The simplest organic compounds (compounds that contain carbon) contain only the elements Carbon and Hydrogen

Some are commonly used as fuelsOilGasolineDiesel FuelNatural gasLiquefied Petroleum Gas (LPG)Coal. In order to work with Hydrocarbons, we need to
know elements Hydrogen and Carbon first, using the Periodic Table of Elements. An arrangement of the elements in which Each element is presented by a
unique chemical symbol, Atomic Number (number of Protons) increases from left to right,Elements with similar properties fall in columns called groups
Saturated Hydrocarbons (Alkanes) Also referred to as Paraffins.Each carbon atom is bonded to the maximum possible number of atoms (either carbon or
hydrogen atoms)The bonds between atoms are all single covalent bonds.All have the general formula.Saturated Hydrocarbons (Alkanes)Each alkane differs
from the previous or the next molecule by the structural unit, the methylene groupAlkanes form a homologous series of compounds Alkanes are commonly used
as fuels Alkanes (cont.) The simplest alkane is Methane (CH4),the main component of natural gas (≈ 90%).The next simplest alkane is Ethane (C2H6). To draw
the structural formula of ethane,Remove one hydrogen atom from methaneReplace it with a methyl (-CH3) group.After ethane, the next alkane is Propane
(C3H8), the main component of LPG (Liquefied Petroleum Gas – Barbecue gas)To draw the structural formula of propane,Remove one hydrogen atom from
ethane.Replace it with a methyl (-CH3) group
Naming Straight-Chain Alkanes The IUPAC (International Union of Pure and Applied Chemistry) system for naming organic compounds rules are used:The
root indicates the number of carbon atoms in the chain.The suffix (-ane) indicates that the compound is an Alkane
Properties of Alkanes Have relatively low boiling points: Methane -161 ˚C, Ethane:-89 ˚C,,Propane:-42 ˚Cutane:-0.5 ˚C.As the number of atoms in the Alkane
molecule increases, the boiling point increases..Have low solubility in water (Immiscible with Water.Alkanes exist in a range of states (Gas, Liquid, and Solid)
under standard (IUAPC) conditions of temperature and pressure (0 ˚C and 1 atm),Methane, Ethane, Propane and Butane are all gases at room temp.Pentane
through DoDecane are liquid at room temperature.Alkanes having over 50 carbon atoms are solid at room temperature
Reactions of Alkanes Combustion Reaction – The reaction of Alkane with oxygen that occurs only at high temperatures (studied in detail
later).Dehydrogenation Reaction – A reaction in which, hydrogen atoms are removed and the product will become an unsaturated hydrocarbon Halogenation: a
reactions in which one or more hydrogen atoms of an Alkane are replaced by some halogen atoms (F, Cl, Br, I).Facts about the halogenation of Alkanes.The
reactivity of the halogens decreases in the following order Halogenation of Alkanes reduce their combustibility. As the number of “C-H” bonds decreases, the
halocarbon product will be less flammable/combustible.Some halocarbons are in fact used as fire extinguishing agents (CCl4)
Unsaturated Hydrocarbons (cont.)
AlkenesResult when certain number of hydrogen atoms are removed from Alkanes through Dehydrogenation Reaction,Contain at least one carbon double bond,
Double bond involves four bonding electrons between two carbon atoms,obey the general formula,Each alkene is different from the previous or the next
member by the unit. Therefore, forming a homologous series The simplest alkene is Ethene, C2H4, also called Ethylene.Ethylene is used to make Polyethylene, a
widely used plastic. Ethylene is the agent used to ripen fruitsAlkenes (cont.)Naming Straight-chain Alkenes. The IUPAC (International Union of Pure and
Applied Chemistry) system for naming organic compounds rules is followedThe root indicates the number of carbon atoms in the chain.The suffix (-ene)
indicates that the compound in an Alkene Properties and uses of Alkenes Have boiling points that are slightly lower than corresponding Alkanes,Ethene at - 104
˚C, compared to Ethane (-89 ˚C),Propene (also called Propylene) at - 48 ˚C, compared to Propane(-42 ˚C),Butene at almost - 6 ˚C, compared to Butane(-0.5
˚C).Most Have low solubility (immiscible) in water. The double bond makes them more reactive than Alkanes.Use of Alkenes: Mainly used as starting material
for making plastics
Reactions of AlkenesCombustion reaction – The reaction of an Alkene with oxygen). The reaction in which an Alkene and either bromine or chlorine react to
give a di-bromo or di-chloro compound.Hydrogenation Reaction – in which, hydrogen atoms are added and the product will be a saturated hydrocarbon
AlkynesResult when certain number of hydrogen atoms are removed from Alkanes or Alkenes.Contain at least one carbon triple bond.Triple bonds involve six
bonding electrons between two carbon atoms. Obey the general formula. Each compound is different from previous one unit. Therefore,They form a
homologous series.The simplest alkyne is Ethyne, C2H2, also called “Acetylene”.Acetylene is used as a fuel in welding / cutting torches
Naming straight-chain AlkynesThe IUPAC (International Union of Pure and Applied Chemistry) system for naming organic compounds rules is used.The root
indicates the number of carbon atoms in the chain.The suffix (-yne) indicates that the compound in an Alkyne.Have low solubility (Immiscible) in water.The
triple bond makes them much more reactive than Alkanes.Used as:minority components of gasoline or,to make agricultural and pharmaceutical products
Reactions of Alkynes Combustion reaction – The reaction of Alkyne with oxygen.Addition reaction – The reaction in which an Alkyne and either bromine or
chlorine react to give a di-bromo or di-chloro compoundReactions of Alkenes (cont.).Hydrogenation Reaction – in which, hydrogen atoms are added and the
product will be a saturated hydrocarbon. Unsaturated Hydrocarbons (cont.:Aromatic Hydrocarbons Contain a six-membered ring of carbon atoms, called the
Benzene ring (C6H6):Unsaturated Hydrocarbons (cont.).Aromatic Hydrocarbons (cont.):Are important in fire chemistry because they can produce sooty smoke
easier than aliphatic hydrocarbons.
