Automotive Internal

Combustion Engines

Lecture # 4: Thermochemistry

Dr. Muhammad Ali Shahbaz

Lecture contents

 Ideal gas laws (revision)

 Composition of air and fuels
 Combustion stoichiometry
 Application of 1st law on combustion
 Combustion efficiency
 Application of 2nd law on combustion

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Ideal gas laws

 𝑝𝑉 = 𝑚𝑅𝑇 = 𝑛𝑅𝑇

𝑅 = 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡
𝐽
𝑅 = 𝑈𝑛𝑖𝑣𝑒𝑟𝑠𝑎𝑙 𝑔𝑎𝑠 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡 = 8.314
𝑚𝑜𝑙 𝐾

 = 𝑐𝑜𝑛𝑠𝑡𝑎𝑛𝑡

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 Composition of air and fuels

Air

 Consists of many gases: mainly nitrogen and air

 Volumetric composition
• Nitrogen: 78 %
• Oxygen: 21 %
• Other gases: 1 %
• For simplification: 79 / 21 ratio is used
 Mass composition is slightly different
• In English texts, molar ratios are used. In some texts mass ratios are used
• We will use molar ratios

 Molar mass of air: 28.96 g/mol

 Density of air: 1.18 kg/m3

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Composition of air and fuels

Fuel

 Commercial fuel are blends of different hydrocarbons

 Consists mainly of C and H
• Typically 86 % C and 14 % H
• May contain O and S
 Different classes of hydrocarbons
• Alkanes (paraffins) • Cylanes (cycloparaffins) • Alkenes (olefins)

• Alcohols
• Aromatics

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Combustion stoichiometry

 A complete combustion reaction results in two products

• CO2 and H2O
 RULE: conservation of mass

 For example: C3H8 + 502 = 3CO2 + 4H20

 General equation for balance

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 Combustion stoichiometry

 Stoichiometric combustion
• Just enough oxygen for complete conversion of all fuel into just CO2 and H2O
• Or SO2 in case
• With other inert gases remain unreacted

 y=b/a
• Fuel can be written as CHy

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Combustion stoichiometry

 Fuel/air equivalence ratio Ø

( )
• Given by: Ø=
( )
 Relative air/fuel ratio is also used sometimes. We will use Ø
( )
• Given by λ=
( )
 For stoichiometric combustion, Ø=λ=1
 For lean combustion, Ø<1 , λ>1
 For rich combustion, Ø>1 , λ<1

 Stoichiometric air/fuel ratio(per unit mass) of fuel)

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Combustion stoichiometry

Example 3.1
A hydrocarbon fuel of composition 84.1 percent by mass C and 15.9 percent
by mass H has a molecular weight of 114.15. Determine the number of moles
of air required for stoichiometric combustion and the number of moles of
products produced per mole of fuel. Calculate (A/F)s , (F/A)s , and the
molecular weights of the reactants and the products.

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Heating values

 For fuels where the precise fuel composition is not known, the enthalpy of the
reactants cannot be determined from the enthalpies of formation
 The heating value of the fuel is then measured directly
 QHV,p = (Δ H’)p,T Used more frequently
 QHV,v = (Δ H’)v,T

 Higher and lower heating values

• Difference of phase of water in products
• Mostly lower heating value is used in ICEs

 Heating values are measured in calorimeters

• Experiment??

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 End of lecture

?
Questions

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