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Chemical reactions
Physical changes do not involve the production of new substances and are easily reversible. Chemical changes involve
the production of new substances as a result of a chemical reaction between two or more substances. Some indicators
of a chemical reaction (or chemical change) are:
Reactants are permanently converted into new products that have different physical properties.
Chemical reactions are difficult to reverse
Changes to the enthalpy of the system occurs, i.e. heat is released or absorbed
Energy changes in chemical reactions
The enthalpy of the system represents the stored chemical potential energy and depends on the chemical bonding
present in the substance. Exothermic reactions are associated with the decrease in the enthalpy of a system, while
endothermic reactions are associated with an increase in the enthalpy of a system.
For exothermic reactions (reactions that release energy), the change in enthalpy (H) has a negative value
For endothermic reactions (reactions that absorb energy), the change in enthalpy (H) has a positive value
Bond-breaking and bond-making

Chemical reactions such as exothermic or endothermic reactions require either the breaking of bonds or the
formation of new bonds, which explain the resulting changes in enthalpy to the system.
From the Law of Conservation of Energy, the quantity of energy released when one bond is formed is the same
amount of energy as when absorbed when this bond is broken (i.e. the energy input required).
If the energy absorbed to break bonds is greater than the energy released when new bonds are formed to make
products, then the reaction will be endothermic.
If the energy absorbed to break bonds is less than the energy released when new bonds are formed to make
products, then the reaction will be exothermic.
The bond energy is the amount of energy that is associated with breaking that particular bond. The stronger the
chemical bonding is in a compound, the higher the bond energy. For this reason triple bonds between carbon
atoms require more energy to break than double bonds between carbon atoms.
Heat of combustion
The combustion reactions especially those of hydrocarbons are exothermic releasing large quantities of energy from
the system. This is because the enthalpy of the products, i.e. water and carbon dioxide is much less than those in the
reactants.
For example the combustion of methane: CH
4 (g)
+ 2O
2 (g)
CO
2 (g)
+

2H
2
O
(l)
+ 890kJ energy


There is a decrease in the enthalpy of the system of 890kJ for every mole of methane that burns.
This large decrease in enthalpy indicates that much less energy is needed to break the bonds in the reactants than
the energy that is released when the products are formed.
The molar heat of combustion (H) of a substance is the heat released when one mole of the substance undergoes
complete combustion with oxygen at standard atmospheric pressure (100 kPa). Since it is defined in terms of heat
released it has by definition a positive value. The minus sign in H ensures that the value is always positive because
all combustion reactions are exothermic and release energy.
When new substances are formed, i.e. bonds are made, energy is released. When bonds are broken, for example in
decomposition, energy is absorbed from the surroundings in order to break the bond.
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Activation energy
Activation energy (E
A
) is the minimum energy input required to start the reaction. All reactions require this input
of energy, including exothermic reactions. For example the combustion of methane requires an ignition
temperature of 630C, or alternatively either a flame or spark to initiate the reaction.
The activation energy is often described as an energy hill that has to be overcome to allow the reactants to react
and become the products. Reactants without enough energy to overcome this energy barrier will not react, but
once this activation energy is reached, the reaction continues without need for additional energy.

Ignition temperature
The temperature will be reached where the fuel ignites and burns without the need for a flame or sparks. This is
called the ignition temperature.
The ignition temperature can be used to estimate the activation energy for a reaction between a fuel and the air.
In the case of hydrocarbons, the smaller hydrocarbon molecules such as methane are more stable and therefore
have a higher ignition temperature, and therefore more energy is required to overcome the activation energy
barrier.
Fuel Ignition Temperature (C) Fuel Ignition Temperature (C)
Hydrogen 585 Butane 405
Natural Gas 540-560 Pentane 260
Petrol 390-420 Hexane 225
Kerosene 380 Heptane 215
Diesel 300-350 Octane 206
Methane 580
Activated complex
The activated complex is an unstable transition stage in the reaction that exists at the activation energy hill.
At this point, the bonds in the reactants have been partially broken while those present in products are just being
formed. After a small period, this complex breaks apart.
The two possible paths for the reaction after the activated complex has broken apart are that either the reaction
will continue resulting in the formation of the products, or the reaction will not continue resulting in the
reformation of the reactants instead.

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Determining the rate of a reaction
In general, reaction rate can be determined by noting the rate of disappearance of reactants or rate of appearance of
products. Some reactions occur quickly, while others are slower.

By examining many different reactions, chemists have been able to produce some guidelines that are useful for
predicting reaction rates:
If a reaction does not involve bonding rearrangements, it is likely to be rapid at room temperature. For example,
the reaction between Ag
+
(aq)
and Cl

