I.

Energy and Chemistry

A. Chemical Energy from the Combustion of Fuels
Outline

A. Chemical Energy from the Combustion of Fuels

1. The First Law of Thermodynamics

2. Enthalpy
3. Enthalpies of Reaction
4. Calorimetry
5. Hess’s Law
6. Enthalpies of Formation
7. Fuels
Learning Outcomes
• State the first law of thermodynamics.
• Differentiate endothermic and exothermic
processes.
• Calculate H from quantities of reactants and
products.
• Relate heat, temperature and heat capacity.
• Measure H from calorimetry data.
• Use Hess’ law to calculate H
• Calculate an enthalpy of reaction from enthalpies of
formation.
• Describe energy sources: fossil fuels (petroleum,
natural gas, coal) and biomass.
Overview

On this first part of Energy and Chemistry, we will

discuss how energy is obtained from burning
chemical fuels. We will center on the principles of
thermochemistry, which is the application of
thermodynamics to chemical reactions. Lastly, we
will have a survey of different kinds of chemical fuels,
and how we can determine the amount of energy
that can be obtained from the combustion of these
materials.
 Energy can be Obtained from the
Combustion of Fuels

Man first utilized fuels when

fire was discovered and
controlled during the Stone
Age.

Vladimir Servan / Getty Images

Burning or combustion is the
reaction of a carbon-
CO2 + H2O +
containing substance with
oxygen which produces carbon
FUEL + O2 dioxide, water, and energy in
ENERGY the form of heat and light.
Fossil Fuels are Currently the Main Energy
Source of the World

World primary energy supply by share in 2017

Source: https://www.worldenergydata.org/world/
Fossil Fuels are Nonrenewable Energy
Sources

Source: https://www.assignmentpoint.com/science/chemistry/fossil-fuel.html
 Temperature is the Average Kinetic Energy
of the Particles in a Sample

The Celsius scale is

based on the physical
properties of water.
Pure water freezes at 0
°C and boils at 100 °C.

https://www.clivemaxfield.com/what-the-faq-are-kelvin-and-rankine-
et-al/
 There are Several Temperature Scales

The Kelvin is the SI unit

for temperature. The
temperature expressed
in kelvins is also called
the thermodynamic or
absolute temperature.
K = C + 273.15

https://www.clivemaxfield.com/what-the-faq-are-kelvin-and-rankine-
et-al/
 There are Several Temperature Scales

The Fahrenheit is not used in

science.
F = 9/5(C) + 32
C = 5/9(F − 32)

The Rankine is common in

engineering
°R = °F + 459.67

https://www.clivemaxfield.com/what-the-faq-are-kelvin-and-rankine-
et-al/
Heat and Work are Forms of Energy

• Energy is the ability to do work or transfer heat.

• Energy used to cause an object that has mass to
move is called work.
• Energy used to cause the temperature of an
object to rise is called heat.
Definitions: Potential Energy

Potential energy is energy an object possesses by

virtue of its position or chemical composition.

https://www.quora.com/What-are-examples-of-potential-energy
Definitions: Kinetic Energy
Kinetic energy is energy an object possesses by
virtue of its motion.
1 mv2
KE = 
2

https://blog.myrank.co.in/kinetic-energy/
Units of Energy

• The SI unit of energy is the joule (J).

kg m2
1 J = 1 
s2
• An older, non-SI unit is still in widespread use: the
calorie (cal).
1 cal = 4.184 J
The System and its Surroundings are Basic
Concepts in Thermodynamics

• The system is the portion of

the universe we want to study
• The surroundings are
everything else.

https://nptel.ac.in/content/storage2/courses/112103016/module1/lec1/2.html
There are Several Types of Systems

https://www.e-education.psu.edu/eme504/node/534
Definition: Work (w)

• Energy used to move

an object over some
distance is work.
•w = F  d
where w is work, F is
the force, and d is the
distance over which the
force is exerted.

https://www.mathsisfun.com/physics/energy-work.html
 Definition: Heat (q)

• Energy can also be

transferred as heat.
• Heat flows from
warmer objects to
cooler objects.

https://www.pathwayz.org/Tree/Plain/HEAT
 The First Law of Thermodynamics
• Energy is neither created nor destroyed but can be
converted from one form to another.
• In other words, the total energy of the universe is a
constant; if the system loses energy, it must be gained
by the surroundings, and vice versa.

https://www.qsstudy.com/physics/significance-first-law-thermodynamics
Definition: Internal Energy (E)
The internal energy of a system is the sum of all kinetic
and potential energies of all components of the
system; we call it E.
Change in Internal Energy (E)
By definition, the change in internal energy, E, is the
final energy of the system minus the initial energy of
the system:

E = Efinal − Einitial
Definition: Endergonic

• If E > 0, Efinal > Einitial

• Therefore, the system
absorbed energy from the
surroundings.
• This energy change is
called endergonic.
Definition: Exergonic

• If E < 0, Efinal < Einitial

• Therefore, the system
released energy to the
surroundings.
• This energy change is
called exergonic.
Mathematical Statement of the First Law

• When energy is
exchanged between the
system and the
surroundings, it is
exchanged as either
heat (q) or work (w).
• That is,
E = q + w
E, q, w, and Their Signs
First Law Calculations
• Calculate the value of ΔE in joules for a system that loses 50 J of heat and
has 150 J of work performed on it by the surroundings.
First Law Calculations
• A gas is compressed and during this process the surroundings does 128 J
of work on the gas. At the same time, the gas loses 270 J of energy to
the surroundings as heat. What is the change in the internal energy of
the gas?
Exchange of Heat between System and
Surroundings

• When heat is absorbed by the system from the

surroundings, the process is endothermic.
Exchange of Heat between System and
Surroundings

• When heat is absorbed by the system from the

surroundings, the process is endothermic.
• When heat is released by the system into the
surroundings, the process is exothermic.
 The Internal Energy is a State Function
• It depends only on the present state of the system, not
on the path by which the system arrived at that state.
• And so, E depends only on Einitial and Efinal.
Heat and Work are Path Functions

• However, q and w are not

state functions.
• Whether the battery is
shorted out or is
discharged by running the
fan, its E is the same.
• But q and w are different in
the two cases.
State vs Path Functions

• The area between the

curve and x-axis labeled
q will depend on the
shape of the path
between the initial and
final states. This is also
true for the area
labeled w.
• w and q are path
functions
State vs Path Functions

• The total area

E = q + w
will only depend on the
final and initial states,
and not on the shape of
the curve.
• E is a state function
Work

Usually in an open
container the only work
done is by a gas pushing
on the surroundings (or by
the surroundings pushing
on the gas).
Work Done by a Gas
We can measure the work done by the gas if the
reaction is done in a vessel that has been fitted
with a piston.
w = -PV
Definition: Enthalpy (H)
• If a process takes place at constant pressure (as the
majority of processes we study do) and the only work
done is this pressure-volume work, we can account
for heat flow during the process by measuring the
enthalpy of the system.
• Enthalpy is the internal energy plus the product of
pressure and volume:

H = E + PV
Enthalpy is also a State Function

• When the system changes at constant pressure, the

change in enthalpy, H, is
H = (E + PV)
• This can be written
H = E + PV
Enthalpy is Heat Gained or Lost at Constant
Pressure
• Since E = q + w and w = -PV, we can substitute
these into the enthalpy expression:
H = E + PV
H = (q+w) − w
H = q
• So, at constant pressure, the change in enthalpy is
the heat gained or lost.
Endothermicity and Exothermicity

• A process is
endothermic when
H is positive.
Endothermicity and Exothermicity

• A process is
endothermic when
H is positive.
• A process is
exothermic when H
is negative.
 Definition: Enthalpy of Reaction (H)

The change in enthalpy,

H, is the enthalpy of the
products minus the
enthalpy of the
reactants:

H = Hproducts − Hreactants
Enthalpy of Reaction

This quantity, H, is called the enthalpy of reaction,

or the heat of reaction.
Properties of Enthalpy

1. Enthalpy is an extensive property.

2. H for a reaction in the forward direction is
equal in size, but opposite in sign, to H for the
reverse reaction.
3. H for a reaction depends on the state of the
products and the state of the reactants.
Enthalpy Calculations

• The value of H for the reaction below is -790 kJ. Calculate the enthalpy
change accompanying the reaction of 0.95 g of S in kJ.
2S(s) 3O 2 (g)  2SO3 (g)
Calorimetry is the Measurement of Heat
Transfer due to a Physical or Chemical
Change

Since we cannot know the exact enthalpy of the

reactants and products, we measure H through
calorimetry, the measurement of heat flow.
Definition: Heat Capacity (C)

The amount of energy required to raise the

temperature of a substance by 1 K (1C) is its heat
capacity.
Definition: Specific Heat (c)

We define specific heat capacity (or simply specific

heat) as the amount of energy required to raise the
temperature of 1 g of a substance by 1 K.
Heat Capacity and Specific Heat

Specific heat, then, is

heat transferred
Specific heat =
mass  temperature change

q
c=
m  T
Constant-Pressure Calorimetry

By carrying out a reaction in

aqueous solution in a
simple calorimeter such as
this one, one can indirectly
measure the heat change
for the system by
measuring the heat change
for the water in the
calorimeter.
Constant-Pressure Calorimetry