Stoichiometry Definition: The numerical relationships among chemical quantities in a balanced chemical equation.Application:Stoichiometry allows us to:
predict the amount of one reactant required to completely react with a certain amount of another reactant. Predict the amounts of products that form in a
chemical reaction based on the amounts of reactants.A combustion reaction happening at stoichiometric condition, results in: Maximum Temperature,Maximum
Heat Release Rate,Maximum Efficiency.Molar mass of Carbon is 12 grams of Carbon.Molar mass of Oxygen is 16 grams of Oxygen.Molar mass of Hydrogen
is 1 gram of Hydrogen.Molar mass of Nitrogen is 14 grams of Nitrogen
Combustion Process – Formal Definition“A chemical process of oxidation that occurs at a rate fast enough to produce heat and usually light in the form of
either glow or flame” Combustion Process – General PropertiesA chemical reaction,An exothermic reaction, Occurs so rapidlyReleases heat within the
combustion zone,the temperature of the reaction zone becomes much higher than that of the surroundings.
Complete combustion (of hydrocarbons):When a hydrocarbon undergoes complete combustion, the products of the reaction will be Carbon dioxide and water
vapour.
Incomplete Combustion (of Hydrocarbons):The incomplete combustion of hydrocarbons results in soot, smoke and Poisonous and/or Irritant gases (CO,
HCN, Acrolein, etc.) as well as carbon dioxide and water vapor. Fire: A form of combustion reaction,Soot: Black particles of carbon produced in a
flame,Smoke: The airborne solid and liquid particulates and gases evolved when a material undergoes Pyrolysis or combustion Some common Products of
Incomplete Combustion: Carbon monoxide: CO (Narcotic/Asphyxiant).A Colourless, Odorless, and Tasteless gas: Toxic (20,000 ppm concentration in air
causes incapacitation in 2 min.).Produced in Oxygen-limited atmosphere or, When the combustible material contains Cyclic Hydrocarbons or Hydrocarbon
derivatives
Some common Products of Incomplete Combustion (cont.): Hydrogen Cyanide: HCN (Narcotic/Asphyxiant),A colourless gas. Smells like bitter
almond:Produced in oxygen-limited atmosphere or When burning material contains:Wool,Nylon,,Polyurethanes, and similar polymers10 to 40 times as toxic as
Carbon Monoxide Some common Products of Incomplete Combustion: Acrolein: CH2=CH-CHO or (C 3H4O).A colourless and extremely Irritant Vapour. It
smells like burnt fat.Produced from Pyrolysis of Wood, Paper and Cotton,As low as 1 ppm concentration in air causes irritation of eyes and nose.Other harmful
or irritant products of incomplete combustion include: Oxides of Nitrogen, NO (Nitric oxide),NO2 (Nitrogen dioxide)
and many more (NH3, SO2, H2S, HF, HCl, etc…).Note: CO, NO, NO2, CO2 are all Oxides
Flaming combustion is one that involves flame, such as:The yellow flame of a candle,The blue flame of a gas burner. Its Properties: Very fast reaction,Involves
very high temperatures A gas phase reaction Non-flaming combustion is combustion without flame. Such as: The burning of a cigarette or The burning of
charcoal. Other names for Non-flaming combustion: Smoldering combustion,Glowing combustion. Its Non-flaming combustion Properties: Slow reaction
Involves lower temperatures Involves incomplete combustionMay involve char formation Occurs at the surface of some solid combustibles Direct Oxidation
The combustible material burns without undergoing Decomposition.Examples are combustions of: Methane (gas),Heptane (liquid),Sulfur (solid)
Direct Oxidation of Sulfur: Solid sulfur, when heated to 207°C burns with a blue flame:Pyrolysis-then-Oxidation.The fuel undergoes Chemical
Decomposition(due to heat) before oxidation takes place,Pyrolysis is a chemical change and an endothermic reaction,Some complicated hydrocarbons or
hydrocarbon derivatives are involved in this form of combustion
The combustion process comprises three consecutive stages:Initiation of Combustion (ignition),Spread of Combustion,Termination of Combustion. Ignition
is defined as the process of initiating self- sustained Combustion..To start a fire, some heat (thermal energy) is required.The heat is provided by an Ignition
Source.Common Ignition Sources: A pilot flame,Static spark,Friction,Overheating in an electrical circuit, Lightning,Non-flaming source (cigarette),Spontaneous
(self generated) ignition
Spread of Combustion Begins with the branching chain reactions.The free radicals or atoms recombine with other free radicals or atomsThe recombination
process produces more heat in the combustion zone. Spread of Combustion Depends on: the state, either fuel,Gas,Liquid,Solid.
