CHEM ICAL

REACTIONS
Thermodynamics II
Introduction Non Reacting
Sensible
internal energy
System (Associated with T
and P Change)

In Chemical
reactions the
composition of
Latent internal
the system energy
changes during a Chemical
internal energy
(Phase change)

process
• Focus on combustion due to its importance in engineering.
• Principles developed so far are applicable to other chemical
reactions as well.
Our Scope of study
• Types of Chemical Reactions

Our Scope of
study
 Topics to be covered

Fuels and
combustion
Mass and
Energy
Balance of the
reacting
systems
Fuels and Combustion
• Fuel- Any material that can be burned to release thermal energy
• Most fuels consist primarily of Hydrogen and Carbon.
• Also known as Hydrocarbon Fuels.
• Denoted by general formula CnHm
• Exists in all phases (Solid, Liquid, Gas)
• Coal, Gasoline and Natural gas being the examples.
Coal
• Main constituent- Carbon.
• Also contain varying amount of Oxygen, Hydrogen, Nitrogen,
Sulfur, moisture and Ash.
• Most volatile HC vaporize first followed by the
less volatile.
•Coal • Liquid HC • Gas- Natural
• The main • Mixture of various Gas
constituent of coal is HCs but for
carbon. convenience we • Mainly Methane
consider it as a • (Ethane, Propane, H, He,
• Coal also contains single HC.
varying amounts of CO2,N2, Hydrogen Sulfate,
oxygen, hydrogen, • Gasoline-Octane Water vapors)
nitrogen, sulfur, (C8H18)
moisture, and ash. • CNG- 150-250 atm
• Diesel- Dodecane pressure.
• It is difficult to give C12H26.
an exact mass • Methanol CH3OH. • LNG (-162oC)
analysis for coal
since its • Natural Gas- CH4. • LPG- A byproduct
composition varies of Natural gas
considerably from processing or
one geographical crude oil refining.
area to the next and
even within the • Ethanol
same geographical
location • Methanol
Environmental Aspect
• Vehicles- Major source of Pollutants.
• Nitric oxide, Carbon monoxide, HCs, Greenhouse gas Carbon
dioxide.
• An increasing shift towards greener fuel is seen in the last two
decades.
• Environmental friendly fuels such as CNG, Alcohols, LPG, and
Hydrogen.
• Use of Electric and hybrid vehicles.
Combustion Pure Oxygen
Oxidizer
Welding, cutting

A Chemical reaction 20.9 % Oxygen

78.1 % Nitrogen
during which a fuel 0.9 % Argon
get Oxidized and Small amount of CO2, He, Neon, H
large quantity of 79 % N2, 21 % Oxygen
Air is used as an
energy is released Oxidizer
Why
is called combustion
Free
Readily available
Combustion
• Each mole of Oxygen entering a combustion chamber is
accompanied by 3.76 mole of Nitrogen (0.79/0.21)
• Figure
• 1 𝑘𝑚𝑜𝑙 𝑂2 + 3.76 𝑘𝑚𝑜𝑙 𝑁2 = 4.76 𝑘𝑚𝑜𝑙 𝑎𝑖𝑟
 Reactants
Components that
exist before the
reaction

Products
Components that
exist after the
reaction
Ignition Temperature
Substance Ignition Temperature (oC)
Gasoline 260
Carbon 400
Hydrogen 580
Carbon Monoxide 610
Methane 630

• Moreover, the proportions of the fuel and air must be in the

proper range for combustion to begin.
• For example, natural gas does not burn in air in concentrations
less than 5 percent or greater than about 15 percent
Conservation of Mass
• Chemical equations are based on the principle of conservation of
Mass.
• The total mass of each element is conserved during a chemical
reaction That is, the total mass of each element on the right-hand
side of the reaction equation (the products) must be equal to the total
mass of that element on the left-hand side (the reactants) even
though the elements exist in different chemical compounds in the
reactants and products.
• Also, the total number of atoms of each element is conserved during
a chemical reaction since the total number of atoms is equal to the
total mass of the element divided by its atomic mass
Total mass of the reactant is equal to total mass of the
products

Moles of the reactant and product are not the same.

The total number of moles is not conserved during a

Chemical Reaction
Air fuel Ratio
• Frequently used terms in analysis of combustion process.
• Used to quantify the amount of fuel and air.
• Denoted by AF.

Ratio of mass
of the air to the 𝑚𝑎𝑖𝑟
𝐴𝐹 =
mass of the 𝑚𝑓𝑢𝑒𝑙
fuel for a
combustion
process
 AF ratio can also be expressed as the ratio of mole
numbers of air to the mole numbers of fuel

m = NM
 Theoretical and Actual combustion
process
• Complete combustion
• Incomplete combustion
A combustion process is
A combustion process is incomplete if the
complete if all the Carbon combustion products
of the fuel burns to CO2, All
contain any unburned
the Hydrogen Burns to H20
and all the sulfur burns to fuel or components such
SO2 as
C, H2, CO or OH
Reasons for Incomplete combustion.

Insufficient
More O2O2
Reasons for Incomplete combustion.
• Greater tendency of Oxygen to combine with Hydrogen rather
than with Carbon.
• Hydrogen in the fuel normally burns to completion forming
water.
• CO or plain Carbon particles remain at the end.
Stoichiometric or theoretical Air
• The minimum amount of air needed to complete a combustion
of a fuel is called the stoichiometric or theoretical air.
• When a fuel is completely burned with theoretical air, no
uncombined oxygen is present in the product gases.
• The ideal combustion process during which a fuel is burned
completely with the theoretical air is called stoichiometric or
theoretical combustion of that fuel
• Theoretical combustion of methane is