Experiment # 9

CHEMICAL KINETICS

Diane F. Falculan
Sunshine Charisse Abadilla
Chem 157.1
Prof. Yambot

Department of Physical Sciences and Mathematics

College of Arts and Sciences
University of the Philippines Manila
I. Introduction

Chemical kinetics is a branch of physical chemistry that deals with the study of the rates
of chemical reactions. It also includes investigations of how different experimental conditions
can influence the speed of a chemical reaction and yield information about the reaction's
mechanism and transition states, as well as the construction of mathematical models that can
describe the characteristics of a chemical reaction. It complements thermodynamics by supplying
information about the rate of approach to equilibrium and the mechanism responsible for the
conversion of reactants to products.
A mathematical expression relating the rate of a reaction to the concentration of either
reactants or products is called the rate law of a reaction. It tells how fast the reaction proceeds
and how the reaction rate depends on the concentrations of the chemical species involved.

Usually rate laws take the form, where x, y, z, are small whole
numbers or simple fractions and k is called the "rate constant." The sum of x + y + z + . . . is
called the "order" of the reaction. The rate equation is a differential equation and it can be
integrated in order to obtain an integrated rate equation that links concentrations of reactants or
products with time.
There are common types of rate laws. A Zero-order reaction has a rate which is
independent of the concentration of the reactant(s). Increasing the concentration of the reacting
species will not speed up the rate of the reaction. Zero-order reactions are typically found when a
material required for the reaction to proceed, such as a surface or a catalyst is saturated by the
reactants. The rate law for a zero-order reaction is r = k, where r is the reaction rate and k is the
reaction rate coefficient with units of concentration/time. A reaction is zero order if concentration
data are plotted versus time and the result is a straight line. The slope of this resulting line is the
negative of the zero order rate constant k.
In a first order reaction, the rate is proportional to the concentration of one of the
reactants. That is, v = rate = k [B], where B is a reactant. If a reaction which is known to be first