Because the specific heat

for water is well known
(4.184 J/g-K), we can
measure H for the
reaction with this equation:
q = m  c  T
Using Specific Heat Capacity
• The specific heat of liquid bromine is 0.226 J/g-K. How much heat (J) is
required to raise the temperature of 10.0 mL of bromine from 25.00 °C
to 27.30 °C? The density of liquid bromine: 3.12 g/mL.
Using Specific Heat Capacity
(a) Determine the amount of heat energy is associated with heating a 154
gram iron bar from 20.0 °C to 485 °C. cFe= 0.449 J/g °C
(b) Calculate the final temperature reached when 324 J of heat is added to
a 24.5 g iron bar initially at 20.0 °C.
Constant-Pressure Calorimetry
Ammonium chloride is very soluble in water. When 4.50 g NH4Cl is
dissolved in 53.00 g of water, the temperature of the solution decreases
from 20.40 °C to 15.20 °C. Calculate the enthalpy of dissolution of NH 4Cl in
kJ/mol. Assume that the specific heat of the solution is 4.18 J/g °C and
that the heat absorbed by the calorimeter is negligible.
 Instant Hot and Cold Packs are Applications
of Exothermic and Endothermic Reactions
Reusable instant hot packs contain a
supersaturated solution of sodium
acetate. The crystallization of this
substance is an exothermic process and
https://2012books.lardbucket.org/books/pri
is initiated by clicking an aluminum
nciples-of-general-chemistry-v1.0m/s09-02-
enthalpy.html
disk.

Instant cold packs involve the

endothermic reaction of water and
ammonium nitrate or urea.

https://opentextbc.ca/chemistry/chapter/11-1-the-dissolution-process/
 Constant-Volume or Bomb Calorimetry

• Reactions can be carried

out in a sealed “bomb”
such as this one.
• The heat absorbed (or
released) by the water is
a very good
approximation of the
enthalpy change for the
reaction.
 Bomb Calorimeters Measure E

• Because the volume in

the bomb calorimeter is
constant, what is
measured is really the
change in internal
energy, E, not H.
• For most reactions, the
difference is very small.
Learning Activity

Watch “How a bomb calorimeter works”

by Marci Harvey

https://www.youtube.com/watch?v=VG9YG0VviHc
 Bomb Calorimetry Calculations
A 0.444-g sample of sucrose (C12H22O11) is burned in a bomb calorimeter
and the temperature increases from 20.00 °C to 22.06 °C. The calorimeter
contains 748 g of water and the bomb has a heat capacity of 420 J/ °C.
Calculate DE for the combustion reaction per mole of sucrose burned
(kJ/mol).
Hess’s Law

H is well known for many reactions, and it is

inconvenient to measure H for every reaction
in which we are interested.
However, we can estimate H using published H
values and the properties of enthalpy.
Hess’s Law is a Consequence of the First
Law

Hess’s law states that “if a

reaction is carried out in a
series of steps, H for the
overall reaction will be
equal to the sum of the
enthalpy changes for the
individual steps.”
Hess’s Law: Thermochemical Reactions can
be Treated Algebraically

Because H is a state
function, the total enthalpy
change depends only on
the initial state of the
reactants and the final
state of the products.
Using Hess’s Law
Given the following reactions:
2S(s)  3O 2 (g)  2SOΔH 3 (g)
= -790 kJ
S(s)  O 2 (g)  SO 2 (g) ΔH = -297 kJ
Calculate the enthalpy of the reaction in which sulfur dioxide is
oxidized to sulfur trioxide
2SO 2 (g)  O 2 (g)  2SO3 (g)
 Using Hess’s Law
Given the following reactions
H2O (l) → H2O (g) ΔH = 44.01 kJ
2 H2 (g) + O2 (g) → 2 H2O (g) ΔH = -483.64 kJ
Calculate the enthalpy for the decomposition of liquid water into gaseous
hydrogen and oxygen
2 H2O (l) → 2 H2 (g) + O2 (g)
Enthalpies of Formation (Hf)

An enthalpy of formation, Hf, is defined as the

enthalpy change for the reaction in which a
compound is made from its constituent elements in
their elemental forms.
Standard Enthalpies of Formation

Standard enthalpies of formation, Hf°, are

measured under standard conditions (25 °C and
1.00 atm pressure).
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in three steps:

C3H8 (g)  3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in three steps:

C3H8 (g)  3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• Imagine this as occurring
in three steps:

C3H8 (g)  3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)
 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
• The sum of these
equations is:

C3H8 (g)  3 C (graphite) + 4 H2 (g)

3 C (graphite) + 3 O2 (g)  3 CO2 (g)
4 H2 (g) + 2 O2 (g)  4 H2O (l)

C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)

Calculation of H

We can use Hess’s law in this way:

H = nHf°products – mHf° reactants

where n and m are the stoichiometric coefficients.

