TITLE: A VELOCITY CONSTANT BY TITRATION METHOD

Aims and Objectives:

1. To determine the velocity constant of a reaction by titration method.
2. To determine the rate of a reaction.
3. To be able to determine the order of a reaction.
4. To be conversant with measuring the temperature of a substance using a thermometer.
5. To be able to handle concentrated acids and appropriately dispose off waste acids

INTRODUCTION
Chemical kinetics is the area of chemistry concerned with the speeds, or rates, at which a chemical
reaction occurs. The word ‘kinetics’ suggests movement or change. Here kinetics refers to the rate of
reaction, or the reaction rate, which is the change in the concentration of a reactant or product with time
(M/s).
The rate of a reaction therefore gives information about how fast a given reactant is consumed or how
much of a given product is formed within a given time. During chemical reactions, reactants are changed
into products and the amount of reactants and products change as the reaction proceeds.

The rate equation may be expressed in the form of:

∆c = k (A) n1(B)n2 (1)
∆t
where k is the velocity constant of the reaction. The order of the reaction n is the sum of the exponents in
the rate equation, i.e.
n = n 1 + n2 + n 3

In the second order reaction involving the oxidation of iodide with persulphate
2I- + S208 → I2 + 2SO4-2

The rate equation may be written

∆c = K2 (a-x) (b-x) (2)
∆t

Where a and b are the initial concentrations of persulphate and iodide respectively. If one of the reactants
is present in excess such that its concentration remains sensibly constant during the course of the reaction,
the reaction will follow first order kinetics.
Suppose the concentration of iodide in the above reaction is so large that it will be approximately
unaltered during reaction, equation (2) will reduce to
∆c = k2 (a-x) b (3)
∆t

By applying calculus, integrate and apply the condition that when t = 0, x = 0, we have
 bk2 = - 1 ln a
t a-x
ln (a-x) = - k’t + lna (4)
where k’ = b.k2

Eqn (4) has the form of a linear equation, y = mx + c

Where m = slope of the line
y = ln (a-x)
m = -k
x=t
c = ln a
Thus, a plot of log (a-x) versus t will give a straight line with a slope of –k. This will allow us to calculate
the rate constant / velocity constant, k.

Any of six factors can affect the rate of a chemical reaction: the nature of the reactants; the temperature;
the presence of a catalyst; the concentration of the reactants in the solution; the presence of gaseous
reactants and the state of subdivision of solid reactants. For a reaction to occur, the atoms, molecules, or
ions must come into contact with one another with enough energy to rearrange chemical bonds in some
way. Increased concentration, gas pressure, or surface area of a solid tends to get the particles to collide
more frequently and with greater energy to accomplish more effective collisions. Catalysts work in very
many different ways.
Some reactions, such as an explosion TNT, inherently tend to proceed rapidly. Others, such as the
reaction of solid limestone with carbon dioxide in water to form calcium hydrogen carbonate, tend to
proceed slowly. It may take centuries for underground steam to form caverns by reaction with limestone
for a given reaction, chemists have no control over the nature of the reactants.
Raising the temperature generally increases the rate of a chemical reaction. A general approximation is
that a 10oC raise in temperature doubles the rate of the reaction. The actual increase for any given reaction
will not follow this rule exactly, of course, but a great many reactions follow it approximately.

CHEMICALS AND EQUIPMENT

Thermostat Saturated solution of potassium persulphate
Pipette 0.4N potassium iodide solution
Beaker 0.1N sodium thiosulphate solution
Thermometer Distilled water
Conical flask
Graduated cylinder
Stop watch

PROCEDURE
1. 50ml of the 0.4N solution of the potassium iodide is delivered into a weighed conical flask from a
pipette and the flask suspended in a bath with a thermostat at 25°C.
2. 20ml of the saturated solution of potassium persulphate is diluted with 80.0ml of water.
3. 50ml of the resulting solution is placed in a conical flask and suspended in the thermostat.
4. When the temperatures of the solutions became steady at 25°C, the potassium iodide solution was
poured into the potassium persulphate solution and the stop watch started simultaneously.
5. At measured and recorded intervals in time (3, 8,15,20,30,40,50,60 mins), 10.0 ml of the reaction
mixture was withdrawn with a pipette and allowed to run into a large volume of water.
6. Each 10.0ml sample was titrated with freshly prepared 0.01N sodium thiosulphate (x ml) using
starch indicator.
 7. 50ml of potassium iodide solution was mixed with the remainder of the diluted potassium
persulphate solution and maintained at 60°C for the duration of the experiment.
8. The solution was cooled and maintained at 25°C f at least 15 minutes.
9. 10.0ml was titrated with 0.1N sodium thiosulphate (a ml).

