆Hɵlatt is the enthalpy
change when 1 mole of an ionic compound is
formed its from its gaseous ions under
standard conditions (298K, 100KPa). Eg.
• Li+(g) + F-(g) → LiF(s) ∆Hɵlatt = -1049.5KJmol-1
• Ionic radius
The cations, Mg2+, Ca 2+, Sr 2+ and Ba 2+ ,increase in radii as you
go down the group, the attraction of the nucleus for the
anion decreases with distance, hence the ionic lattice is not
strongly held. The lattice enthalpy decreases with
increasing ionic radius.
• Ionic charge
The cations Na+, Mg2+ and Al3+ increase in ionic charge as you
go across the period. This results in anions being held more
strongly, hence more energy is required to break the bonds.
Lattice enthalpy increases with increasing ionic charge
 Born-Haber cycle to determine lattice energy
• Lattice enthalpies cannot be calculated directly by
experiments
• However enthalpy cycles can be constructed to
calculate lattice enthalpy
• These cycles are called the Born-Haber cycles
• Before constructing a Born-Haber cycle you need
to know the definitions of the following terms:
• Standard enthalpy change of formation
• Standard enthalpy change of atomisation
• Ionisation energy
• Electron affinity
 Standard enthalpy change of atomization
• The standard enthalpy change of atomisation of
an element is the enthalpy change which occurs
when an element is converted into 1 mole of its
gaseous atoms under standard conditions, and
with everything in its standard state.
• Enthalpy change of atomisation is always positive.
Example:
 Ionization energy, ∆H Ɵ
I.E.

• The standard enthalpy change accompanying

the removal of one mole of electrons from
one mole of gaseous atoms, forming one mole
of gaseous ions with a +1 charge
Example:
H(g) → H+(g) + e- HƟ = -1312.0 kJ/mol
 Electron Affinity, ΔH Ɵ
ea1

• ΔHea1The first electron affinity is the enthalpy

change when one electron is added to one
mole of gaseous atoms forming one mole of
gaseous ions with a -1 charge.
Example:
F(g) + e- → F-(g) ∆HƟ = -328.0 kJ/mol
 Born-Haber cycles
• Used primarily to determine the lattice enthalpy
of an ionic solid
• It is used when lattice enthalpy cannot be
determined experimentally
• It is essentially a more complicated Hess’ law cycle
• The cycle always begins with the elements in their
standard states
• Lattice enthalpy is always an exothermic reaction
and hence the values are always negative
 Born-Haber Cycles
eg for sodium chloride:
Na+ (g) + e- + Cl (g)
enthalpy H
H first ionisation energy H first electron affinity

Na (g) + Cl (g)
Na+ (g) + Cl- (g)
H atomisation

Na (g) + ½ Cl2 (g)

H atomisation H lattice
Na (s) + ½ Cl2 (g) enthalpy

H formation
NaCl (s)
 Born-Haber Cycles : applying Hess’s Law
There are two routes from elements to ionic compound

Na+ (g) + e- + Cl (g)

enthalpy H
H first ionisation energy H first electron affinity

Na (g) + Cl (g)
Na+ (g) + Cl- (g)
H atomisation

Na (g) + ½ Cl2 (g)

H atomisation H lattice
Na (s) + ½ Cl2 (g) association
Apply
Hess’s H formation
Law:
NaCl (s)

HatmNa + HatmCl + H1st IE + H1st EA + Hlattice = Hformation

 Born-Haber Cycles
HatmNa + HatmCl + H1st IE + H1st EA + Hlattice = Hformation

Rearrange to find the lattice energy:

Hlattice = Hformation - (HatmNa + HatmCl + H1st IE + H1st EA)

So Born-Haber cycles can be used to calculate a measure of

ionic bond strength based on experimental data.
 Check point
• 1. Draw a Born-Haber cycle for the compound
LiCl and using the data below calculate the
lattice energy of LiCl
• 2. Determine the lattice energy of CaF2 using
the following data
• Use the following data draw the Born-Haber cycle for MgO and calculate the lattice enthalpy of
MgO.
• Enthalpy of formation MgO : -601 kJ mol-1
• Enthalpy of atomization Mg: +148 kJ mol-1
• 1st ionisation energy Mg: +738 kJ mol-1
• Bond dissociation O2: +498 kJ mol-1
• 2nd ionisation energy Mg: +1451 kJ mol-1
• 1st electron affinity O: -141 kJ mol-1
• 2nd electron affinity O: +744 kJ mol-1
 Factors affecting lattice energy
• 1. The size of the ions
• 2. The charge on the ions
• 3. The way the ions are arranged in the ionic
lattice