Spread of Combustion in Flammable Gases Depends on: The extent of mixing with air prior to combustion Diffusion, Pre-mixed, The motion and turbulence in
gas movement,Laminar,Turbulent
Spread of Combustion in Flammable/Combustible Liquids,Depends on: Subdivision (form) of the liquid,Pool,Foam,Spray,Thin film,Vapor Pressure of the
liquid,Ambient Temperature,Air movement,Motion of the liquid,Stationary,Flowing
Spread of Combustion in Combustible Solids: Depends on: Subdivision (shape) of the solid Dust or powder,Thin sheet (higher spread rate),Thick slab ,Surface
Orientation,Vertical spread,upward (much faster),Downward,Horizontal spread(air current is important), Termination of Combustion.
Four Methods to extinguish a fire:Removal of, or blanketing the fuel,Cutting off or diluting the Oxygen supply,Removal of heat (cooling),Breaking the
combustion chain reaction
Removal of, or blanketing the fuel:Close valves to cut supplying of gas or liquid fuel,Remove solid combustibles from the fire area,Apply foam to blanket the
liquid fuel,Apply Chemicals (Dry Powder) to blanket the burning metal
Cutting off or diluting the oxygen supply:Apply CO, Apply Inert gasRemoval of Heat - Cooling,Apply water,Apply halocarbons.
How does heat removal suppress combustion?Removal of heat: Slows down the combustion reaction.Less heat is generated.Temperature of reaction zone
decreases.Reaction does not sustain.
Flame:A body or stream of gaseous material involved in the combustion process and emitting radiant energy at specific wavelength determined by the
combustion chemistry of the fuel. In most cases, some portion of the emitted radiant energy is visible to the human eye.
Flames Categories:Flames are categorized in three ways:Degree of Fuel and Air Mixing,Flow of Reactant Gas Molecules within the Flame,Flame Movement
1)Degree of Fuel and Air Mixing:Diffusion Flames and Premixed Flames
Diffusion Flames Fuel and air are diffused into each other after the combustion begins
Diffusion Flames Characteristics: Spread slowly ( some cm/s),Yellow and sooty,involve low temperatures (Few Hundred °C), Have slow rate of heat
release,Involve incomplete combustion
Premixed Flames:Fuel and air are mixed before combustion takes place.Characteristics: Spread rapidly ( 3m/s or faster),Usually involve complete combustion at
stoichiometric ratios,Are blue and without visible smoke,Involve high temperatures (1900 – 2700 °C for Methane)
2)Flow of Gas Molecules within the Flame: Laminar Flames and Turbulent Flames Laminar Flames:Small with little side to side movements,Gas molecules
follow a smooth path when moving within the flame,At a specific point inside the flame,Temperature remains constant,Gas velocity remains constant,Heat
release rate remains constant,A laminar diffusion flame, has a height less than 10 cm.Turbulent FlamesUsually are large (flames of natural fires),Gas molecules
follow erratic paths while moving within the flame,involve many changes in direction,At a specific point in the flame,Temperature changes constantly,Gas
velocity changes constantly,Heat release rate changes constantly.A turbulent diffusion flame has a height taller than 30 cm
3) Flame movement:Stationary and propagating.Burns in a fixed position.Fuel is brought to the flame (such as in burners).Used to measure flame properties of
different combustibles.Cloud of combustible gas spreads through flammable fuel/air mixture.Propagates (moves) through the combustion zone
Smoke-Point Height: The height of the shortest, laminar-diffusion flame, that will just release black smoke from its tip for a given combustible gas or
vapour..The Smoke-Point Height is a convenient and useful measure of:Combustible Smokiness :Flame Radiative Emission
Correlation between Smoke-Point Height and fuel properties:Smoke point height is lower for complicated fuels with higher molecular weights fuels with double
or triple bonds (unsaturated fuels)
Heat (H): A form of energy characterized by vibration of molecules and capable of initiating and supporting chemical changes and changes of state. Heat is
measured in: Joule (J),Calorie (4.18 J),BTU (252 Cal)
Heat Release Rate (HRR): The rate at which thermal energy is generated by burning.
