Chapter 1

The rate of a chemical reaction is the rate of change of concentration of a reaction or product
with time, units in mol dm-3 s-1.
Collision theory- for a reaction to take place, reactants must collide with kinetic energy greater than or
equal to the activation energy of the reaction and the correct orientation.
The molecules move at different speeds, they possess different amounts of kinetic energy. The total
number of molecules with energy equal or greater to the activation energy is given by the area under the
end of the curve. The use of a catalyst affects the position of the activation energy, meaning more
molecules have sufficient energy to collide and react.
Temperature affects the rate of a reaction; higher amount of kinetic energy, higher proportion of
successful collisions within a given time.
If the pressure of a gaseous system s increased, the molecules are packed more closely together.
Theres no change in the speed of the molecules. Theres a higher frequency of successful collisions.
8 Ways to measure the rates of reaction:
1) Titration:
Used to measure the rate of reaction. Determined by the concentration and time taken for the reaction to
complete.
Measure samples of the reactants of known concentrations
Mix them together, start clock and stir
At regular intervals withdraw samples using a pipette, quench the reaction (stop it) by
adding ice cold water. The time it takes for the reaction to stop, by adding a certain volume of
quenching solution at a time, is noted.
The quenched solution is then titrated against a suitable standard solution.
Find the concentration of the substance
The titre is proportional to the concentration of the reactant or product being titrated.
2) Colorimetry:
If the reactants or products are coloured, the concentration of the coloured species can be measured
using a spectrophotometer. The amount of light of a specific frequency absorbed, depends on the
concentration of the species.
The reactants are mixed and the clock is started; the light absorbed is measured at a set time intervals.
A suitable example:

Br2 + HCOOH > 2Br + CO2 + 2H+

If the reaction is conducted in a breaker, the colour of bromine slowly fades. The spectrophotometer is
used to absorb light through the bromine solution.
Can use a calibration curve
3) Infrared Spectroscopy:
This is used in a similar way to colourimetry. The spectrometer is set at a specific frequency and the
amount of infrared radiation that is absorbed is measured at regular time intervals; proportional
to the concentration. A graph is produced with absorption peaks at different m/e values.
4) Polarimetry:
If a reactant is optically active (it can be rotated about the plane) and the product is differently optically
active or is a racemic mixture (when rotated, the entities on the left are equal to the right). The reaction
rate can be measured using the extent to which the plane of polarisation of light is rotated.
When the polarised light is passed through a solution of an optically active substance, it causes the light
to rotate. Angle of rotation is measured at regular time intervals. The angle of rotation is proportional
to the concentration of the optically active substance.

5) Volume of gas evolved:

This is measured using a gas syringe at regular time intervals. The volume of gas produced is
proportional to the moles of the gas, this can therefore be used to calculate the concentration of the
product.
This method can be modified by measuring the change in mass of the reactants over a set amount of
time. The mass is measured at set time intervals. This is not a good method because the change in
mass is very small and hard to calculate. A very sensitive balance must be used to measure this.
6) Time taken for a reaction to finish
Adding the two reactants and measuring the time taken for the reaction to finish. The experiment can be
repeated with different concentrations of either reactant or at a different temperature to measure the
effects of these changes.
7) Clock reactions
Reactants are mixed, measure the time taken to produce a fixed amount of product. Repeat the
experiment using different concentrations of reactants.
Iodine clock:

H2O2 + 2I- + 2H+ > I2 + 2H2O

-

25cm3 of H2O2 added to 25cm3 of H2O and a few drops of starch solution
25cm3 of KI added to 5cm3 of dilute Na2S2O3 in a second beaker
Two beakers are mixed; time taken for the solution to turn blue is

measured
The reaction produces iodine; which then reacts with the sodium thiosulfate. Iodine produced will
react with the starch and then the solution turns into a blue/black colour. The amount of iodine
produced, measured over time, is proportional to the volume of sodium thiosulfate used.
Sulfur clock:

S2O32- + 2H+ > S + SO2 + H2O

-

A large X drawn on a white tile

2cm3 of Na2S2O3 added to 25cm3 of H2O placed over X
25cm3 of dilute HNO3 added to the first beaker
Mixture is stirred; time taken for the X to be hidden is measured
Repeated with different concentration

8) pH measurements
Change in pH over time can be measured. The method required a very sensitive and accurate pH
meter which of course would be very expensive. This method is not suitable for school laboratories.
Rate equations:

nA +mB > products

The rate of the equation is explained as:

k(A)p(B)q = rate
A and B are the substances, n and m are the ratios, p and q are the powers of the concentrations of the
substances. k is the rate constant; this can vary due to the type of reaction, the temperature and the
presence of a catalyst.
The order of a reaction is the sum of the powers to which the concentrations of the reactants are
raised in the experimentally determined rate equation.
The partial order of one reactant is the power to which the concentration of that reactant is raised
in the equation.