order in B, such as B + other reactants → products, the rate law is written as,
The constant, k, in this rate equation is the first order rate constant. A plot of ln[A] vs. time t
gives a straight line with a slope of − k.
 In a second order reaction the rate is proportional to concentration squared. For example,
possible second order rate laws might be written as Rate = k [B]2 or as Rate = k[A][B]. That is,
the rate might be proportional to the square of the concentration of one of the reactants, or it
might be proportional to the product of two different concentrations. However, measuring a
second order reaction rate can be problematic: the concentrations of the two reactants must be
followed simultaneously, which is more difficult; or measure one of them and calculate the other
as a difference, which is less precise. A common solution for that problem is the pseudo first
order approximation. If either [A] or [B] remain constant as the reaction proceeds, then the
reaction can be considered pseudo first order because in fact it only depends on the concentration
of one reactant. If for example [B] remains constant then: where k' = k[B]0 and we have an
expression identical to the first order expression above. By collecting k' for many reactions with
different (but excess) concentrations of [B]; a plot of k' versus [B] gives k (the regular second
order rate constant) as the slope. Meanwhile, for a third order reaction, a rate law can be written
in several different ways. One might have cases where Rate = k[A]3, or Rate = k[A]2[B], or Rate
= k[A][B][C],and so on.
Several factors affect the rate of a chemical reaction. With the exception in certain
reactions, upon which concentration is without effect, an increase with the initial concentration
of reactants also results in an acceleration of the rate. This is in accordance with the collision
theory which assumes that for a reaction to occur, the reactant particles must collide. Therefore,
increasing the concentration will also increase the frequency of the molecules colliding, striking
each other faster by being in closer contact at any given point in time causing collisions to
happen more often. However, the rate for a given initial concentration does not remain constant
all throughout the reaction rather is highest at the beginning and decreases with time as the
reactants are consumed. The rate becomes low after a time that the reaction may be considered
complete.
Temperature also has a pronounce effect on the speed of reaction. When reactants in a
chemical reaction are heated, atoms or molecules gain more thermal energy and become more
energetic giving a greater probability to collide with one another. More importantly however, is
the fact that at higher temperatures molecules has more vibrational energy that is, atoms are
vibrating much more violently. Raising the temperature therefore, not only increases the number
of collisions but also collisions that can result in rearrangement of atoms within the reactant. In
addition, many reactions are influenced by the presence of substances that possess the ability of
accelerating or decelerating the rates of such reactions. These substances are called catalysts
which accelerate the rate of a chemical reaction but remain chemically unchanged afterwards.
The catalyst increases rate reaction by providing a different reaction mechanism to occur with a
lower activation energy. A catalyst does not affect the position of the equilibrium, as the catalyst
speeds up the backward and forward reactions equally
Increasing the pressure in a gaseous reaction will increase the number of collisions
between reactants, increasing the rate of reaction. This is because the activity of a gas is directly
proportional to the partial pressure of the gas. In addition, depending upon what substances are
reacting, the time varies. Acid reactions, the formation of salts, and ion exchange are fast
reactions. When covalent bond formation takes place between the molecules and when large
molecules are formed, the reactions tend to be very slow. The physical state of a reactant is also
an important factor of the rate of change. When reactants are in the same phase, as in aqueous
solution, thermal motion brings them into contact. However, when they are in different phases,
the reaction is limited to the interface between the reactants. Reaction can only occur at their area
of contact, in the case of a liquid and a gas, at the surface of the liquid. This means that the more
finely divided a solid or liquid reactant, the greater its surface area per unit volume, and the more
contact it makes with the other reactant, thus the faster the reaction. With a few exemptions,
homogeneous reactions generally take place faster than heterogeneous reactions.
For this experiment, the reaction of hydrochloric acid with zinc metal was observed with
the chemical equation: 2HCl + Zn  ZnCl2 + H2. This is a single displacement or a substitution
reaction, in wherein hydrogen was displaced by zinc which is a more reactive element. This
experiment aims to determine the order of the reaction and the activation energy of both
catalyzed and uncatalyzed reactions. More specifically, this experiment intends to determine the
effects of concentration, temperature and presence of a catalyst in the reaction of hydrochloric
acid and zinc.
II. Methodology
A. Effect of Concentration

Prepare serial dilution from concentrated

HCl, 5M, 4M, 3M, 2M and 1M solutions

Place 10mL of 1M HCl in a clean and dry

30mL ignition tube

• Add Zn metal
• Close the ignition tube with a stopper
Dip the tip of the delivery tube in a beaker
of water and measure the required time for
30 bubbles to emerge the tip of the delivery
tube

Repeat using concentrations 2M, 3M, 4M

and 5M

B. Effect of Temperature

Place 10mL of 2M HCl in a clean and dry

30mL ignition tube.

• Warm in a water bath until 40oC

• Remove the tube from water bath
• Add Zn metal
Determine the time required for 30 bubbles
to emerge from the tip.

Repeat with temperatures 50oC, 60oC and

70oC

C. Effect of Catalyst

Place 10mL of 2M HCl and 2mL Cu

(NO3)2 in a clean dry ignition tube

• Heat to 40oC in a water bath

Remove the test tube from the water bath
 • Add Zn metal
Determine the time required for 30 bubbles
to emerge from the tip.

Repeat for temperatures 50oC, 60oC and

70oC

III. Data and Results

A. Effect of Concentration

Concentration (M) time (s) Rate (1/time)

1 4863 2.056 x 10-4
2 4527 2.2090 x 10-4
3 3112 3.2134 x 10-4
4 1851 5.4025 x 10-4
5 993 1.0070 x 10-3

Plot of Rate vs [HCl]

0.0012

0.001
Rate (1/s)

0.0008

0.0006
m=0.9249
0.0004 y-int= - 8.76

0.0002

0
0 1 2 3 4 5 6
[HCl]
Determination of Rate Law:

Rate= k[HCl]n
ln Rate= nln[HCl] +lnk

Plotting [HCl] vs ln Rate:

n= m=0.9249
y-int= ln k= -8.76
k= 1.57 x 10-4

Rate Law: 1.57 x 10-4[HCl] 0.9249

B. Effect of Temperature

t (oC) T (K) 1/T time (s) 1/time k

40 313 3.1949 x 10-3 120 8.3333 x 10-3 4.39 x 10-3
50 323 3.0960 x 10-3 95 0.0105 5.53 x 10-3
60 333 3.0030 x 10-3 25 0.04 2.11 x 10-2
70 343 2.9155 x 10-3 22 0.0455 2.40 x 10-2

Sample Calculation for k:

k = Rate/[HCl]n
= 8.3333 x 10-3/ [2M] 0.9249
= 4.39 x 10-3

Plot of lnk vs 1/T

0
0.0029 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
-1

-2
lnk

-3
m= - 6,911.18
-4

-5

-6
1/T
Calculation of Ea:
lnk= (Ea/R)(1/T) + lnA

Plotting 1/T vs lnk:

m= - Ea/R= - (-6,911.18)
Ea= (6,911.18) (8.314 J/mol K) = 57, 459 J

C. Effect of Catalyst

t (oC) T (K) 1/T time (s) 1/time k

40 313 3.1949 x 10-3 237 4.2194 x 10-3 2.22 x 10-3
50 323 3.0960 x 10-3 226 4.4248 x 10-3 2.33 x 10-3
60 333 3.0030 x 10-3 182 5.4945 x 10-3 2.89 x 10-3
70 343 2.9155 x 10-3 169 5.9172 x 10-3 3.12 x 10-3

Plot of lnk vs 1/T

-5.75
0.0029 0.00295 0.003 0.00305 0.0031 0.00315 0.0032 0.00325
-5.8

-5.85

-5.9
lnk

-5.95
m= -1,1324.72
-6

-6.05

-6.1

-6.15
1/T
Calculation of Ea:
lnk= (Ea/R)(1/T) + lnA
Plotting 1/T vs lnk:
m= - Ea/R= - (-1, 1324.72)
Ea= (1, 1324.72) (8.314 J/mol K) = 11,013.75 J

IV. Discussion

It was observed that as concentration of reactants increases the rate of reaction also
increases. An increase in concentration causes an increase in effective collision for reaction to
occur. Temperature apparently has a major effect on the speed of reaction. By heating the
mixture, the energy levels of the molecules involved in the reaction are raised. As stated in
kinetic theory, increasing temperature means the molecules move faster. If the molecules have
enough energy, two molecules will then collide and react in accordance with the collision theory.
Thus, at higher temperature, more collisions take place. As demonstrated in this experiment, the
Arrhenius equation is adequate for demonstrating the effect of temperature on the rate of a
chemical reaction. The Arrhenius equation not only describes how reaction rates change with
increasing temperature but also can be used to predict activation energy, Ea, of a chemical
reaction. When a catalyst was added, it was observed that the catalyzed reaction is faster than
that of the uncatalyzed reaction. Only very minute quantities of the catalyst are required to
produce a dramatic change in the rate of the reaction. This is really because the reaction proceeds
by a different pathway when the catalyst is present.

V. References
http://en.wikipedia.org/wiki/Rate_law#Summary_for_reaction_orders_0.2C_1.2C_2_and_n
[Accessed May 9, 2008]
E:\Introduction to Chemical Kinetics, First Order Precesses, Half-Life.htm [Accessed May 9,
2008]
http://en.wikipedia.org/wiki/Chemical_kinetics [Accessed May 9, 2008]
http://www.purchon.com/chemistry/rates.htm. [Accessed May 9, 2008]
MARON, S. and JEROME LANDO, 1974. Fundamentals of Physical Chemistry. New York:
Macmillian Publishing Co., Inc., 673-702.