Heat flux: The measure of the rate of heat transferred to a surface area. Cal/hr x m*2
Heat Transfer : The exchange of thermal energy between materials through:Conduction,Convection,Radiation
Conduction: Heat transfer to another body or within a body by direct contact.Conduction is not a significant factor in fire spread.
Convection: Heat transfer by circulation within a medium such as a gas or a liquid
Convection (cont.).Convection is the primary mode of heat transfer in enclosure fires. (50% to 75%)
Radiation:Heat transfer by way of electromagnetic energy
In fire scenarios, radiant heat transfer from an upper hot gas layer, smoke, and the flame, is a significant concern.Heat transfer by radiation accounts for almost
30% of the total heat released during combustionRadiant heat from flames causes:Feedback of energy to unburned fuel,Spread of fire to nearby combustibles
Close approach of fire fighters to become difficult or impossible
Radiation from smoke layer,Smoke layer radiates heat to unburned material,Radiant heat from smoke may affect fire (flame) spread,Assuming an ideal radiator,
smoke layer emits:,≈ 33 kW/m2 at 600°C,≈ 75 kW/m2 at 800°C
Radiant fraction from hydrocarbon diffusion flames:increases with increasing molecular weight and increases with progressive un-saturation
Smoke-Point Height of a Combustible material.The height of the shortest laminar diffusion flame for a combustible that will release black smoke from its tip.
Smoke-point height is a convenient and useful measure of combustible smokiness and of flame radiation emission.
Correlation between Smoke-Point Height and radiant fraction
Smoke point height is low for complicated fuels with higher molecular weights and fuels with double or triple bonds (unsaturated fuels)
One may conclude that: Radiative fraction of flames increases as the Smoke-point height of the fuel decreases
Heat transfer: g/s x kj/g= kJ/s
Flammable Gases:Undergo Direct Oxidation with oxygen,Need no initial energy for Phase Change,Need No initial energy for Pyrolysis,Produce high Heat
Release Rate upon reacting with oxygen,Flammable Gaseous Mixtures,Stoichiometric MixturesNonstoichiometric mixtures are Lean mixtures asnd Rich
mixtures.With Stoichiometric Mixtures:Upon termination of the combustion reaction:There is no surplus of Oxygen,There is no surplus of the fuel
Stoichiometric oxygen(air)/fuel mixtures involve Complete combustion,Production of water vapour and Carbon dioxide only,Maximum Flame Spread Rate (~ 3
m/s),Maximum Flame Temperature (depends on the fuel type) Stoichiometric oxygen(air)/fuel mixtures.Mixtures of fuel & Oxygen produce higher
temperatures than mixtures of fuel and Air. Any impurity (such as extra Nitrogen) lowers the flame temperature
Lean mixture
A fuel / Oxygen (air) mixture containing more Oxygen than required to fully oxidize the fuel molecules
Rich mixture
A fuel/ Oxygen (air) mixture containing insufficient Oxygen toully oxidize the fuel molecules.
Ignition of Flammable Gases Gases are easier to ignite than liquids and solids because::No initial energy is needed for change of phase,No initial energy is
needed for pyrolysis
Ignition of flammable GasesDepends on:Chemical composition and structure of the gas Concentration of the gas in gas / Oxygen (air) mixture Temperature and
humidity,Pressure
Types of Ignition:Spark Ignition that is accomplished by heat from a spark/pilot flame.Thermal Ignition is accomplished by contact with a hot solid surface.
Example: the ignition of carbon disulfide (CS2) in contact with a steam pipe at 100°C
Spark Ignition of Combustible Gases Requires minimum energy at stoichiometric mixtures,Gas/oxygen mixtures are much easier to ignite than gas/air mixtures
Saturated Hydrocarbons (alkanes) ignite similarly in air,Progressive unsaturation (double or triple bonds) favors ease of ignition,Certain gases (CS 2, H2, and
C2H2) can ignite with a very small sparkenergy
Factors Affecting Flammability Limits of Gases (cont.):Temperature:The UFL increases substantially by increasing temperature.The LFL is minimally affected
by change in temperature.The Flammability Range increases with increasing temperature.Atmospheric Pressure.The UFL is significantly affected by pressure
variations.The LFL is relatively unaffected by the change in pressure.The Flammability Range increases as pressure increases.
Oxygen Concentration:As the Oxygen concentration decreases:The UFL decreases significantly and The LFL increases slightly The Flammability Range
decreases