Kinetics (Rates): Part 1

2021
Unit 1 Chemistry
 Objectives
● Explain the concepts associated with reaction rate

● Design experiments for studying factors that affect

the rate of reaction

● Explain the effect of temperature, catalyst and other

factors on the rate of reaction using boltzmann
distribution energies
 What is the Rate of a Reaction
• The study of the factors that affect the rate of
reactions is called kinetics.
• Rate is really a measure of time take for a reaction
to be completed.
• This can be determined in one of two ways:
– The rate of use/ consumption of a reactant over time
– The rate of creation/ formation of a product over time
 Rate of a reaction
• This the speed at which a reaction happens.
• If a reaction has a low rate, that means the molecules combine at a slower
speed than a reaction with a high rate.

• Measures the rate of consumption of a reactant

• Measures the rate of formation of a product

Rate = amt of products formed or reactant consumed

time taken
 Rate of Reaction
The average rate of a reaction can be
represented as:
– Amount of product formed or reactant consumed /time taken

Or more specifically
– Change in concentration (of product or reactant) / time take for change
• Therefore : rate = moldm-3s-1
 Rate of Reaction
• Rate = moldm-3s-1
• You can also see it expressed for a reaction where
A B as:
– With respect to A
-d A t /dt (meaning loss in concentration of A over time )

– With respect to B
d B t
/dt (meaning gain in concentration of B over time )
 Measuring Reaction Rate
• Depending on the type of reaction a method
can be selected to determine how the reactants
or the products are changing over time.

• The exact method will be dependent on the

nature of the reaction.
 Gas measurement method
Measuring the Amount of Product Formed
• If a gas is formed, its volume may be measured at
suitable time intervals using a graduated gas syringe
 Gas Measurement Method
Measuring the Amount of Product Formed by
Displacement of Water
• If the gas is insoluble in water, it may be measured by the
displacement of water from a measuring cylinder filled with water
 Determining Rate using
Concentration/time graph Method
 FINDING THE RATE FROM A CONCENTRATION
VERSUS TIME GRAPH
•To determine the rate of a reaction, changes in concentration
at suitable time intervals must be obtained

•A graph of concentration versus time is plotted

•The rate of the reaction at time (z) is determined by drawing a

tangent at time(z) and calculating the gradient at this point

•The tangent at zero is called the initial rate which is the rate at
the start of the reaction

•The rate of the reaction is greatest at the start of the start of

Determining Rate using Concentration/time graph
Method
•
Continuous vs initial rate data
When we follow one experiment over time recording the change in
concentration we call it a continuous rate method.

• The gradient represents the rate of reaction. The reaction is fastest at the start
where the gradient is steepest. The rate drops as the reactants start to get used
up and their concentration drops.

• The graph will eventually become horizontal and the gradient becomes zero
which represents the reaction having stopped.

• Sometimes when doing multiple rate experiments varying something like

concentration and temperature we just focus on the initial rate for each different
experiment.

• We may still have to draw concentration vs time graphs to be able to calculate

the initial rate.
 Continuous vs Initial rate data
• When a graph of concentration of reactant is plotted vs
time,the gradient of the curve is the rate of reaction.
• The initial rate is the rate at the start of the reaction
where it is fastest
• Reaction rates can be calculated from graphs of
concentration of reactants or products vs time by drawing
a tangent to the curve and calculating the gradient of the
tangent.
• This can be done at several different points on the graph
 Colorimetric Method
https://www.youtube.com/watch?v=HoPvgn-Wxns

• In physical and analytical chemistry, colorimetry or

colourimetry is a technique used to determine the
concentration of colored compounds in solution.

• A colorimeter is a device used to test the concentration

of a solution by measuring its absorbance of a specific
wavelength of light.
 Colorimetric Method
• When a reactant or a product is coloured, the time
taken for the colour to disappear or appear can be
measured

• The colour change can be recorded using a

colorimeter or spectrophotometer. These measure
the absorption of visible light due the presence of a
coloured substance.
 Colorimetric Method
• A standard
calibration graph of
absorbance vs.
Concentration is
plotted

Absorba
nce
• Reaction rate can be
taken by determining
the tangent.
 Colorimetric Method
• For example with the following reaction
CH3COCH3(aq) + I2(aq) ⎯⎯→ CH3COCH2I(aq) + H+(aq) + I- (aq) colourless (brown/yellow) colourless
colourless

• The concentration of iodine decreases and the brown/yellow

colour intensity of the reacting solution also decreases.

