LESSON 3 - FUEL

Objectives

• State the first law of thermodynamics

• Define enthalpy and calculate enthalpy change to hydrocarbon fuels.
• Write and balance thermochemical equation.
• Calculate the air-fuel ratio for liquid fuels.

Introduction:
The discovery of petroleum and Its exploration has resulted in massive
accumulation of oil and gas which were used and consumed as energy to fuel our
electricity, and other needs of humans. The fuel called fossil fuel is a material resulting
from the decays of living things ,and for million of years, it was extracted then refined.
We now have the gasoline, diesel, alcohols and other sort of chemical compounds to
utilize as fuel to do the work of engines and equipment to produce another goods for
our consumption.

As the car runs its destination, a chemical reaction happens in the engine. We
call this, combustion or burning.

Rockets can work in space and must carry with them fuel and oxygen to store the
energy that rockets needed .

As the fuel is burned, energy is shifted from the chemical store and from the
chemical energy it is converted to mechanical energy to run the engine. The energy is
measured in joules.

As the fuel in the cars does its job, so in our body that stores energy to convert it
to physical activities like jogging , walking and other kinds of activity. The source of fuel
in our body comes from the input of food measured in calories.
A fuel is any material that can be made to react with other substances so that it releases
energy as heat energy to be used for work.

Heat Energy
 Is the result of the movement of tiny particles called atoms, molecules or ions in
solid, liquids and gases.
 Can be transferred from one object to another.
 The transfer or flow due to the difference in temperature between two objects is
called HEAT.
 The direction of energy flow is from a higher temperature to the substance of
lower temperature.
 It is measured in units of energy usually calories or Joules.

Thermal- Heat energy- depends on how fast the atoms and molecules are
moving( Kinetic energy)ex. the burner from stove, air conditioner, solar heat, boiling
water.

Chemical - ex. Coal and wood combustion reaction converts chemical energy into light
and heat, petroleum can be burned to release light and heat or changed to another
form of chemical energy.

Hydrocarbons- are molecules consisting of both hydrogen and carbon. They are most
famous for being the primary constituent of fossil fuels, namely natural ga, petroleum
and coal.

Hydrocarbon combustion- refers to the chemical reaction where a hydrogen reacts

with oxygen to create carbon dioxide, water and heat

Chemical Thermodynamics

Thermodynamics - means power developed from heat.

 - It is the science which deal with the transformation of energy of all
kinds from one form to another.
- It enables chemist to predict whether a particular chemical
reaction is theoretically feasible or not under a given set of condi

Thermodynamics Terms:

System - part of the universe under study

Surrounding - part of the universe outside the system.

Universe - the system and its surroundings

Open System - a system that can interchange matter and energy with its
surrounding.

Closed System - a system that allows the flow of energy but not matter

Isolated System - a system that cannot interact with its surrounding

Internal Energy - the total of the kinetic and potential energy for a system or part
of a system

State - a situation within a system that can be defined by properties such as

pressure, temperature and chemical composition

State functions - conditions that make up the state of a system and the
variables that measure them. The value of a state function depends on the initial and
final state of the system.

Adiabatic wall - one that does not permit heat transfer between the system and
surroundings.

Diathermal wall - allows the energy to pass through the wall.

Fundamental Quantities
 Time - the fundamental unit of time is seconds, ( s ). It is presently based on the
variant property of Cesium 133.

Length - the fundamental unit of length is meter (m). It is defined in terms of the
wave length of orange – red light from Krypton 86.

Mass - the fundamental unit of mass is kilogram (kg). The primary standard is a
cylinder of platinum – iridium alloy kept at the International Bureau of Weight and
Measures at Serves, Paris and France.

Force - the fundamental unit is Newton ( N) which is the force when applied to a
1,000 kg mass that will produce an acceleration of 1m/sec 2.

Temperature - the degree of hottest or coldest of a body and the fundamental

unit is Kelvin (K).

Volume - represents the amount of space occupied by a dimensional figure as

measured in cube units

Pressure - the pressure of a fluid on a surface is defined as the normal force

exerted by the fluid per unit area of the surface. In the SI system of units, it is the force
measured in N and the area in square meters, the unit of measure is Newton per square
meter (N/m2 ) called Pascal.

Work - the force acting through a distance. The unit of work in the system is
joule (J).

Heat - when a hot object is brought in contact with a cold one, the cold object
becomes warm. That something that is transform between such bodies is called heat
and is symbolized by Q.

Energy - the capacity to do work. In thermodynamics, it is easy to regard the

body on which work is done as separate and distinct from its surroundings.

The body on which attention is focused is called the system. Transfer of energy can
either be from the system to surroundings or from surroundings to the system.
First Law of Thermodynamics

The first law of thermodynamics is also called Law of Conservation of Energy.

It states that in any chemical or phase change , energy can neither be

created nor destroyed.

This means that total energy in the universe is constant.

A definite quantity of heat gives a fixed amount of mechanical energy and vice versa.
Since any transformation produced in a body is proportional to the heat equivalent, the
change in energy content of the body depends only on the difference between the
original and the final states.

Free energy - the maximum net amount of work obtained from a given process,
changing at a constant temperature and pressure from a higher to a lower state.

According to the first law, the internal energy of an isolated system is constant. The
actual value of energy for any system is not known and cannot be calculated.

Internal energy is therefore a state function.

