ENERGETICS

Objectives
1. State that chemical reactions take place through energy changes (usually in the form of
heat) associated with the breaking and making of bonds
2. State that energy changes occur in chemical reactions associated with the making and
breaking of bonds
3. Explain the differences between exothermic and endothermic reactions using energy
profile diagrams
4. Explain the term ‘bond energy’
5. Explain how bond energy data may be used to show the relationship between strength of
covalent bonds and reactivity of covalent molecules
6. Apply concepts associated with enthalpy changes
7. Explain the effect of ionic charge and radius on the magnitude of lattice energy
8. Calculate enthalpy changes from appropriate experimental data
9. State Hess’ law of constant heat summation
 Energy & Chemical Reactions
Chemical reactions take place through
energy changes (usually in the form of heat)

Enthalpy (H) is the heat content in a species

Enthalpy it self cannot be measured but
changes in enthalpy can

− Enthalpy change or ΔH is the energy change

in a reaction. An enthalpy change is the
difference between the enthalpy of the
products and the reactants
 Enthalpy Change in a System

Enthalpy Change (ΔH) = Eproducts – Ereactants

 If Eproducts > Ereactants then ΔH is positive

 reaction is endothermic
 reaction absorbs heat from the surroundings
 reaction vessel gets colder

 If Eproducts< Ereactants then ΔH is negative

 The reaction is exothermic
 reaction releases heat to the surroundings
 reaction vessel gets hotter
Enthalpy Change in a System
 Chemical Reactions
Two steps necessary in a chemical
reaction:
•FIRST
- bonds are broken
- energy is needed or absorbed during
bond breaking (endothermic)

•AFTER
- bonds are formed
- energy is released during bond
formation (exothermic)

BOTH processes ALWAYS occur in a

chemical reaction http://employees.csbsju.edu/cschaller/Reactivity/thermo/TDbondmakebreak.png
 Chemical Reactions
Chemical reactions may be classified as
endothermic or exothermic
• Exothermic - more energy is released than is
absorbed in a chemical reaction (ΔH is negative)

• Endothermic - less energy is released than is

absorbed in a chemical reaction (ΔH is positive)
http://www.gcsescience.com/rc24-energy-level-diagram.htm
Energy Profile Diagrams: Exothermic Reactions
• Energy of reactants is higher than energy of
products. ΔH is negative

• Temperature of the system increases

• Activation Energy is the minimum

amount of energy needed to begin or start
a reaction.

• Most reactions are exothermic eg. acid-base

reactions, combustion reactions and
respiration
Energy Profile Diagrams: Endothermic Reactions
• Energy of reactants is lower than
energy of products. ΔH is positive
• Temperature of the system decreases.
• Endothermic reactions have a higher
activation energy compared to
exothermic reactions
• Fewer reactions are endothermic eg.
Photosynthesis, thermal
decomposition, dissolving some salts
in water
http://www.gcsescience.com/rc25-exothermic-endothermic-reaction.htm
 Bond Energy

Bond energy is :
 the amount of energy required to dissociate a molecule into its
respective atoms
 directly related to the strength of the covalent bond and is indirectly
related to its reactivity
 Factors affecting Bond Energy

1. Strength of covalent bond

2. Size of the atoms in the molecule

3. Degree of orbital overlap in the covalent bond

4. Bond Order (single, double or triple)

 Bond Energy and Reactivity
1. If bonds can be broken easily, the reaction would occur quickly

2. If the bonds cannot be broken easily, the reaction would occur

slowly

Which is more reactive?

N2 B.E = 945 kJ mol-1 ; bond length = 110 pm
OR
O2 B.E = 498 kJ mol-1 ; bond length = 121 pm
 Bond Energy & 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 H 2O

• Hydrogen peroxide will be more chemically reactive than

water
 Classwork
State whether the following processes are
exothermic or endothermic:
• Reaction between sodium hydroxide and
hydrochloric acid
• N2 + 3H2 → 2NH3 ΔHrxn= - 92 kJ mol-1
• The burning of gasoline
• The dissolving of potassium nitrate in
water
Standard Enthalpy Changes and Definitions
 Standard Enthalpy Changes
The standard enthalpy change of a reaction is represented by
or
 What do we mean by standard conditions?
 How do we indicate that an enthalpy change is measured
under standard conditions?
The “r” for the reaction may be replaced by a specific letter
for a particular standard enthalpy or a particular reaction.
http://www.chemguide.co.uk/physical/energetics/definitions.html
 Standard Enthalpy Change of Reaction ()

The standard enthalpy change when the mole

quantities in the balanced equation react under
standard conditions (1 atm and 298 K)
At 1 atm and 25°C (298 K) reactants and products are in their
usual or standard states
 Standard Enthalpy Change of Formation ()

