Chemical Kinetics

Introduction:

Chemical kinetics is the study of rate of chemical reactions and how they are controlled. It also
investigates the pathway or mechanism that a reactant progresses from its reactants to its products.
Generally, a factor that decreases the number of collisions between particles will decrease the
chemical reaction rate and a factor that increases number of collision between particles will do the
opposite. Among the factors that affect reaction rate is the concentration of reactants. Effective
collisions per unit time increases when there is a higher concentration of reactants but a higher
concentration of products will result in a lower reaction rate. Next, a higher temperature suggests that
there is a higher average kinetic energy of molecules and therefore more collisions per unit time. For
every 10ºC increase in temperature, the reaction rates will approximately double its original rate.
However, some of the chemical characteristics may be altered once the temperature reaches a certain
point and the chemical reaction will slow or stop. The rate of a chemical reaction also depends on the
type and state of medium, whether it be aqueous, organic, polar, nonpolar, liquid, solid or gaseous.
Lastly, the presence of catalysts and competitors will either increase or decrease reaction rate.
Catalysts lower the activation energy needed for particles to undergo a chemical change and will not
be consumed in the process. It increases the frequency of collisions between reactants, reduce
intermolecular bonding, donate electron density to reactants or alters the orientation of reactants so
that more chemical reactions are effective. Competitors however, may compete with a reactant and
decrease the rate of reaction.

The rate of reaction may be mathematically represented by a rate law. The rate constant for the
reaction can be derived by changing the concentration of one reactant and keeping the other
concentrations constant, thereby determining the variation in the rate of the reaction for each reactant.

Aims/Objective:

i) To determine the factors affecting reaction rates and its effects to the chemical reaction.
ii) To determine the rate of a reaction of a solution mixture at fixed temperature through
mathematical means described by a rate law.

Procedure:

A) Factors affecting reaction rates

a) Nature of the reactants
1. Different acids affect reaction rates
Materials: 3 M H2SO4 , 6 M HCl , 6 M of CH3COOH , 6 M H3PO4 , 4 strips of 1
cm magnesium strip.

Four labelled text tubes were added with 3 M H2SO4 , 6 M HCl , 6 M of CH3COOH
and 6 M H3PO4 of around 2 cm in depth each. A 1 cm strip of magnesium was
submerged into each test tube. Reaction rates of each acid with magnesium were
compared and its observations were recorded.

2. Different metals affect reaction rates

Materials: 6 M HCl, zinc strip, magnesium strip, copper strip

Three test tubes were labelled and filled with 6 M HCl of depth around 2 cm each. 1
cm strips of Zinc, magnesium and copper were submerged separately into the test
tubes. The reaction rates of each metal with HCl were compared and its observations
were recorded.
 b) Presence of catalyst
Materials: 3% H2O2 solution , MnO2

A test tube was added with 3% H2O2 solution of around 2 cm in depth. A small amount of
MnO2 was added to the solution and observations were recorded.

c) Concentration of reactants
Materials: 6 M HCl , 4 M HCl , 3 M HCl and 1 M HCl, 4 magnesium strip, steel
wool

1. Four clean and labelled test tubes were pipetted with 1 mL of 6 M HCl , 4 M HCl , 3
M HCl and 1 M HCl respectively. Masses of four magnesium strips which were
initially polished with steel wool were determined separately. Number of moles of
magnesium were calculated in each strip.
2. The first magnesium strip was added to the 6 M HCl solution. The stopwatch was
started and the time taken for all traces of magnesium strip to disappear was recorded.
The experiment was repeated with the remaining three magnesium strips and the 4 M
HCl , 3 M HCl and 1 M HCl solution.
𝑚𝑜𝑙 𝐻𝐶𝑙
3. A graph of 𝑚𝑜𝑙 𝑀𝑔 (y-axis) versus time in seconds (x-axis) was plotted for the four
tests

B) Determination of rate law

Materials: KI, Na2S2O3, H2O, KBrO3, HCl, starch indicator

1. Reagent volumes were prepared using the following table and were used to carry out
several reactions whose rates need to be known in order to find the general rate law for
the reaction between I- and BrO3- in acidic condition. A measuring cylinder was used to
measure the volumes needed.