4 ways to deduce the order of reaction:

1) Initial rates:
The initial rate; rate at which the reaction occurs the instant the two reactants are mixed. This can be
found by measuring the time taken for the concentration of the reactant or product to change. The
experiment can be repeated with different concentrations.
A + B + C > products
- Initial rate measured with all reactants at the same concentration; 1.0mol dm-3
- Repeated with A of concentration 2.0mol dm-3
- If the rate does not change; the reaction is zero order with respect to A
- If the rate doubles; it is first order in A
- If the rate increases by four times; it is in second order in A
- Third experiment with B of concentration 2.0mol dm-3 ; deduce the partial order of B
- Fourth experiment with C of concentration of 2.0mol dm-3 ; deduce the partial order of C
The overall order is the sum of all the partial orders.
2) Half-lives
Half-life is the time taken for the concentration of a reactant to halve
st
1 order; half-life is constant at a fixed temperature. If it takes 25s for the concentration to decrease from
8-4 units, it will take the same amount of time to decrease from 6-3 or 4-2 units.
2nd order; half-life increases in a regular geometric manner. If it takes 25s for the concentration to
decrease from 8-4 units, it will take 50s to fall from 4-2 units.
3) The slope of a concentration-time graph
When a graph of A is plotted against time the shape of the graph will depend on the order of the reaction.
The slope of the graph at any value of A is the rate of reaction at that concentration
- If the slope is horizontal; theres no reaction taking place
- If the slope is straight and negative correlation; theres a constant rate. this only occurs
when theres zero order
- If theres a downward curve, with a decreasing slope; the rate is decreasing as the
concentration of A falls. The reaction is in first order or greater
The rate at any concentration can be calculated by drawing a tangent on the curve on the graph and
measuring the slope of the tangent. The rate is minus the slope of the graph.
By drawing tangents at two points, or comparing the initial rate with the rate of the tangent, the order of
reaction can be determined.
4) The slope of rate-concentration graph
If a quantity that is proportional to the rate of reaction is plotted against the concentration of one of the
reactants, the order of that reactant can be found.
- If the graph of rate against the reactant is a straight line, the reaction is first order for that
reactant
- If the graph of rate against the reactant 2 is a straight ling, the reaction is second order for
that reactant
Units of rate reactions
For a first order = k[A]1
The concentration and the rate of reaction double together.

k = rate/[A]
time-1 , s-1 , min-1
For a second order = k[A]2 , k[A][B]
The concentration may double whilst the rate of reaction quadruples

k = rate/[A] or k = rate/[A][B]
concen.-1 time-1 , mol-1 dm3 s-1

Zero order reactions are straight lines on a graph, either horizontal or declining negatively.
Effect of temperature and a catalyst on the rate constant
Value of the rate constant depends on
- Orientation factor; if 1 in 10 collisions is successful the orientation factor is 0.1
- Activation energy
- Temperature
The 2nd and 3rd factors cause the rate constant to be equal to

k = e(-Ea/RT) ; Ea is the activation energy, R is the gas constant, T is the temperature in kelvin
A large Ea = lower rate of reaction, small value for rate constant. A catalyst lowers the Ea and
therefore more collisions occur successfully, (the exponent becomes less negative) and the k
gets larger. The rate constant increases.
A rise in temperature means theres more kinetic energy in the system and so there are more
successful collisions; this increases the value of k. The rate constant increases.
Lowering the temperature means theres less energy within the particles and so fewer successful
collisions occur; this decreases the value of k. The rate constant decreases.
Rate constant and temperature
In k = InA - Ea/RT
A is the constant
The rate constant can be measured at different temperatures, a graph can be plotted of In k against
time. The graph is a straight line of -Ea/R, the activation energy can be determined
Mechanisms to determine the rate
Single step reactions:
SN2 reactions occur in one step. Anhydrous sodium hydroxide plus a primary halogenoalkane.
Some secondary halogenoalkanes can also follow this mechanism. Some The Carbon atom
makes 5 bonds, two of which are weak, and this is the transition state; the halogen atom leaves
and the hydroxide molecule bonds fully.
Reaction energy profile is exothermic.
This is a single step reaction; the reaction is in second order

rate = k[A][B]
rate = k[OH-][CH3I]
The weaker the C-halogen bond the faster the reaction occurs. C-I > C-Br > C-Cl
Optical activity of the product compared to the reactants can be measured as evidence.
Multistep reactions:
SN1 Hydrolysis of a tertiary halogenoalkane is a two step reaction. Most secondary
halogenoalkanes also tend to follow this mechanism.
1st step: C-Cl bond breaks heterolytically (first order)