• The change in colour intensity allows the use of colorimetry to

follow the reaction kinetics.
 Titration Method
https://www.youtube.com/watch?v=eJUNWJl7_qE
• This is suitable for reactions in solutions e.g. hydrolysis of an ester
– CH3COOC2H5 (l) + OH- (aq) => CH3COO-(aq) + C2H5OH (aq)

• A small sample of an aliquot is pipetted at intervals during the course of the reaction and
quenched by
– Quick freezing in an ice bath
– Quickly adding sodium carbonate

• Note the aim of quenching –

– Remove K.E. so that particles lack energy to react or
– to neutralize one of the reactant without affecting the other reactant so it can be analysed.

• Analysis of the sample is done by titration against a standard solution to determine its
concentration at every time interval

• A graph of concentration versus time may be plotted

• Rate can be found by drawing tangents at different times and the gradient determined
 Conductometric Method:
Measuring change in electrical conductivity
• Measuring the conductivity of reaction
mixture can be used if there is a change in the
number of ions in the reaction mixture.

• The reaction on the right would increase in

conductivity over time as the ionic products
are produced.
 Measurement of change of mass

• If a reaction gives off a gaseous product then the

mass of the whole reaction mixture could be
monitored over time if the gas produced is
allowed to escape.

• This method works better with heavy gases such

as CO2 rather than light gases like hydrogen.
Measurement of change by mass
Mass vs Time graph
 Collision theory
•Two species can only react together if they come into
contact with each other. They first have to collide, and then
they may react.

•Why "may react"?

–It isn't enough for the two species to collide
• they have to collide the right way around (orientation),
• and they have to collide with enough energy for bonds to break.
(only a fraction of the reactant particles have energy greater than
activation energy)
Collision Theory
•Molecules possess kinetic energy
•Molecules will collide with each other due to random motion

Consider A + B → C

•Collision Theory:
–Both molecules must collide
–Collision must be accompanied by adequate energy
–Collision must be of the correct orientation
 Collision Theory
Consider a simple reaction involving a collision between
two molecules –
ethene, CH2=CH 2, and hydrogen chloride, HCl, for
example.
These react to give chloroethane.

•The reaction can only happen if the

hydrogen end of the H-Cl bond
approaches the carbon-carbon double
bond. Any other collision between the
two molecules doesn't work. The two
simply bounce off each other.

•Of the collisions shown in the diagram,

only collision 1 may possibly lead on to a
reaction.
 Activation energy
•Even if the species are oriented
properly, you still won't get a reaction
unless the particles collide with a
certain minimum energy called the
activation energy of the reaction.

•Activation energy is the minimum

energy required before a reaction can
occur.

•You can show this on an energy

profile for the reaction. For a simple
overall exothermic reaction, the
energy profile looks like this:
Collision Theory
• An
energy profile diagram representing the
conversion of reactants to products.
Potential
Energy
 What factors influence the rate of a
chemical reaction?

• Concentrations of reactants
• Catalysts
• Temperature
• Surface area of a solid reactant
• Pressure of gaseous reactants or products
Effect of CONCENTRATION on the rate of reaction
•For many reactions involving liquids or gases, increasing the
concentration of the reactants increases the rate of reaction.
–In a few cases, increasing the concentration of one of the reactants
may have little noticeable effect on the rate. Collisions involving two
particles
–The same argument applies whether the reaction involves collision
between two different particles or two of the same particle.

•In order for any reaction to happen, those particles must first
collide.

–This is true whether both particles are in solution, or whether one is

in solution and the other a solid.
–If the concentration is higher, the chances of collision are greater.
 Effect of Pressure
•Increasing the pressure on a reaction involving reacting gases increases
the rate of reaction.

•Changing the pressure on a reaction which involves only solids or liquids

has no effect on the rate.