The change in internal energy can be mathematically stated as:

ΔE = EB - EA

Where

EB = final state

EA = initial state

If the system uses some of its energy to do work (w) on the surroundings, the internal
energy of the system in the final system is:

Ef = E i + q - W
 Ef - Ei = q - W

ΔE = q – W

Where: q = heat absorbed from surrounding ( +q) ;

heat evolved (-q)

Ef = final state

Ei = initial state

W = work done on the system by the surroundings (+ W) ;

= work down by the system on the surroundings ( - W)

ΔE = change in the internal energy.

Enthalpy

Enthalpy is defined as the heat content per unit mass.

H = E - PV

Where:

H = enthalpy

E = internal energy

P = pressure

V = volume

Enthalpy, like internal energy is a function of state of the system and is independent of
the manner in which the state was achieved.

H = Hi - Hf

H (positive) = endothermic
 H ( negative) = exothermic

To determine the heat flow of a system , a calorimeter is used. This instrument uses
water as a standard. Thus, by measuring changes temperature of an accurately
measured amount of water, the amount of heat given off or absorbedat constant
volume, ΔE can be calculated.

Application of the First Law of Thermodynamics

The heat formation ( ΔHf ) of a compound is the H of the reaction ( ΔHf ) in which 1
mole of the compound is formed from its elements in their standard state.

ΔH = ( ΔHf ) products - ( ΔHf ) reactants

Example :

1. If 200 kcal of heat energy is absorbed by a system and 50 kcal of work is done
on the surroundings, calculate the change in energy.
Solution:
ΔE = q - W
ΔE = 200 kcal - 50 cal
ΔE = 150 Kcal

2. The heat combustion of CH4 at constant volume is measured in a calorimeter at

25 C and is found out to be -885.4 kJ/mol. Calculate ΔH.

Solution:
CH4 + 2 O2 CO2 + 2 H 2O E = -885.4 kJ /mol

ΔE = ΔH + RT

Δn = mols of gaseous product - mols of gaseous reactants

 = 1 mol - ( 1 mol + 2 mol ) = - 2 mol

Therefore:

ΔH = E + ( Δn ) RT

= - 890.25 kJ + 4.848

= - 890. 25 kJ

3. Determine the air–fuel( A/F) ratio on both a molar and mass basis for the
complete combustion of octane, C8H18.

Solutions:
Standard form of equation of combustion:
C8 H18 + Air CO2 + H2O
Or

C8 H18 + (O2 + N2) CO2 + H2O + N2 + Heat

Step 1. Balance the equation:

C8 H18 + 12.5 (O2 + 3.76 N2) 8 CO2 + 9 H2O + 47N2 + Heat

Step 2. Write the stoichiometric form

C8H18+ 12.5 O2 + 3.76 N2 8 CO2 + 9 H2O + 47N2 + Heat

Step 3. Get the molecular weight of Air

O2 =16 kg/mol x 2= 32 x 0.21 = 6.72

N2 = 14 x 2 = 28 x 0.79 = 22.12
Total = 28.84

Step 4. Get the molecular weight of fuel:

C= 8mol x 12 kg/ mol = 96 kgs.

H= 18 mols x 1 kg/mol = 18 kgs.

total = 114 kgs.
 The air –fuel ratio on molar basis : 12.5 (O2 + 3.76 N2

A/F = 12.5 + 12.5 x 3.76 = 59.5 kmol air/

1 kmol fuel
 
The air-fuel ratio on mass basis:

A/F = 59.5 kmol air / x 28.84 kg air / kmol air

Kmol fuel 114. kg fuel/ kmol fuel

= 15.05

4. How much heat is liberated in the combustion of 5.65 g. of octane?

Solutions:

Write the combustion equation, then balance

C8 H18 + 12.5 O2 8 CO2 + 9H2 O

Write the standard values of Enthalpy of formation of each element that are involved
in the equation.

Standard heat of formation: ∆Hf @ 298.15 K, 1atm from the Table of Enthalpy

C8 H18 = - 249.73 kJ/mol (liquid)

O2 = 0 (all elements in its standard form has 0 enthalpy)

CO2 = -393.5 kJ/mol (gas)

H2O = -285.83 kJ/mol (liquid)

Substitute in the formula:

∆Hc = ∑ mHf (products) - ∑ mHf (reactants)

={ 8 (-393.5) + 9( -285.83)} – {1(-249.73 + 0) }

 = - 5,470.67 kJ/ mol
The negative sign indicates exothermic-that means it gives off heat

Given is 5.65 grams of octane

Solve for the number of moles of octane equivalent to this weight:

Using the formula:

moles = weight / molecular weight = w /MW

To get the molecular weight refer to periodic table of elements:

for octane (C8 H18 ): C = 12 ; H = 1

C = 8 mols x 12 grams /mol = 96 grams

H= 18 mols x 1 gram/mol = 18 grams
total MW = 114 grams

moles = w / MW = 5.65 /114 = 0.049 moles

Based from our computed ∆Hc = -5,470.67 kJ/mol

Using ratio and proportion:

- 5,470.67 kJ / 1 mol = x / 0.049 mol

x = - 268.06 kJ of Heat is needed for combustion of 5.65

grams octane, negative sign means its an exothermic reaction.
 Exercises:

1. Calculate ΔH of the reaction

ZnS (s) + O2 (g) ZnO (s) + SO2 (g)

From the following data: ΔH in Kcal/mol

ZnS(s) = - 48.50
SO2 (g) = - 70.99
ZnO (s) = - 83.20

2. Calculate the heat evolved by 4.5 g of propane from the equation

C3 H8 + 5O2 3CO2 + 4 H 2O

From the following data ΔH in kJ/mol

C3 H8 = - 2043
CO2 = - 393.5
H2O = - 255.83