(CH3)3CCl > (CH3)3C+ + Clrate = k1[(CH3)3CCl]

2nd step: OH- bonds to the C atom (second order)

(CH3)3C+ + OH- > (CH3)3COH

rate = k2[(CH3)3C+][OH-]
The rate of the overall reaction is determined by the slowest step; the first step is slower. Step 1
is therefore a rate-determining reaction; rate = k1[(CH3)3CCl]

Rate-determining reactions are the slowest reactions in a multi-step mechanism

Evidence for mechanisms:
The Main evidence for a mechanism is the order of reaction with respect to the reactants. Hydrolysis of a
halogenoalkane can occur in two mechanisms; both nucleophilic substitutions. SN1 reactions however,
first order reaction, depend on the concentration of the halogenoalkane and not the nucleophile. During
the first step the Halogenoalkane has an order of 1, whilst the hydroxide has zero order. The nucleophile
enters the reaction after the rate-determining step.
Secondary Halogenoalkanes can react by SN1 or an SN2 mechanism.
- SN1 mechanism: due to the intermediate carbocation being increasingly stabilised by the
electron pushing effect of the alkyl group.
- SN2 mechanism: due to increasing steric hindrance by the alkyl groups on the attacking
nucleophile.
First step is the rate-determining step for an SN1 mechanism.
The reaction equation for the overall mechanism is the same as the equation for the rate-determining
step.

rate = k[(CH3)3CCl]
If a substance enters the mechanism after this step the partial order will be zero. In this case the alkali
has a partial order of zero.
In the following reaction; the overall reaction is in second order, and zero order with respect to iodine.
This is because iodine does not react yet.

CH3COCH3 + I2 + OH- > CH2ICOCH3 + H2O + Irate = k[CH3COCH3][OH-]

Iodine must enter the reaction after the rate-determining step
The rate determining step is in second order in this reaction.
1. CH3COCH3 + OH- > CH3COCH2- + H2O
SLOWER
OH- removes a H+ from -CH3, this is the rate determining step
2. CH3COCH2- + I2 > CH3COCH2I + IFASTER
the lone pair of electrons on the C- carbanion forms a bond with iodine as the I2 bond breaks
The rate of the reaction is the same whether Chlorine, Bromine or Iodine is used. This is evidence that
the first reaction is the rate-determining reaction
Second or subsequent step is the rate-determining step

A + 2B + C > D + E
Step 1 :
A + B > Int
Step 2 :
Int + B > X
X is needed for the next step therefore this is the slow step and also the rate-determining step
Step 3 :
C + X > D + E
The overall rate is determined by step 2 therefore:
overall rate = k2[B][Int]
Reaction profiles for multi-step reactions:

A. The activation energy to produce the intermediate is greater than the activation energy to
make the products. Ea1 is greater than Ea2 - the first step is the rate-determining step.
B. The activation energy to produce the intermediate is smaller than the activation energy to
make the products. Ea1 is smaller than Ea2 - the second step is the rate-determining step.
Pseudo-zero-partial-order reactions
These are enzyme-catalysed reactions inside living organisms.
The rate of reaction depends on the concentration of the enzyme.
The enzyme rapidly absorbs the reactant and slowly converts it into the product and it is then released
rapidly by the enzyme. If theres enough enzyme then the rate of reaction does not depends on the
concentration of the reactant. Because theres enough of the enzyme - enough active sites. The reaction
therefore has an apparent zero-partial order even though the substrate enters the reaction before the
rate-determining step.
If the concentration of the substrate drops too low then the reaction becomes dependent on the
concentration.
Catalysis
Heterogeneous catalysts
These are in a different state to the reactants. They can be separated from the equilibrium
mixture easily. E.g. solid iron catalyst to react gaseous nitrogen and hydrogen in the Haber
process. The catalyst stays in the reaction chamber.
This occurs in most metal-catalysed gaseous reactions.
- Haber process, nitrogen and hydrogen is catalysed by iron
- Manufacture of hydrogen, steam and methane is catalysed by nickel
- Oxidation of ammonia by air, catalysed by platinum
These are all in zero-order with respect to both gases unless the pressure s very low.
Homogeneous catalysts
These are in the same state to the reactants. The rate of reaction depends on the concentration
of the catalysts and one of the reactants.