A REPORT ON EXPERIMENTAL PHYSICAL CHEMISTRY

TITLE:

THE OXIDATION OF ISOPROPANOL BY CHROMIUM (VI)

 ABSTRACT

The experiment on the oxidation of Isopropanol (C 3H7OH) by HCrO4- was performed to

determine the order of reaction with respect to the substances that are taking part in the
reaction. The equation of reaction is given below:

3C3H7OH + 2HCrO4- + 8H+ → 3CH3C=OCH3 + 2Cr3+ 8H2O

The complete rate law is:

Rate = K[HCrO4-]x[C3H7OH]y[H+]z

From the expression above, the rate law shows that the partaking substances to be HCrO 4-,
C3H7OH, and H. This shows that the reaction rate is proportional to reactants only.

x, y and z refers to the order of reaction with respect to [HCrO4-],

[C3H7OH], [H+] respectively, and K represent rate constant.

After the experiment, it was it was discovered that the rate of the reaction with respect to
[HCrO4-] is one(1), and with respect to [C 3H7OH] is also one(1) while that of [H +] is assumed
to be one(1) also .

The overall order of the reaction is therefore

Order = x + y + z = 1 + 1 + 1 = 3

The rate constant for this reaction was found to be =

In this experiment, the solution used was a standard solution of K 2Cr2O7(a strong oxidizing
agent) and Na2S2O3 and 4ml of 3% aqueous KI. 10ml of HCrO 4- was pipetted and 4ml of 30%
aqueous KI was added . On titration with Na 2S2O3 solution, a green colour was observed
wherein starch was used near the end point. Further titration gave a pale blue green end point.
 INTRODUCTION

Chemical kinetics is an aspect of chemistry that deals with the study of rate of reaction. Some
reactions are spontaneous while some are slow. This Experiment was performed in order to
determine the order of reaction using a well defined titration procedure of oxidation of
Isopropanol by Chromium (VI) (Strong oxidation agent).

3C3H7OH + 2HCrO4- + 8H+ → 3CH3C=OCH3 + 2Cr3+ 8H2O

The order of reaction with respect to C 3H7OH and HCrO4- wasdetermined assuming [H+] to
be one.

It was observed from the experiment that the concentration of the solution varied with time
(10 minutes from 80minutes).

More so, it was observed that the addition of Isopropanol to the solution caused a change in
colour which on titration gave a quick end point.

THEORY

In the study of kinetic analysis reactions, one should first establish the stoichiometry of the
reaction. The basic idea is the monitoring the rate at which the concentration is changing with
time as reactants are being changed to product. To study the rate of chemical reaction,
chemical method or physical method may be employed. The chemical method involve the use
of gravimetry or titrimetric method while physical method involve the monitoring the
physical property of the system. E.g. change in volume or pressure of the reactant or product

Rate of reaction is defined as the change in the advancement of the reaction with time. i.e.
change in the concentration of reactant with time.

Rate law is an equation that relates rate of reaction as a function of the concentration of all
the species present in the reaction at the same time. It is determined experimentally.

Order of reaction with respect to a species is the power to which the concentration is raised in
the rate law.

E.g. aA + bB → cC + dD

R = K[A]a[B]b
Where “R” is the rate, “K” is the rate constant, “a”, and “b” are order of reaction with respect
to reactants “A” and “B” respectively.

The overall order of reaction is the sum of the order of individual species involved in the
reaction. For the above hypothetical reaction,

Overall order = a + b

Order of reaction could be zero whole number or fraction. If the overall order is zero, the
reaction is called zero order reaction, if the order is two, the reaction is called second order
reaction and so on.

The “R” is a function of reactants concentration at a fixed temperature.

This experiment is based on reaction rates in relation to

 Time(t):- Some reaction proceed very rapidly and some very slowly, therefore it
requires longer time for completion at ordinary temperature.

 The concentration of the reactants and product:-There is always a change

whenever reactants are being used up and product formed. Usually the concentration
of the reactant decreases while that of the product increases with time.

There are some factors that affect the rate of reaction. These are listed below

 Temperature:- The higher the temperature, the higher the effective collision of the
reactant molecule, this eventually lead to higher rate of reaction.
 Concentration/Pressure:-The higher the concentration of the reacting solid or liquid
molecules, the higher the rate of reaction. Whereas, the higher the pressure the higher
the rate of reaction for gaseous molecules.
 Catalyst:- Catalyst provide an alternative pathway of lower activation energy.
Thereby, introduction of catalyst increases the rate of chemical reaction
 Nature of reacting species: This depends if the reacting species are both in the same
phase i.e. homogenous or in different phases i.e. heterogeneous
 Surface area: The higher the surface area, the higher the number of particles of the
reactant available for reaction.

Measurement / determination of rate of reaction can be done through any of these methods:
  Differentiation method
 half life method
 integrated method
 graphical method

In general the rate of reaction is concerned with the speed of at which a reaction proceed.