Reaction Reaction mixture I (mL) Reaction Flask II (mL)

mixture KI (0.01M) Na2S2O3 H2O KBrO3 HCl
(0.001M) (0.04M) (0.10M)
1 10 10 10 10 10
2 20 10 0 10 10
3 10 10 0 20 10
4 10 10 0 10 20

2. Around 10 drops of starch indicator were added to reaction flask II. The stopwatch was
started when the contents of reaction flask II was mixed with the contents of reaction
flask I. The solution mixture was swirled. The stopwatch was stopped when the blue
colour appeared in the solution mixture.

Results:

A) Factors affecting reaction rules

a) Nature of reactant
1. Different acids
When magnesium was mixed with 6 M HCl, magnesium reacted very
vigorously and transparent gas bubbles were seen throughout the acid. The bottom of
the test tube become hot during the reaction. When magnesium was mixed with 3 M
 H2SO4, magnesium reacted vigorously and gas bubbles were released emitting a
pungent smell. The bottom of the test tube became warm. When magnesium was
mixed with 6 M H3PO4, magnesium reacted less vigorous and took a longer time to
dissolve, gas bubbles were also seen in the test tube. When magnesium was mixed
with 6 M CH3COOH, magnesium reacted slowly and took a very long time to
dissolve. Gas bubble were only seen on the surface of magnesium. The arrangement
of acids in order of decreasing reaction rate with magnesium is HCl, followed by
H2SO4, then H3PO4 and lastly CH3COOH.

2. Different metals
When magnesium was mixed with 6 M HCl, magnesium reacted vigorously
with the acid and gas bubbles were seen throughout the acid. White fumes were seen
emitted from the reaction. When 6 M HCl was mixed with zinc, it reacted slowly and
gas bubbles were seen on the surface of the zinc strip. When copper was mixed with
6 M HCl, copper had very minimal to no reaction with the acid. The arrangement of
metals in order of decreasing reaction rate with 6 M HCl is Magnesium, followed by
zinc, then copper.

b) Presence of catalyst
No particular reactions were seen when MnO2 and 3% H2O2 was added together.
The MnO2 was seen sinking to the bottom and the 3% H2O2 can be seen nor mixing with
the MnO2.

c) Concentration of reactants

HCl Mol HCl Mass of Mg Mol Mg 𝑚𝑜𝑙 𝐻𝐶𝑙 Time (s)

(g) 𝑚𝑜𝑙 𝑀𝑔
6M 0.006 0.0137 5.64 x 10-4 10.64 29
4M 0.004 0.0152 6.25 x 10-4 6.40 68
3M 0.003 0.0148 6.09 x 10-4 4.93 80
1M 0.001 0.0178 7.32 x 10-4 1.37 1200

B) Determination of rate law

Reaction Time, t (sec) Relative rate Reactant concentration (M)

-
Mixture (1000/t) I BrO3- H+
1 172 5.814 0.002 0.008 0.020
2 105 9.524 0.004 0.008 0.020
3 89 11.236 0.002 0.016 0.020
4 43 23.256 0.002 0.008 0.040

Discussion:

A) Factor affecting reaction rates

a) Nature of reactants

Acids react with magnesium to form salt and hydrogen gas. Hydrogen is a
colourless and odourless gas. Pungent smell sensed during the experiment may be due
to impurities present in the mixture. Hydrochloric acid and sulphuric acid are
classified as strong acids while ethanoic acid and phosphoric acid are weak acids.
Hydrochloric acid reacts the fastest with magnesium because it only need to
dissociate once, producing one hydrogen atom when reacted with magnesium.
 Sulphuric acid consists of 2 hydrogen atoms and will form 2 hydrogen ions when
reacted with magnesium. However, the full dissociation of the acid occurs in 2
reactions and therefore is slightly weaker than hydrochloric acid. Phosphoric acid has
3 hydrogen atoms, however, it does not dissociated completely to produce 3 hydrogen
ions. However, when compared with ethanoic acid, it produces more hydrogen ions
per unit molecule and is therefore more reactive than ethanoic acid. Ethanoic acid has
4 hydrogen atoms, and its dissociative ability is limited. Only few hydrogen atoms
can be dissociated from one molecule of ethanoic acid, thus making it the weakest
and slowest reacting acid among the four acids.
Metals react with hydrochloric acid to form salt and hydrogen gas. White fumes
noticed during the experiment may be hydrochloric acid vaporized by the heat
emitted during the reaction. Magnesium reacts the fastest, followed by zinc then
copper. This is because magnesium is the most reactive compared to the others.
Magnesium is an active metal and reacts readily with hydrochloric acid. Copper has
very minimal reaction because it is a relatively stable metal and is lower than both
magnesium and zinc in the reactivity series.