The enthalpy change when one moleof a

compound is formed from its elements in their
standard states (at 1 atm and 298K)
 of an element is ZERO

 values can be found from tables or will be given

 Standard Enthalpy Change of Formation ()

Example
Write the equation representing the enthalpy
change of formation () for ethane
Answer
2C(s) + 3H2 (g) → C2H6 (g)

(N.B. Rxn written and balanced to show

formation of one mole of product)
 Standard Enthalpy Change of combustion ()
The enthalpy change when one mole of a substance in its standard
state undergoes complete combustion
Example
Write the equation representing the enthalpy change of combustion ()
for ethane
Answer
C2H6 (g) + 7/2O2(g) → 2CO2(g) +3H2O(l)
 NB. Ethane is in its standard state as a gas
 One mole of ethane is combusted
 Standard Enthalpy Change of Neutralization ()

The enthalpy change when an acidreacts with a base to produce

one mole of water under standard conditions

Example
Write the equation representing the enthalpy change of
neutralization () for the reaction between HCl and NaOH

Answer
HCl(aq) + NaOH(aq) → NaCl(aq) + H2O(l)
 Standard Enthalpy Change of Atomization ()
The enthalpy change when one mole of gaseous atoms is
formed from the element under standard conditions
Example
Write the equation representing the enthalpy change of
atomization () for (a) sodium metal and (b) chlorine gas
Answer
Na(s)  Na(g)
Cl2 (g)  Cl (g)
The reaction is balanced so that one mole of gaseous atoms will be the product
 Standard Enthalpy Change of hydration ()
The enthalpy change when one mole of gaseous ions is
completed hydrated in water to infinite dilution under
standard conditions

Example
Write the equation representing the enthalpy change of
hydration (for gaseous sodium ions

Answer
Na+(g) + water → Na+(aq)
 Standard Enthalpy Change of solution ()
The enthalpy change when one mole of a solutedissolves in a solvent to
form an infinitely dilute solution under standard conditions

Example
Write the equation representing the enthalpy change of solution (for sodium
chloride

Answer
NaCl(s) + water → Na+(aq) + Cl- (aq)
NB. Further dilution produces no further enthalpy changes
 Standard Enthalpy Changes
First Ionization Energy
The enthalpy change when one mole of gaseous atoms is converted to gaseous ions with a single
positive charge
Na(g)  Na+(g) + e-

First Electron Affinity

The enthalpy change when one mole of gaseous atoms is converted to gaseous ions with a single
negative charge
Cl(g) + e- Cl- (g)

Lattice Energy ()
The enthalpy change when one mole of an ionic solid is formed from its gaseous ions under standard
conditions
Na+ (g) + Cl- (g)  NaCl (s)
 Factors affecting
1. Size of the ions 2. Charge on the ions

http://chemistry.tutorvista.com/inorganic-chemistry/lattice-energy.html

http://www.chemhume.co.uk/A2CHEM/Unit%202b/9%20Lattice%20enthalpy/Ch9Lattice.htm
Determining Enthalpy
Changes
 Determining enthalpies of reaction )

1. Experimentally (measured directly)

2. From Bond energies (calculated value)
3. From values (calculated value)
4. Calculation using Hess’ Law (measured
indirectly)
https://www.learner.org/courses/chemistry/text/text.html?dis=U&num=Ym5WdElUQS9PQ289&sec=YzJWaklUQS9OeW89
Assumptions in measuring experimentally

− calorimeter perfectly prevents

the gain or loss of heat from
the solution to its surroundings

− heat gained by the solution is

produced by the chemical
reaction or heat lost by the
solution is absorbed by the
chemical reaction
Measuring of a salt
 Measuring of a salt
Question
A student dissolves 5.35g of ammonium chloride in 100 cm 3 of distilled
water. The initial temperature of the water is 22.5 0C. After mixing a
minimum temperature of 16.4 0C is recorded by the student. Determine the
molar enthalpy change of solution and draw an energy profile diagram for
the solution process. Assume mass of 1cm 3 of solution = 1g
Q = mc ∆T
m= 100g
c=4.2 J g-1K-1
∆T= 22.5 - 16.4= 6.1
 Solution
• Enthalpy change for the reaction
• Q = mc ∆T
• Q = 100 x 4.2 x 6.1 J
= 2562 J
Number of moles of 5.35g ammonium chloride = 5.35 = 0.1
53.5
Enthalpy change for 0.1 mol = 2562J
Enthalpy change for 1 mol = X
0.1 X = 2562
X = 2562 = 25620 J = 25.62 kJ
0.1
• Enthalpy change of solution for ammonium chloride = +25.62kJ mol-1
Energy profile diagram
 Question