(aq)
occurs as a result of simple collisions between these two types of ions. No
complex bond-breaking and bond-forming processes are required.
If a reaction involves the breaking of bonds, it is slow at room temperature. For example, the reaction between
methane and oxygen involves the breaking of bonds in both the methane and oxygen.
These processes will only take place if the collisions between the molecules occur with sufficient energy and have
suitable orientation.
Combustion and reaction rates
Slow combustion
Slow combustion is the reaction usually between metals and oxygen. When a very active metal such as sodium, the
reaction occurs in a few seconds, while in the case of iron, the reaction rate is slower. These reactions are relatively
slow; releasing considerable amounts of heat, but because of their slow reaction rate and the oxide layer formed is
very thin, the rise in temperature is not significant. Some examples of slow combustion reactions include:
Rusting is the reaction occurs between iron and oxygen to form rust, which is iron oxide.
Burning of wood, coal and coke is another slow reaction, due to the small surface area of the fuel used.
Spontaneous combustion
Spontaneous combustion is when the fuel starts burning for no apparent reason, when the temperature is higher
than the ignition temperature. This is because the reactants already have sufficient energy to overcome the activation
energy barrier, and just need to be mixed to ensure a reaction. Some examples of spontaneous combustion reactions
include:
White phosphorus (P
4
) is an allotrope of phosphorus that must be stored underwater, otherwise it will combust
spontaneously when present in air, at low temperatures.
Brown coal deposits are known to combust spontaneously when exposed to air, due to the temperature change
when it starts oxidisation.
Explosive combustion
Explosive combustion reactions are extremely fast reactions that occurs when gases expanded at an extremely fast
rate, and is caused by a chemical between a fuel and air. The difference between spontaneous combustion and
explosive combustion is that the former requires the mixing of the fuel and the air in the right ratio (to ensure
complete combustion).
Some examples of explosive combustion reactions include:
Hydrogen and oxygen react to form water, when hydrogen gas in air is sparked. This explosive combustion is used
in rocket engines to produce the necessary thrust to propel the rocket forward.
The rate of a reaction, at any particular time, is defined as the change in concentration of a substance per unit
time, and therefore is measured in mol L
1
s
1

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Hydrogen and chlorine are stable unless in the presence of light, where a chain reaction resulting an explosive
combustion reaction and the form hydrochloric acid.
Dust particles can form explosive mixtures in air, since they have high surface area.
Factors affecting the rate of reaction
Concentration of reactants
The rate of reaction can be altered by altering the concentration of the
reactants. As the concentration of the reactant increases so do this rate of
the reaction. This can be determined experimentally, for example the
reaction between hydrochloric acid and magnesium.
Surface area of reactants
The surface area of the solid or liquid has an effect on the reaction rate.
The relationship is the larger the surface area, the faster the reaction. For example: a log of wood that is smaller pieces
burns faster than larger pieces of wood. This is also true with particular matter whose surface area is large, despite
being small in size, has the potential with sparking, combust explosively.
Temperature
The temperature also has an effect on the reaction rate, as temperature increases the reaction becomes faster. This is
notable also when cooking, that cooking time is quicker, when done at higher temperatures.
Catalysts
The addition of a catalyst has the effect of dramatically increasing the rate of the reaction. A catalyst is a substance or
mixture that increases the rate a chemical reaction without being permanently consumed in the reaction.
In industry, a wide variety of processes utilise catalysts to make industrial reactions faster and therefore more
economically viable. Some of the uses include the purification of metals, and also in the formation of plastics, rubbers
and synthetic fibres. An example of a catalyst
that is used is magnesium oxide MgO
2
, which
when added to hydrogen peroxide H
2
O
2

increases the rate of its decomposition into
water and oxygen gas.
Collision theory
The collision theory assumes that if particles
are to react, they must first undergo an
appropriate collision. The collision theory
requires that for a collision between reactant
particles to lead a chemical reaction, the
following conditions must be fulfilled:
The molecules must collide with enough energy to cause the bonds of the reactant molecules to break
The molecules must collide with an orientation that is favourable for bond-breaking and bond-forming
For a reaction to occur between reactant molecules, they must collide with a certain amount of energy, called the
activation energy. Unless this quantity of energy is reached, the colliding molecules simply bounce back of the
molecules and disperse.
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In addition to this, subsequent collisions require to have a favourable orientation that is the colliding substances must
do so at the appropriate angles and in the right position to allow the breaking of bonds (in the reactants) and the
formation of bonds in the products.

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Applying collision theory
The different activation energies for different reactions correspond to the ease in which the bond-breaking and
bond-making process can occur.
Concentration
The result of increasing the concentration is an increase in the number of collisions that occur, and therefore the
reaction rate will increase. For gases, increasing the pressure results in an increase of collisions, and therefore the
reaction rate will increase.
Surface area
In a solid or liquid, increasing the surface area means that more of the reactant is able to be collided with. This as a
result, means an increased rate of reaction. Solids often powdered as this increases surface area and therefore reaction
rate. Liquids are often used as sprays or subject to vigorous agitation in order a larger surface area is available.
Temperature
Moving particles possess kinetic energy. As these particles are heated, they become excited and move with a faster
vibrations. This results in an increase of kinetic energy of the particles. The increased velocity results in a greater rate of
reaction, as there are more frequent collisions. However this change in reaction rate is small due to velocity increase
alone.

However the main contributor to an increased rate of reaction is that more reactant molecules have sufficient energy
to overcome the activation energy barrier and therefore react to form products.
Catalysts
Catalysts lower the activation energy by allowing the reactants to partially react with them, and assisting in the
bond-breaking process. The catalyst means that less collision energy is required, so increased likelihood of successful
collisions and results in a faster reaction rate.

The kinetic energy of a particle is proportional to its temperature: E
K
T
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