CHM 431

PHYSICAL CHEMISTRY

TITLE : KINETICS- ORDER OF REACTION

NAME : NURFADHILAH BINTI JAAFAR

ID NUMBER : 2016675256

GROUP : AS 246 3B

LAB PARTNER : SITI FATIMAH BINTI SHAIKH ABDUL MUNAIM

SUBMITION DATE : 8TH NOVEMBER 2016

LECTURERS NAME : MADAM ZARILA MOHD SHARIFF

TITLE

Kinetics- Order of Reaction

OBJECTIVES

a) To determine the order of a reaction

INTRODUCTION

The study of rates of chemical process is related to chemical kinetics which is a branch
of chemistry and also known as reaction kinetics. The rate of homogenous reaction at any
instant is proportional to the product of the molar concentration of the reactants raised to power
determined from the experiment. The order of the reaction can be express on the following form:

Rate= k[A]x [B]y[C]z

The letters A, B and C represent the concentration of the reactants. k is referring the rate
constant, while the exponents x, y and z are called the rate law of exponents or also known as
the orders of the reaction. The methods of initial rates were used, in which the reaction of
interest is carried out at different concentrations and the rate of trial is measured. They do not
change in temperature and must be determined experimentally and the temperature must hold
at constant during the kinetic experiment. The magnitude of the rate constant indicates the
speed of the reaction. Hence, a small rate constant indicates a slow reaction, while large rate
constant indicates a faster reaction.

The experiments that need to be observed are between potassium permanganate and oxalic
acid. A deep purple colour of potassium permanganate will change to light brown when react to
oxalic acid and it can be observed visually. The rate of reaction can be described by the general
equation called the rate law equation:

Rate= k[KMnO4]x [H2C2O4]y

The Rate Method of Initial Rates

The initial rates method is a way to make the reaction of a reactant effectively constant. Initial
rate of a reaction is defined as the rate of reaction at the instant the reactants are first mixed.
The time it takes to use up the permanganate and the speed are the subjects that need to be
focused to determine the speed of the reaction.
 Rate =-d[KMnO4]/dt= {[KMnO4]final [ KMnO4]initial}

(tfinal tinitial)

Since [KMnO4]final = 0, and if we set tinitial = 0, the above equation simplifies to:

Rate= -(-[KMnO4]initial/tfinal) = [KMnO4] /t

The exponents x and y can find by using the method of initial rates. It is impossible to make the
measurements from the exact instant a reaction starts because the initial rates are always
estimation. Hence the method involves the measurement and comparison of the initial rates of
reaction when different initial concentrations are used. The initial rate for each being potassium
permanganate concentration divided by time. The rate of expressions for experiment 1 and
experiment 2 can be written as follow:

Rate1 = k[ KMnO4]1 x[H2C2O4]1y Rate1 = [KMnO4]1/t1

Rate2 = k [KMnO4]2 x[H2C2O4]2y Rate2 = [KMnO4]2/t2

Taking the ratio of the two rates:

Rate1/Rate2 =([ KMnO4]1/[KMnO4]2)x

(Note that in these two reactions [H2C2O4]1 = [H2C2O4]2, thus can be cancelled out). Thus we
can determine x. In a similar manner, y, the order of reaction with respect to oxalic acid can be
determined if we compare experiment 1 and 3)

PROCEDURE

1. Three burettes were set up; one contained 0.02 M KMnO4, one with 0.5M H2C2O4 and
one with distilled water. A label was placed on each because it was difficult to
differentiate between water and oxalic acid. The exact molarities of the KMnO4 and
H2C2O4.
2. The required amount of H2C2O4 and distilled water was place into a thoroughly washed
and dried conical flask. The amounts are dictated by the experiment that you are doing
as Table 4.1. When we was overshoot we need to start again. This lab is very
dependent on dispensing the exact quantities.
 Reagents Exp 1 (cm3) Exp 2 (cm3) Exp 3 (cm3)
H2C2O4 20 20 10
KMnO4 10 5 10
H2O 0 5 10

Table 4.1 Volume of reagents required

3. The required amount of KMnO4 was placed into a 15 cm test tube.
4. Permanganate was added to the oxalic acid and the timing was started when the
permanganate tube was emptied. The conical flask was mixed thoroughly by swirling
until the solution turns a light yellow/ brown colour. The timing was stopped and the time
it actually took for the reaction to take place was recorded.
5. The experiment was repeated with a second and third trial. The average of these 3 was
took as the reaction time.
6. Steps 3 through 5 were repeated for experiments 2 and 3.
7. The rate for each of the three experiments was determined. That was just the
[KMnO4]/taverage
8. The full rate equations for each of the 3 experiments were determined. Note that

Rate = k[KMnO4]x[H2C2O4]y
The values of k, x and y were determined.

CHEMICALS

1. Potassium Permangante (KMnO4), 0.020 M

2. Oxalic acid, (H2C2O4), 0.50 M
DISCUSSIONS

The experiment was done to observe the order of the reaction of oxalic acid and
potassium permanganate by changing their initial molar concentration. The molarity for
experiment 1, experiment 2 and experiment 3 for H2C2O4 and KMnO4 are 0.50 M and 0.020 M
respectively. The volume used for H2C2O4 and KMnO4 are 20 ml and 10 ml respectively in
experiment 1. For experiment 2, the volume of H2C2O4 used remain the same, 20 ml, but volume
KMnO4 is reduce to 10 ml. Volume for KMnO4 and H2C2O4 used in experiment 3 both reduce at
the same volume which are 10 ml . Each experiment conducted with 3 trials. In experiment 1 the
average time it took to completely react are 191s while in experiment 2 it took 218s on average.
Experiment 3 took the longer time on average for the solution to change is colour which is 348s.
The correct mechanism for this reaction at experiment 3 could be slow since the rate of reaction
dependent on the concentration of KMnO4.

