SOME TECHNIQUES FOR MEASURING RATE OF REACTION

There are a variety of techniques that can be used to measure the rate of reaction. The most commonly used are: titration,
colorimetry, conductivity, measurement of the mass or volume changes.
Whichever technique is being used, it is important to keep the reaction mixture at a constant temperature during the
reaction, because temperature has a great effect on the rate of reaction. For this reason it is usual to immerse the reaction
vessel in a water bath at the required temperature. It is also preferable to immerse the reactants in the water bath, to allow
them to reach the required temperature before mixing.
USING TIME AS A MEASURE OF RATE
In some reactions it is easy to measure the time taken for a particular stage of reaction to be reached e.g. sodium thiosulfate
with hydrochloric acid. The effect of changing concentrations of two reactants can be investigated by carrying out reaction
and measuring the time taken to form precipitate. The same total volume of solutions must be used in each experiment.
TITRATION
This method involves removing small samples from the reaction mixture at different times and then titrating the sample to
determine the concentration lf one of the reactants or one of product at this time. The results can be used directly to
generate a graph of concentration against time. In its simplest form it is suitable for quite slow reactions in which the time
taken to titrate the mixture is significant compared to the total time taken for the reaction. To overcome this difficulty is to
quench the reaction before carrying out the titration. This means altering conditions so as to stop the reaction. It can be done
by rapidly cooling the reaction mixture to a very low temperature or by adding an excess of a compound that rapidly reacts
with one of reactants. This method is suitable for reaction in solutions such as that between iodide and propanone catalyzed
by acid: CH3COCH3 (aq) + I2 (aq) → CH2ICOCH3 (aq) + H + (aq) + I - (aq)
If portions of the reaction mixture are pipetted into sodium hydrogencarbonate solution this quenches the reaction by
neutralizing the acid catalyst. Another example of reaction that can be measured by this technique is the rate of reaction of
hydrogen peroxide with iodide ions in acidic solution: H2O2(aq)+ 2H + (aq) + 2I (aq) → I2 (aq) + 2H2O (l)
The reaction can be quenched by adding excess ofan insoluble solid base (e.g. CaCO3) to neutralize the acid required for the
reaction or by diluting in ice-cold water. The other example involves hydrolysis of ester or formation of ester.
COLORYMETRY
This method is especially convenient if one of reactants or products is highly coloured.
( e.g. the reaction betweeniodide and propanone catalyzed by acid). The intensity of colour can be followed during the
reaction using a photoelectric colorimeter. If a reactant is coloured, the colour of mixture will fade during reaction. If a
product is coloured, the reaction mixture will gradually become more intensely coloured. The absorbance is measured and
the values are directly proportional to concentration.

THE EASIEST REACTIONS TO STUDY ARE ONES IN WHICH GAS IS EVOLVED

Gas evolution means that two things can be measured
1. The decrease in mass of the reaction mixture
2. The volume of gas produced
Measuring the volume of gas produced with time
The gas produced in the reaction is colleted either in a gas syringe or in a graduated vessel over water. The volume of gas is
collected at different times can be recorded. An alternative technique is to carry out the reaction in a vessel of fixed volume
and monitor the increase in the gas pressure. These techniques are suitable for measuring the rate of reaction between
reactive metal and acidZn(s) + 2H+ (aq) → Zn2+ (aq) + H2
2 methods:
Although both of these methods are basically straightforward a slight complication arises at the time of mixing the reactants.
A divided flask (test-tube) must be used to ensure that the reaction does not start until all the apparatus is assembled and
gas tight.
Measuring the mass loss with time
This simply involves carrying out the reaction on a top pan balance and taking readings every predetermined period of time.
This technique would be suitable for measuring the rate of reaction between a metal carbonate (e.g. calcium carbonate) and
an acid (e.g. hydrochloric acid), by measuring the rate of mass loss resulting from evolution of CO 2

RATE OF REACTION
rate of chemical reaction is the change in concentration per unit of time (generally seconds)
Δ Cm
rate=  t may by in seconds, minutes, days and even years as radioactive decay may last millions of years.
ΔT
experimental techniques of rate measurements
If we measure the rate, the following quantities can be measured:
change in concentration by titration technique for aqueous solution
change in colour (absorbance; for example for d-block elements)
change in mass of reactant (when the gas is used)
change in volume of product (used)
change in pH (for reaction involving this change)
change in conductivity (for reactions involving electrolytes)
rate is described as 1/t when the change is rapid, not continuous, gradual
(e.g. iodine clock, titration)
Determining the rate
it is done by graphical technique
draw the tangent to the curve at a particular period of time (at the beginning)