• A sample of salt of 2.54g was dissolved in 150 cm3 of

water. The temperature of the solvent before addition of
the salt which is calcium chloride is 30 degrees Celsius
and the final temperature is 35 degrees after mixing.
Determine the molar enthalpy change of solution
Measuring the for acid-base reactions
 Measuring the for acid-base reactions
Question
A volume of 50 cm3 of NaOH solution of concentration 1M and
temperature of 26 0C is added to 50 cm3 of HCl of concentration 1M and
temperature of 27 0C. After mixing the maximum temperature is 33.2 0C.
Determine the enthalpy of neutralization and draw an energy profile
diagram from the reaction. Assume 1cm 3 = 1g
Q = mc ∆T
m= 50 + 50 = 100g
c=4.2 J g-1 0C-1
∆T= 33.2 T2 - ( 26+ 27)/2= 26. 5 T1
= 6.7 0C
• Write a balanced equation for the reaction.
• Determine the number of moles of water made in the reaction.
1000 cm3 of NaOH contains 1.0 mol NaOH
50cm3 of NaOH contains x moles
x = 50 x 1 = 0.05 moles
1000
1000 cm3 of HCl contains 1.0 mol HCl
50cm3 of HCl contains x moles
x = 50 x 1 = 0.05 moles
1000
From the equation NaOH: HCl: H2O = 1:1:1
0.05 moles NaOH reacts with 0.05 moles HCl to produce 0.05 moles of H 2O
• Enthalpy change for forming 0.05 mol H2O = 100 x 4.2 x 6.7
= 2814 J
Enthalpy change for forming 1.0 mol H2O = 2814
0.05
56280J = 56.28kJ
Enthalpy change of neutralization = - 56.28kJ kJ mol-1
Question
Measuring the of fuels
 heatfrom combustion of the fuel is used to heat up
the water

 assumeenergy released by combustion of fuel is

absorbed by the water in the calorimeter

 heatcapacity of the water and the temperature rise

are needed to calculate how much heat was
released by a specific mass of fuel

 veryinaccurate method because of huge losses of

heat e.g. radiation from the flame
• Weighthe spirit lamp and fuel to determine
mass before combustion
• Set-up apparatus as shown in the diagram
• Record the initial temperature of the water in
the container
• Lightspirit lamp and allow the flame to heat
the water for a specific period of time and
record the final temperature
• Weigh spirit lamp after combustion
• Determine mass of fuel burnt by subtracting
the initial mass from the final mass
 Measuring the of fuels
Question
200 cm3 of water was measured into a calorimeter. A spirit
burner containing ethanol fuel, C2H5OH, weighed 18.62 g at the
start. The initial temperature of the water was measured. After
burning some time, the flame was extinguished and the water
stirred gently. The final temperature of the water was measured.
The burner and fuel are then reweighed to see how much fuel
had been burned. After burning, 17.07g of ethanol remained
and the temperature of the water rose from 34 to 89 oC.
Calculate the enthalpy of combustion for ethanol.
http://www.docbrown.info/page03/3_51energyD.htm#Calculations
 Solution

Q = mc ∆T
m = 200g
c = 4.2 J g-1 0C-1
∆T = 89 – 34 = 55 0C

Q = 200 x 4.2 x 55 = 46200J

# of moles of ethanol = 1.55/46 = 0.0337

Enthalpy change for 0.0337 moles = 46200 J
Enthalpy change for 1 mole ethanol = 46200/0.0337 =1370920 J
Enthalpy of combustion for ethanol = -1371 kJ mol-1
Enthalpy of Reaction

Question
 2. Calculating from Bond Energies

• Bond energy is the energy absorbed when a bond is broken or the

energy released when a bond is formed
• The overall change in energy when bonds break and then new bonds
form is calculated as the Enthalpy Change for the Reaction
 2. Calculating from Bond Energies
Calculate the
enthalpy of
combustion of
methane from
bond energy
values.
 2. Calculating from Bond Energies

http://www.ausetute.com.au/heatbond.html
 Calculating from Bond Energies
Use Bond enthalpies to estimate the enthalpy change
in the following reaction:
 3. Calculating ΔHr from ΔHf

ΔHr = ΣΔHf, products– ΣΔHf, reactants

ΔHr is the enthalpy change of reaction

ΔHf, products is the enthalpy change of formation of products
ΔHf, reactants is the enthalpy change of formation of reactants
 Calculating ΔHr from ΔHf values
Question
Calculate the enthalpy of the following reaction:
C2H5OH(l) + 3 O2(g) → 2 CO2 (g) + 3 H2O (l)

Standard enthalpies of formation are:

C2H5OH = -228 kJ/mol

CO2 = -394 kJ/mol

 Calculating ΔHr from ΔHf values
Answer:

C2H5OH + 3 O2 → 2 CO2 + 3 H2O

ΔHr= ΣΔHf, products– ΣΔHf, reactants

ΔHr = [(3 x -286) + (2 x -394)] – [(-228) + (3 x 0)]

= -1418 kJ mol -1