•Increasing the pressure of a gas is exactly the same as increasing its

concentration.

•If you have a given mass of gas, the way you increase its pressure is to
squeeze it into a smaller volume.
–If you have the same mass in a smaller volume, then its concentration is higher.
 Pressure cont’d
•In order for any reaction to
happen, those particles must first
collide.

•This is true whether both particles

are in the gas state, or whether one
is a gas and the other a solid.

•If the pressure is higher, the

chances of collision are greater.
 Effect of surface
area
• The more finely divided the solid is, the faster
the reaction happens.
– A powdered solid will normally produce a faster
reaction than if the same mass is present as a
single lump. The powdered solid has a greater
surface area than the single lump.

• You are only going to get a reaction if the

particles in the gas or liquid collide with the
particles in the solid.

• Increasing the surface area of the solid

increases the chances of collision taking
place.
 Effect of Temperature
•An increase in temperature increases the kinetic energy of
the reactant particles.
–This increases the number of collisions and also the fraction of
particles having kinetic energy higher than the activation
energy.
• Thus increasing the effective collision frequency and hence increasing
the rate of reaction

•Maxwell and Boltzmann calculated the distribution

velocities amongst molecules of gases using the laws of
probability.
–The kinetic energy of molecules is shown graphically
 The Maxwell-Boltzmann Distribution

The Maxwell-Boltzmann distribution shows how the speeds (and hence the
energies) of a mixture of moving particles varies at a particular temperature
If a particle is not in the shaded area, then it will not have the required
energy so it will not be able to participate in the reaction
 Maxwell Boltzmann Distribution
• The Maxwell-Boltzmann energy distribution shows the spread of
energies that molecules of a gas or liquid have at a particular
temperature.

• It is not a symmetrical distribution. The particles have such a range

of energies because in a sample of gas with many millions of
particles there are constant collisions between particles

• Often when there is a collision between two particles which bounce

off each other, one particle may gain energy and speed up and the
other particle must therefore lose this energy and slow down.
– This process results in there being a range of energies
 Maxwell Boltzmann Distribution
• The particles that collide with energy greater than the activation energy
will react successfully. The ones that collide with energy less than the
activation energy will just bounce off each other.

• You might ponder how a reaction go to completion if few particles have

energy greater than the activation energy.

• The particles can gain energy, through collisions,so eventually a lower

energy could potentially gain energy greater than activation energy.
– The size of the activation energy is an important limiting factor here
though.
– Chemical reactions with high activation energies will be slow
reactions.
 Maxwell Boltzmann Distribution
• At higher temperatures the energy of the particles
increases. They collide more frequently and more often
with energy greater than the activation energy. More
collisions will be successful and result in a reaction.

• As the temperature increases, the Maxwell Boltzmann

distribution shows that a significantly bigger proportion of
particles have energy greater than the activation energy,
so the frequency of successful collisions increases
Catalyst
•Affects the rate of a
reaction without being
consumed.

•It provides an alternative

pathway which has a lower
activation energy
 CATALYST
Catalysis is the process in which the rate of a
chemical reaction is either increased or decreased
by means of a chemical substance known as a
catalyst.

A catalyst is not consumed by the reaction itself.

Catalysts that speed the reaction are called positive

catalysts.
 CATALYST
•Catalyst are divided into two (2) groups. These are
–Synthetic catalysts
–Biological Catalyst (known as enzymes which are proteins and are found in living
things)

•Synthetic Catalysts are further divided into two groups. These are

–Homogeneous Catalysts – the catalyst and the reactant are in the same physical
state
–Heterogeneous Catalysts – the reactant and the catalyst are in different physical
state e.g. in the Haber Process

–(read extra in maraj and note relevant equations pg 128 to 132)

 Effect of Catalysts
• Definition: Catalysts increase reaction rates without getting used
up.

• Explanation: They do this by providing an alternative route or

mechanism with a lower activation energy

• Nb- A heterogeneous catalyst is in a different phase from the

reactants

• Heterogeneous catalysts are usually solids whereas the reactants

are gaseous or in solution. The reaction occurs at the surface of the
catalyst.
Effect of Catalyst
Effect of catalyst