COLLISION THEORY
Reactant particles must collie with each other to have a chemical reaction. Colliding particles must satisfy two conditions:
 They must collide with energy equal to, or greater than, the activation energy of the reaction,
 They must collide with the correct orientation (geometry),
Collisions that result in a chemical reaction are known as successful or effective collisions.
Correct orientation

Unsuccessful collision Successful collision

 

Activation energy is the minimum energy required by the reactants to form products and collide successfully

activated
complex
FACTORS AFFECTING THE ACTIVATION ENERGY

Experiment 1: The effect of concentration

in the first test tube a lot of bubbles/foam is produced, much more than in the second test
tube. The greater the concentration is, the faster is the reaction.
greater probability of successful collision. more product per unit of time means higher rate.
greater concentration means greater frequency of collisions, also successful, this means
greater amount of product per unit time – the reaction is faster

Experiment 2: The effect of temperature

in the first test tube not much gas was evolved and in the second much more gas was
evolved and the solution become cloudy
the higher the temperature is, the faster the reaction is. Increasing the temperature
increases the average kinetics energy of the particles.

Effect of temperature on molecular level – temperature means

energy. On higher temperature move faster so they have greater
kinetic energy and the frequency of collisions is greater and they
collide more successfully; their energy is greater so more particles
have enough energy to collide with each other.
when the temperature increases, the particles move faster so they
collide more frequently and more product is formed. what’s more,
greater amount of particles have enough energy to collide
successfully hence this also leads to greater amount of product.

Maxwell-Boltzmann distribution curve shows the number of particles that have

a certain value of kinetics energy plotted against the values of kinetics energy.
Factors that affect the rate of reaction
Temperature
Concentration
Particle size
Pressure
Catalysts
The area under the graph represents the total number of particles with appropriate kinetic energy

Experiment 3: The effect of surface area (only for solid reactants)

In the first tube – bubbles of gas are evolved and faster than in the 2nd test tube. the
smaller the surface area is, the slower the reaction. the bigger the SA, the faster the
reaction
lumps – big pieces

Experiment 4: The role of catalyst is to lower the activation energy by providing the alternative pathway of reaction
catalyst is the substance that influence (increases or decreases - inhibitors) the rate of
reaction without being chemically changed (theoretically).
in the 1st test tube no changes were visible, in the 2nd after the catalyst was added, a lot of
steam is evolved and the gas is evolved. after adding catalyst, the reaction is much
vigorous.
At the end reaction goes to completion

RATE EQUATION AND ORDER OF REACTION [rząd reakcji]

A+BC+D
k – the rate constant rate = k x [A]x [B]y
overall order = x + y [x and y are not coefficients from equation]
rate expression/equation – równanie kinetyczne
the order of reaction with respect to [w odniesieniu do] particular reactant is determined only experimentally.
if the concentration double and the rate double, the concentration is directly proportional to the rate.
rate
k=
[ A ] x [B]y
first order reaction is in s-1. second order reaction is in dm3 mol-1 s-1. third order reaction is in dm6 mol-2 s-1
Graphical representation of reaction kinetics:

by manipulating the variables (concentration and time) the straight line is obtained and the gradient of it is used to
determine the rate constant in the following way
Determining rate constant by graphical techniques:

half-life – okres półtrwania; this is the time taken for concentration to cut to half its original value. The half-life for the first
order reaction is constant, for zero order reaction half-life time decreases, for second order reaction the half-life time
increases.

