V Arvind Balakrishnan

CHEM 102-087
Winter 2015-16
Instructor: Ms. Junyang Xian

Lab 2: Kinetics of Alcohol Oxidation

Introduction
:

Chemical Kinetics is the branch of chemistry that deals with the study of reaction
rates and mechanisms. Its imperative that we understand the rate, the factors
controlling the rate as well as the mechanisms of a chemical reaction in order to
understand it fully.

Reactions such as ionic reactions usually take place very quickly. As an example, the
precipitation of silver chloride after the mixing of the aqueous solutions of silver
nitrate and sodium chloride is almost instantaneous. There are some reactions that
take place at a moderate pace, such as the inversion of cane sugar or hydrolysis of
starch. At the other end of the spectrum are extremely slow reactions like the
rusting of iron in the presence of air and moisture.

Using chemical kinetics to determine the rate of a given chemical reaction involves
the use of the
rate law of the given chemical reaction. The rate law for a given
reaction is an expression in which its rate is defined in terms of the molar
concentrations of the reactants with each term raised to a power that may or may
not be equal to the stoichiometric coefficient of the reactant as seen in the
balanced chemical equation of the given reaction. It is impossible to determine the
rate law for a given reaction by merely looking at the balanced chemical equation of
the reaction ; it has to be determined experimentally.

Consider the below shown chemical reaction in the solution phase:

The rate law for this reaction is

where the exponents

and

may or may not be equal to

stoichiometric coefficients of the reactants.

and

and

, the

are the partial orders of the

reaction, that is, order of the reaction wrt A and B respectively. The net order of the
reaction would be equal to the sum of

and

is a proportionality constant

called the rate constant.

in

and

are the concentrations of the reactant species

It becomes more tedious to calculate the order of a reaction when there is more
than one reactant involved. This is because each reactant contributes to the
reaction. So, in this case, what can be carried out in order to reduce the complexity
in the math that would arise is called
pseudo-order treatment
, which involves
determining the order of the reaction wrt each component independently.

The second part of the experiment involves an application of the Beers Law, which
is described in the following paragraph.

Beers Law: Beers Law states how attenuation of light and the properties of the
material through which the light travels are interrelated. According to Beers Law,

where

stands for the measured absorbance,

is a constant of proportionality

called the molar absorption coefficient,

that the light passes through and

refers to the path length of the solution

is the concentration of the absorbing molecule.

In this experiment, b is to be kept constant at 1 cm because of which the above

expression would reduce to

The third half of the experiment deals with the oxidation of alcohols and involves
the Breathalyzer Test which takes place according to the following reaction:

Here, potassium dichromate acts as the oxidising agent. The dichromate reduces
the Chromium (III) ions and the alcohol undergoes oxidation to get converted into
an aldehyde. The orange colour of the dichromate solution is observed to turn
green at the end of the reaction.
The concept of pseudo-order is put into use while finding the order and the rate
constant of the reaction. Given that the concentration of the alcohol used in the
reaction is large, it can be assumed to be of a constant value throughout the
reaction. This thereby enables us to ignore the value of the concentration of the
alcohol while finding the rate. Therefore, the rate of the reaction can be written as:

The order of the reaction is calculate graphically by applying the concept of linear
regression. The order of the reaction would be of that graph with the value of
correlation factor closest to 1.

Calculations and Discussions:

1. Concentration vs Absorbance

Concentration

Transmittance

Absorbance

13.1

0.00203

30.3

0.519

0.001015

51.43

0.289

0.004059

13.11

0.882

0.000203

85.06

0.07

The slope of the line gives us the value of molar absorptivity (

).

which is of the form y=mx+c. Therefore, the value of

is equal to 216.