 Calculation of H
C3H8 (g) + 5 O2 (g)  3 CO2 (g) + 4 H2O (l)
H = [3(-393.5 kJ) + 4(-285.8 kJ)] – [1(-103.85 kJ) + 5(0 kJ)]
= [(-1180.5 kJ) + (-1143.2 kJ)] – [(-103.85 kJ) + (0 kJ)]
= (-2323.7 kJ) – (-103.85 kJ) = -2219.9 kJ
Calculation of Hrxn from Hf

Given the data in the table below, calculate the enthalpy for the reaction
C 2 H 5OH(l)  O 2 (g)  CH 3CO 2 H(l)  H 2 O(l)
Calculation of Hrxn from Hf

Given the data in the table below, ΔH°rxn for the reaction
4NH3 (g) + 5 O2 (g) → 4NO (g) + 6 H2O(l)
Definition: Chemical Fuels

• A chemical fuel is any material that releases energy

via a chemical reaction like combustion.
• The energy produced can be a source of heat or
used to perform work (via a heat engine).
• Chemical fuels can be classified according to
physical state
1) Solid fuels
2) Liquid fuels
3) Gaseous fuels
Classification of Chemical Fuels

• Primary or natural fuels are found in nature and can

be used without any physical or chemical
transformations.
• Secondary or artificial fuels are derived from
primary fuels through physical or chemical
transformations.
 Classification of Chemical Fuels

https://amjadknotes.files.wordpress.com/2013/11/classification-of-fuels.jpg
Fossil Fuels: Coal
Coal is a sedimentary rock mostly made of carbon.

https://www.quora.com/What-are-the-different-types-of-coal
 Fossil Fuels: Natural Gas

Natural gas is a gas mixture primarily made up of methane.

Malampaya Gas Field

https://www.researchgate.net/figure/Typical-Composition-of-Natural- https://businessmirror.com.ph/2018/06/18/government-eyeing-
Gas_fig23_317840680 malampaya-gas-field-takeover-after-contract-expires-in-2024/
Fossil Fuels: Petroleum or Crude Oil
Crude oil is a complex liquid mixture of hydrocarbons. Refining of
crude oil involves separation into different fractions by distillation.

Petron Bataan Refinery

https://www.cmegroup.com/education/les https://www.hydrocarbons-technology.com/projects/petron-bataan-
sons/a-look-into-the-refining-process.html refinery-philippines/
Definition: Biofuels

A biofuel is a renewable energy source derived from

biomass. Some examples of biofuels include
1. Biogas is methane gas produced by
decomposition of organic matter in the absence
of oxygen.
2. Bioethanol is produced by fermentation of sugars
or starches.
3. Biodiesel is produced from oils and fats via a
chemical reaction called transesterification.
http://2014.igem.org/Team:Concordia/Project/Sustainability
Definition: Fuel Value

The fuel or
calorific value is
the amount of
energy produced
per mass of fuel.
 Fossil Fuel Power Stations Burn Fossil Fuels
to Produce Electricity

https://chem.libretexts.org/Courses/Prince_Georges_Community_College/Chemistry_2000%3A_Chemistry_for_Engineers_(Sinex)/Unit
_6%3A_Thermo_and_Electrochemistry/Chapter_15%3A_First_Law_Thermochem/Chapter_15.7%3A_Fossil_Fuels
Assignment
1. Consider the following reaction:

2 CH3OH(g) → 2 CH4(g) + O2(g) H = 252.8 kJ

(a) Is reaction exothermic or endothermic?

(b) Calculate the amount of heat transferred when 24.0 g of CH 3OH(g)
is decomposed by this reaction at constant pressure.
(c) For a given sample of CH3OH, the enthalpy change during the
reaction is 82.1 kJ. How many grams of methane gas are produced?
(d) How many kilojoules of heat are released when 38.5 g of CH4(g)
reacts completely with O2(g) at constant pressure?
Assignment
2. Given the data in the table below and H for the
rxn
reaction
SO 2 Cl2 (g)  2H 2 O(l)  H 2SO4 (l)  2HCl(g) ΔH° = -62 kJ

Calculate the Hf of HCl(g) in kJ/mol.

Assessment

1. Construct a table comparing natural gas, coal, and

oil according to (a) origin, (b) fuel value, (c) other
uses, (d) chemical composition, (e) environmental
effects, etc.
2. Make a report on biofuels currently being studied
and used in the Philippines.
3. Write an essay or make a presentation on the
advantages and disadvantages of using biofuels as
an alternative energy source in the Philippines.
Reference

• Brown, T.L., LeMay Jr., H.E., Bursten, B.E., Murphy,

C.J., Woodward, P.M. (2015) Chemistry – The
Central Science, 13th ed., Prentice-Hall
International, Inc.