rate expression must be consistened with the mechanism of the reaction. the chemical reaction gives no information of the
mechanism.
type of catalysis (reaction with catalyst)
homogeneous - catalyst and reactant are in the same phases
biochemical processes in the presence of enzymes,
estrification - reaction between acid and alcohol
CH3COOH + C2H5OH ---(H2SO4) H2O + CH3COOC2H5
heterogeneous – catalyst and reactant are in different phases
C2H4 (g) + H2 (g) ---(Ni) C2H6 (g)
NO + CO ---(Pt) 2CO2 + N2
A + BC –(K) AB + C
A + K  [A....K] ---(BC) [A....K...B...C]  AB + C + K
Catalyst react with one of reactant forming very unstable transition state that with next reactant form new activated
complex (also transition state, unstable) with lower activation energy which breaks down the reactants into products.
Heterogeneous catalysis involves two steps more than homogeneous: one at the beginning (it start with the adsorption of
reactant at the surface of catalyst and so called active sites) and at the end (the product is desorbed from the surfaces of
catalyst)
KNaC4H4O6·4H2O + H20
Observations:
the pink colour of solution turns peachy, then it turns into brownish, then olive green, then green. during the
reaction there are a lot of bubbles of gas evolved. AT the end the colour of solution go back to pink
Mechanism of chemical reactant
most chemical reactions involve a series of small steps that occur with different rate. The overall rate of reaction
depends on rate-determining step (RDS, the slowest step), molecularity (number of particles involved in the
individual step; usually the reaction may be unimolecular or bimolecular). Mechanism of reaction must be consistent
with the rate equation
possible mechanisms for the
first order reaction: 2A + B  C + D – rate = k[A] or k[B]
B forms X intermediate, then intermediate will react with second reactant, A, forming another intermediate and
one product - C. this intermediate reacts with second mole of second reactant, A, forming the last product - D
BX
X+AY+C
Y+AD
second order reaction third order reaction
rate = k[A]2 2A + B  C + D
A + A  A2 rate = k [A]2[B]
A2 + B  C+ D A + A  A2 (A2 is intermediate, fast process)
rate = k[A][B] A2 + B  C+ D (rate-determining step, slow process)
A+BX+C A + B  X (fast)
X+AD X + A  C + D (rate-determining step – there must be square A, slow)
always only one step is fast, rest is slow
Arrhenius equation – describes the relationship between rate constant and T
k 2 −Ea 1 1
k = (A x e)-EA/RT ln = ( − ) ln k = ln A – EA/RT
k1 R T2 T1
k – rate constant
A – frequency factor/pre-exponential factor / collision frequency factor
e – base of natural logarithm
EA – activation energy
R – the gas constant
T – temperature in kelvin
Arrhenius constant refers to the geometric orientation of molecules at the point of collision. Both activation energy and
frequency factor are determined from the graph - natural logarithm of rate constant against of reciprocal T {in K}
If temperatures increases, the rate constant increases exponentially. If activation energy increases, rate constant decrease.
The catalyst providing alternative pathway with lower activation energy causes the rate constant bigger. A is related to both
the collision frequency and orientation probability factor (dependent on structural complexity)
OZONE (formation, properties, tipletion - rozpad)
all bonds in ozone have the same lengths and they are shorter than single bonds but longer than double bonds
O2 O3
Colourless, Without smell, Bluish colour (plungent), Characteristic smell, Dissolve in water 13 times better than o2
Dissolve in water – 9 ppm Ozone has greater mass so density is greater, It has ability to kill bacteria and viruses
is maximum solubility, (purification of water for drinking purpose, sanitary, pools), v-shaped, bond 90<angle<120,
Density is smaller sp2 hybradyzation, natural formation in environment
Ozone naturally dissociate and between processes formation and breakdown, the equilibrium should be established in
environment. Sometimes due to the human activity decomposition of ozone increases and ozone depletion occurs [dziura
ozonowa]. How ozone depletion can be speed up? CFCs and NO act as catalyst for breakdown of ozone molecules. Main
source of NO in air is high T combustion of fuel in jets (planes). CFCs (freons) mainly forming agent, in different refrigerator
systems, solvents; Ozone in troposphere is dangerous air pollution, in stratosphere – protection from UV rays
The importance of ozone layer in stratosphere (for humans)
Depending on where ozone resides, it can protect or harm life on Earth. Most ozone resides in the stratosphere (a layer of
the atmosphere between 10 and 40 km above us), where it acts as a shield to protect Earth's surface from the sun's harmful
ultraviolet radiation. With a weakening of this shield, we would be more susceptible to skin cancer, cataracts and impaired
immune systems. Plants cannot live and grow in heavy ultraviolet radiation, nor can the planktons that serve as food for most
of the ocean life. Closer to Earth in the troposphere (the atmospheric layer from the surface up to about 10 km), ozone is a
harmful pollutant that causes damage to lung tissue and plants. Ozone in troposphere is regarded as very dangerous air
pollution, harmful for people and animals