The sample of calculation is shown below:

Calculations for The Concentration of KMnO4

Experiment 1 and 2 = no dilution the concentration remain 0.50 m
Experiment 3 = 0.50 M(0.01) = Cfx (0.02)
Cf = 0.25 M
Calculations for The Concentration of H2C2O4
Experiment 2: CiVi = CfVf
(0.02 M)(0.005 M) = Cf (0.01)
Cf = 0.010 M
The average time
350 s + 343s + 353 s = 348s
3
The Initial Rate
Experiment 1 = Rate 1= [KMnO4] =0.20 M =1.07 x 10-4 Ms-1
T1 191s
Rate 1 = [H2C2O4] = 0.50 M =2.68 x 10-3 Ms-1
T1 186.6 s
 The order of the reaction was determined by one of the common method which is
method of initial rates. The initial concentration for each solution is being consecutively
changed to observe how these factors can affect the rate of reaction. In experiment 1
and 2 the initial concentration of KMnO4 is reduced 2 times cause the reaction rate to
decrease by factor 4.93 x10-5. As shown in calculation the reaction order that we get is 2,
but supposedly we should get the reaction of order is x =1. The reaction should be First
Order with respect to KMnO4. Now we compare Expts 1 and 3. Here a doubling of the
initial KMnO4 concentration causes no change in the Reaction Rate. Hence, making the
overall reaction order y = 2 and the reaction is Second Order with respect to H2C2O4
supposedly. Thus the rate of law of reaction should be:
Rate: k[KMnO4]1[H2C2O4]2
The average rate of constant was calculated to be 128.66 s-1. There were several
potential errors that happen in conducting the experiment that cause for us to not getting
the expected result of the order of the reaction. Some errors could include failing to
dispense the exact amount of reactant into the test tube, failing to mix the solution after
each reactant or failing to time properly for the each of the reaction. For instance, when
the timer was not stopped when the solution reached the desired colour change, it could
alter the results, because each reaction was carried out to different point, not necessarily
the end point. All these errors could affect the rate of reaction from getting the expected
results.

CONCLUSIONS

In conclusion, we could not get the expected result of the order of the reaction due to
some errors. The expected order of the reaction should be Rate: k[KMnO 4]1[H2C2O4]2 . The
average times taken for the reaction to takes place for experiment 1, experiment 2 and
experiment 3 are 191s, 218 s and 348s. On the other hand, the rate reaction for experiment 1,
experiment 2 and experiment 3 are 2.68 x 10-3 and 4.93 x 10-5 and 7.59 x 10-4 Ms-1. However
the average k is 128.66 s-1
QUESTIONS

1. In this experiment the orders of reaction x and y are obtained by taking ratios of
rates for two trials or experiments.
a) Explain how this experiment can be modified so that the orders of reaction can
be obtained by plotting appropriate graphs.
Graphical method can be also be applied to second order of the reactions. A plot of
1/[A]t versus t gives a straight line with a slope of k.

b) What plots must be done and explain how the orders of reaction can be
determined from the plots.
Use the data in the table to separately plot concentration, the natural logarithm of
the concentration, and the reciprocal of the concentration (the vertical axis) versus
time (the horizontal axis). Compare the graphs with those in Figure 14.16 "Properties
of Reactions That Obey Zeroth-, First-, and Second-Order Rate Laws" to determine
the reaction order .Write the rate law for the reaction. Using the appropriate data
from the table and the linear graph corresponding to the rate law for the reaction,
calculate the slope of the plotted line to obtain the rate constant for the reaction.
For zero-order reactions, graph concentration vs. time to get a line with the slope -k.
For first-order reactions, graph the logarithm of concentration vs. time to get a line
with the slope -k. For second-order reactions, graph the reciprocal of concentration
vs. time to get a line of slope -k.

c) Would this method (graphically) be more accurate than what has been done
experimentally?
Yes. It is because plotting the concentration of a reactant as a function of time
produces a graph with a characteristic shape that can be used to identify the reaction
order in that reactant.

2. Orders of reaction are normally integers. Is it possible to have non-integers. E.g

fractions as order of the reaction? if yes give an example of such reaction.
Yes there are reaction inn fractional order reactions, the order is a non-integer,
which often indicates a chemical chain reaction or other complex reaction mechanism
For example, the pyrolysis of ethanal (CH3CHO) into methane and carbon monoxide
 proceeds with an order of 1.5 with respect to ethanal: r = k[CH3CHO]3/2.[13] The
decomposition of phosgene (COCl2) to carbon monoxide and chlorine has order 1 with
respect to phosgene itself and order 0.5 with respect to chlorine: r = k[COCl2] [Cl2]1/2.

REFERENCES

1. Iskandar, A. (2012, April 21). Reaction Order. Retrieved October 25, 2016, from
http://chem.libretexts.org/Core/Physical_and_Theoretical_Chemistry/Kinetics/Rate_Laws
/The_Rate_Law/Reaction_Order
2. Chang, R. (2005). Physical Chemistry for the Biosciences. Sansalito, CA: University
Science
3. Launer, H. F., & Yost, D. M. (1934). The Kinetics of the Reaction between Potassium
Permanganate and Oxalic Acid. II. Journal of the American Chemical Society, 56(12),
2571-2577. doi:10.1021/ja01327a013