• Assignment: Explain how these factors affect

lattice energy
calculating the enthalpy of solution for ionic compounds via
application of Hess’s Law and Born-Haber cycles

• Enthalpy of solution =
ΔHlattice + ΔHhydration
 Check point
• 1. Draw a Born-Haber cycle for the compound
LiCl and using the data below calculate the
lattice energy of LiCl
 1. Draw a Born-Haber cycle for the compound 3
LiCl and using the data below calculate the 2
1
lattice energy of LiCl 4
5
1- ΔHf Li(s) + ½ Cl2 (g)  LiCl (s) - 409(↓)
2- ΔHatm Li(s)  Li(g) +159 ( ↑ ) 4- ΔHatm ½ Cl2 (g)  Cl(g) +122 ( ↑ )
3- ΔHIE Li(g)  Li+(g) + e- +520 ( ↑ ) 5- ΔHEA Cl (g) + e-  Cl -(g) - 349 (↓)
HatmNa + HatmCl + H1st IE + H1st EA + Hlattice = Hformation
Li+(g) + Cl (g) + e-
ΔHatm° Li+(g) + ½ Cl2 (g) + e- +122 - 349 (↓
ΔHEA°
Li+(g) + Cl- (g)

ΔHIE ° +520

Li(g) + ½ Cl2 (g) ΔHlattice°

Li(s) + ½ Cl2 (g) +159 ( ↑ ) Lattice energy

ΔHatm°

ΔHf°
- 409(↓)
LiCl (s)
• 2. Determine the lattice energy of CaF2 using
the following data
• Formation = -1228 KJ/mol
• Use the following data draw the Born-Haber cycle for MgO and calculate the lattice enthalpy of
MgO.
• Enthalpy of formation MgO : -601 kJ mol-1
• Enthalpy of atomization Mg: +148 kJ mol-1
• 1st ionisation energy Mg: +738 kJ mol-1
• Bond dissociation O2: +498 kJ mol-1
• 2nd ionisation energy Mg: +1451 kJ mol-1
• 1st electron affinity O: -141 kJ mol-1
• 2nd electron affinity O: +744 kJ mol-1
 1- ΔHf Mg(s) + ½ O2 (g)  MgO(s) - 601(↓)
2- ΔHatt Mg(s)  Mg(g) +148( ↑ ) 3- ΔHIE 1st Mg(g)  Mg+(g) + e- +738 ( ↑ )
.
4- ΔHIE 2nd Mg+(g)  Mg2+(g) + e- +1451( ↑ )
Mg2+(g) + O2- (g)
5- ΔHBDE ½ O2 (g)  O(g) +498( ↑ ) 6- ΔHEA 1st O (g) ) + e-  O-(g) -141 ( ↓)
7- ΔHEA 2nd O- (g) ) + e-  O2-(g) +744( ↑) +744
ΔHEA°

Mg2+(g) + O (g) + 2e- 2nd

ΔHEA° - 141
ΔH ° +498 Mg 2+
+ O (g) +e-
-
BDE
Mg2+(g) + ½ O2 (g) + e- (g)

2nd
ΔHIE °
+1451
Mg+(g) + ½ O2 (g) ΔHlattice°

1st
Lattice energy
ΔHIE °
+738
Mg(g) + ½ O2 (g)
ΔHatm°
Mg(s) + ½ O2 (g) +148( ↑ )

ΔHf°
- 601(↓) MgO (s)
Born- Haber Cycle Practice & lattice energy
calculation
• Magnesium Chloride Mg(s) + Cl2 (g)  MgCl2(s)

• Enthalpy of formation MgCl2 : -641 kJ mol-1

• Enthalpy of atomization Mg: +148 kJ mol-1
• 1st ionisation energy Mg: +736 kJ mol-1
• 2nd ionisation energy Mg: +1450 kJ mol-1
• Enthalpy of atomization Cl: +122 KJ mol-1
• 1st Electron Affinity Cl: - 348 kJ mol-1
 Factors affecting lattice energy
• 1. The size of the ions
• 2. The charge on the ions
• 3. The way the ions are arranged in the ionic
lattice

• Assignment: Explain how these factors affect

lattice energy
calculating the enthalpy of solution for ionic compounds via
application of Hess’s Law and Born-Haber cycles

• Enthalpy of solution =
ΔHlattice + ΔHhydration