b) Presence of catalyst

In theory, the decomposition of H2O2 should occur when catalyst MnO2 is added to it.
Gas bubbles should be produced from the reaction indicating that oxygen is emitted. The
equation of the decomposition of H2O2 sould be :

2H2O2(aq) → 2H2O + O2(g).

However, the observation from the experiment is that there were no reaction when MnO2
was added to H2O2. This may be due to the low concentration of reactants used or due to
impurities present in the test tubes or reactants.

c) Concentration of reactants
𝑚𝑜𝑙 𝐻𝐶𝑙
Graph of 𝑚𝑜𝑙 𝑀𝑔 against time was plotted on the graph paper. The ratio of
concentration increases as the concentration of hydrochloric acid increase. As the
concentration of hydrochloric acid increase, the time required for a known mass of
magnesium to react decrease. This is because the chances for collision of particles to
occur is greater when concentration is greater as there are more particles to collide
with. From the graph drawn, it takes 375 seconds for magnesium to completely
disappear. (Calculation of number of mole of magnesium and hydrochloric acid is on
the back of graph paper.)

B) Determination of rate law

For this reaction, the rate law takes the form of 𝑟𝑎𝑡𝑒 = 𝑘[𝐼 − ]𝑚 [𝐵𝑟𝑂3 − ]𝑛 [𝐻+ ]𝑝 .
0.004
When comparing reaction mixture 1 and 2, molarity of I- is double ( 0.002 = 2 ), the
9.524
reaction rate is also doubles ( 5.814 = 2 ), Therefore ( 2𝑚 = 2 ) and m=1.
0.016
When comparing reaction mixture 1 and 3, molarity of BrO3 is double ( = 2 ), the
0.008
11.236
reaction rate is also doubles ( 5.814
= 2 ), Therefore ( 2𝑛 = 2 ) and n=1.
0.040
When comparing reaction mixture 1 and 4, molarity of H+ is double ( 0.020 = 2 ), the
23.256
reaction rate is quadruples ( 5.814
= 4 ), Therefore ( 2𝑝 = 4 ) and p=2.
 𝑅𝑒𝑙𝑎𝑡𝑖𝑣𝑒 𝑟𝑎𝑡𝑒
To obtain k, the equation in the form of 𝑘 = [𝐼 −]𝑚[𝐵𝑟𝑂 − 𝑛 + 𝑝 was used and its unit is M-3s-1
3 ] [𝐻 ]
5.814
For reaction mixture 1, 𝑘 = [0.002]1 [0.008]1 [0.020]2 = 9.08 x 108 M-3s-1.
9.524
For reaction mixture 2, 𝑘 = [0.004]1 [0.008]1 [0.020]2 = 7.44 x 108 M-3s-1.
11.236
For reaction mixture 3, 𝑘 = [0.002]1 [0.016]1 [0.020]2 = 8.78 x 108 M-3s-1.
23.256
For reaction mixture 4, 𝑘 = [0.002]1 [0.008]1 [0.040]2 = 9.08 x 108 M-3s-1.
The average of rate constant, k=8.60 x 108 M-3s-1.

A light increase in concentration of starch will decrease the time taken for blue colour
to reappear in the mixture. There are more molecules of reactants in the solution therefore
there is a greater chance of reaction.

Conclusion :

When a strong acid is used to react with magnesium, it will have a faster reaction rate compared to
weaker acids due to the concentration of Hydrogen ions. When a more reactive metal is placed in 6 M
HCl solution, the metal will react more vigorously than the others. A catalyst will decompose a
relatively stable compound to its constituent elements. The greater the concentration of reactant, the
greater the rate of reaction.