Concentration of potassium dichromate for the next part of the experiment is found using the formula

Time

Transmittance Absorbance

[K2Cr2O7]

ln[K2Cr2O7]

0.00166666667

6.39692965

1/[K2Cr2O7]

30

43.64

0.36

216

599.999999

60

36.28

0.44

216 0.002037037037

90

39.25

0.406

216

120

42.32

0.373

216 0.001726851852 6.361455267 579.0884718

150

45.21

0.345

216 0.001597222222

180

48.07

0.318

216 0.001472222222 6.520982304

210

50.79

0.294

216 0.001361111111 6.599453919 734.6938776

240

53.62

0.271

216

270

56.27

0.25

300

58.78

0.231

216 0.001069444444 6.840615976 935.0649351

330

61.08

0.214

216 0.000990740740 6.917057672 1009.345794

360

63.46

0.198

216 0.000916666666 6.994766656 1090.909091

390

65.62

0.183

216 0.000847222222 7.073547534 1180.327869

420

67.57

0.17

450

69.39

0.159

216 0.000736111111 7.214129484 1358.490566

480

71.1

0.148

216 0.000685185185 7.285821413 1459.459459

510

72.74

0.138

216 0.000638888888 7.355780002 1565.217391

540

74.13

0.13

216 0.000601851851 7.415499236 1661.538462

570

75.42

0.123

216 0.000569444444 7.470849331 1756.097561

600

76.68

0.115

216 0.000532407407 7.538101558

630

77.9

0.108

216

6.19625896 490.9090909

0.00187962963 6.276680527 532.0197044

6.43948927 626.0869565
679.245283

0.00125462963 6.680914866 797.0479705

216 0.001157407407 6.761572769

216 0.000787037037

0.0005

864

7.14723525 1270.588235

7.60090246

1878.26087
2000

660

78.91

0.103

216 0.000476851851 7.648304698 2097.087379

690

79.82

0.098

216 0.000453703703 7.698066208 2204.081633

720

80.79

0.093

216 0.000430555555 7.750434194 2322.580645

750

81.63

0.088

216 0.000407407407 7.805696872 2454.545455

780

82.26

0.085

216 0.000393518518

810

82.92

0.081

216

840

83.62

0.078

216 0.000361111111

870

84.11

0.075

216 0.000347222222 7.965545573

2880

900

84.7

0.072

216 0.000333333333 8.006367568

3000

930

85.09

0.07

216 0.000324074074 8.034538445 3085.714286

960

85.4

0.069

216 0.000319444444 8.048927182 3130.434783

990

85.75

0.067

216 0.000310185185 8.078341067 3223.880597

1020

86.06

0.065

216 0.000300925925 8.108646417 3323.076923

1050

86.41

0.063

216 0.000291666666

1080

86.69

0.062

216 0.000287037037 8.155899302 3483.870968

1110

86.86

0.061

216 0.000282407407 8.172159822 3540.983607

1140

87

0.06

216 0.000277777777 8.188689124

3600

1170

87.18

0.06

216 0.000277777777 8.188689124

3600

1200

87.39

0.059

7.84038243 2541.176471

0.000375 7.888584532 2666.666667

7.92632486 2769.230769

8.13989896 3428.571429

216 0.000273148148 8.205496243 3661.016949

Zero Order Reaction:

Correlation Coefficient =

First Order Reaction:

Correlation Factor =

Second Order Reaction:

Correlation Factor =

Observations:

Based on the data obtained from the graphical plots, the oxidation reaction
appears to be of order 2. This is because the

vs time graph has the

value of correlation factor R closest to 1.

Calculation of the rate constant for the reaction:

The rate law for a second-order reaction has the following format:

where k is the rate constant and A is the concentration of the reactant.

Using the above rate law, the integrated rate law for a second order reaction can be
obtained as

where

is the concentration of the reactant at time t and

is the initial

concentration of the reactant.

This integrated rate law resembles a straight line of the formula

where k (the rate constant) is the slope of the line and

is the y-intercept.

So, from the graph, the value of k can be obtained to be equal to

Also, given that the concentration of the alcohol was observed to be very large in
comparison to that of

in the oxidation reaction, its a pseudo-first order

reaction. The pseudo-order rate would therefore give the true order of the reaction.

Conclusions
:

The reaction was observed to be of a pseudo-order equal to 1, and with a

pseudo-order rate constant equal to

These calculations were obtained from graphical plots which were obtained from
data analyzed with the help of Beers Law.

In this lab, we learnt how to use the Vernier LoggerPro software and collect data
using the program installed on the computer. We also learnt to collect the
absorbance of each reaction and the rate constants.

In terms of theory, we gained a lot of insight into chemical kinetics using Beers Law
and also the pseudo-order treatment of reactions.

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