OBSERVATION
When potassium iodide was added to persulphate solution to obtain a mixture, the mixture turned yellow
in colour, then to orange and gradually to a deep orange colour. The mixture also turned blue-black in
colour when starch indicator was added to it when the endpoint was reached during titration thiosulphate,
the blue-black colour turned colourless.
There was also a colour change of the second mixture made with potassium iodide and dilute persulphate
from yellow to orange.

TABLE OF RESULTS

Time (t)/min Titration (a)/ml Titration (x)/ml a-x Log (a-x)

3 7.3 1.2 6.1 0.785
8 7.3 1.6 5.7 0.756
15 7.3 2.3 5.0 0.699
20 7.3 2.8 4.5 0.653
30 7.3 3.5 3.8 0.580
40 7.3 4.0 3.3 0.519
50 7.3 4.4 2.9 0.462
60 7.3 5.0 2.3 0.362

Log (a-x) (t1) = log (7.3 – 1.2)

= log (6.1)
= 0.785

CALCULATION/ POST LAB

Slope/ gradient of graph, -k = ∆log (a-x)
∆t
= 0.653 – 0.362
20 - 60
= -7.28x 10-3 min -1

1) The order of this reaction can be changed by changing the concentration of the reactants.
2) Other experimental methods are following kinetics of this reaction are the isolation method, the
mathematical method and the reasoning method.
3) The starch indicator is used to enable one obtain the endpoint of the reaction. This is because
starch produces a blue-black colour with iodide and decolourises at the endpoint.

DISCUSSION
The colour of the mixture turned to blue-black upon addition of starch indicator because starch turns blue-
black in iodine. It was also observed that, as the time increased, the value of ‘x ml’; (the volume of
thiosulphate used in the first part of the experiment) also increased steadily as the reaction proceeded, the
rate increased more rapidly. This is because with time, persulphate ions reacted with iodide to form more
iodine molecules. Since thiosulphate reacts with iodine when introduced, more thiosulphate will be used
up.
The volume of thiosulphate for the second part of the experiment remained constant throughout titration
since the reaction stopped when the mixture was cooled from 60°C to 25°C. According to the collision
theory, for species to react chemically with each other they must collide. The rate of a chemical reaction
depends on the frequency of effective collisions, the higher the rate of the reaction. Generally increase in
temperature increases the rate of reaction and vice-versa. When the temperature is increased, the colliding
particles gain more kinetic energy therefore there are more effective collisions per unit time between the
reacting particles so the rate of reaction increase. This accounted for the increase in the rate of reaction of
‘x’.
Also, when the temperature is increased, the fraction of molecules with kinetic energy greater than the
activation energy will be increased and the rate of the reaction will increase. Decrease in temperature has
the opposite effect.

The rate constant was also obtained as a negative value. This can be used to infer that, the rate of this
reaction depended on the concentration of reactants, decreased as the reaction proceeded. From the fact
that, the slope of the line for a first-order reaction is equal to -k, this reaction is first-order overall.

SOURCES OF ERROR
1. Parallax occurred while taking the readings of some of the titre values because of poor condition
of the retort stand.
2. The straight line graph passed through only three points because instead of all because some of the
solution poured in the course of swelling, tarnishing the titre value.
3. Inadequacy of conical flask resulted in the use of smaller glassware which caused swelling of
solution to be ineffective, thus affecting the endpoint of the solution.

PRECAUTIONS
1. The burette was ensured to stand upright in the retort stand to avoid parallax.
2. All burette and pipette readings were taken accurately from the bottom of the meniscus.
3. It was ensured that all bubbles were eliminated from the pipette from the pipette before taking the
readings.
4. The glassware was washed with the sample of the solutions before use.
5. Safety glasses and aprons were throughout the experiment.
6. Hands were thoroughly washed before leaving the laboratory.

CONCLUSION
The method used in determining the velocity constant as well as the rate of the reaction was successful.

REFERNECES
1. Chemistry Laboratory Manual, KNUST, Page 33, 34.
2. Physical Chemistry Laboratory Experiments - John M.White (1976), pages 258-360.
3. Essential Chemistry (Second Edition) – Raymond Chang – pages 430 – 439.

PRE-LAB
1. Increase in temperature increases the rate of effective collision. The fraction of molecules with
K.E. greater than the activation energy will be increased and the rate of the reaction will increase.
The 50ml of potassium iodide solution and the remainder of the dilute potassuimpersulphate
mixture were maintained at a constant temperature of 60oC because the activation energy will be
minimal; hence the rate of the reaction will increase.
At 25 oC, there will be cooling since temperature will be reduced hence the reaction will be
brought to an end at the stable temperature.

2. a) It was ensured that all readings were taken accurately.

b) It was ensured that the tip of the thermometer did not touch the sides or bottom of the flask
during heating.
c) The titration process was carried out carefully to obtain accurate results.
d) Avoidance of huge reaction time when recording time readings for the respective temperature.