For a an hypothetical reaction, . aA + bB → cC + dD

Rate of reaction = -1/a d[A]/dt = -1/b [B]/dt = 1/c d[C] = 1/d d[D]/dt

EXPERIMENTAL

APPARTUS:-

 Two Burette (one for acid and the other for base)
 Retort stand
 One measuring cylinder
 One 600 ml beaker
 Two Volumetric flask(10m)
 10 ml Pipette
 Two conical flasks (250 ml)

REAGENTS

 600 ml of 4M HCl,
 0.02M Na2S2O3,
 4ml off 3% aqueous KI (Potassium Iodide) K2Cr2O7,
 Distilled water,
 Pure Isopropanol,
 Starch, which was the indicator used

PROCEDURE

All the apparatus were first rinsed with the water to remove any contamination. The acid
burette was rinsed with acid. It was clamped into the retort stand and HCrO 4- solution was
carefully poured into the clamped burette to form the acid. From this 10ml was measured and
poured into a conical flask and 4ml 3%aqueous KI was added to it which reduces the solution
to reddish brown.

The other burette was filled with Na 2S2O3.The content of the conical flask was titrated against
the Na2S2O3.This was done until the colour changes from reddish brown to green using starch
near end point and this continued until a pale green end point was reached. The volume of
Na2S2O3 used was recorded.

Equation for this reaction

Cr2O72- + H2O → 2HCrO4-

2HCrO4- + 6I- + 14H+ → 3I2 + 2Cr3+ + 8H2O

Further titration to pale blue-green end point

I2 + 2S2O32- → 2I- + S4O62-

For the second part of the experiment

180ml of HCrO4- was measured with a measuring cylinder into the beaker. 2ml of
Isopropanol was added and mixed thoroughly. 10 ml was taken from this mixture and poured
into the conical flask, 4ml of 3% KI was added and titrated against Na 2S2O3.The time for this
first titration was noted and recorded as time zero. The end point was noted and recorded.
This same procedure was repeated at 10 minutes interval 8 times, noting the end point in
each. Also this same procedure was repeated for 3ml and 4ml of Isopropanol, noting and
recording the end point appropriately.

RESULTS

Table 1: Table of Values for 2mL Isopropanol

Time (mins) 0 10 20 30 40 50 60 70 80
Final 8.10 6.80 5.90 4.80 3.90 3.30 2.10 1.20 0.90
Reading(ml)
Initial 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Reading(ml)
Titre 8.10 6.80 5.90 4.80 3.90 3.30 2.10 1.20 0.90
value(ml)
Table 2: Table of Values for 3ml Isopropanol

Time (mins) 0 10 20 30 40 50 60 70 80
Final 8.10 6.50 6.20 5.80 5.50 4.80 2.80 1.00 0.60
Reading(ml)
Initial 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00 0.00
Reading(ml)

Titre 8.10 6.50 6.20 5.80 5.50 4.80 2.80 1.00 0.60
value(ml)

CALCULATIONS

Molar mass of K2Cr2O7 =(39.1) + (52.0x2) + (16x7) = 78.2 + 104 +112 = 294.2g/mol

Concentration of K2Cr2O7 = 3.7x10-3M

Mole of K2Cr2O7 = Concentration x volume = 3.7x10-3M x 600x10-3L =2.22x10-3mole

Mass of K2Cr2O7 = mole x molar mass = 2.22x10-3mole x 294.2g/mol = 0.65g.

Equation of reaction

Cr2O72- + H2O → 2HCrO4-

From this equation,

1 mole of Cr2O72 reacts to produce 2 mole of HCrO4-

i.e 2.22x10-3mole of Cr2O72 will react to produce 2 x 2.22x10-3mole of HCrO4-

Mole of HCrO4- = 2 x 2.22x10-3mole = 4.44x10-3 mole

Molarity of HCrO4- = Mole of HCrO4- /Volume of HCrO4-

Molarity of HCrO4- = 4.44x10-3 mole / 600x10-3L = 7.4x10-3 M

Considering the equation below,

2HCrO4- + 6I- + 14H+ → 3I2 + 2Cr3+ + 8H2O (1)

I2 + 2S2O32- → 2I- + S4O62- (2)

Multiplying (1) by 1 and (2) 3

2HCrO4- + 6I- + 14H+ → 3I2 + 2Cr3+ + 8H2O (3)

3I2 + 6S2O32- → 6I- + 3S4O62- (4)

Adding (3) and (4) to give the overall equation

2HCrO4- + 6S2O32- +14H+ → 2Cr3+ + 3S4O62- + 8H2O (5)

Volume of Na2S2O3 required to reduce 8.1ml HCrO4- solution was 8.1ml

Molarity of Na2S2O3 is 0.02M

Mole of Na2S2O3 = Molarity x Volume

Mole of Na2S2O3 = 0.02M x 8.1x10-3L = 1.62x10-4 mole.

To calculate the mole HCrO4-, from equation 5,

2 mole of HCrO4- react with 6 mole of 6S2O32-

Mole of HCrO4- = 1/3 mole of Na2S2O3

Mole of HCrO4- = 1/3 x 1.62x10-4 mole

Mole of HCrO4- = 5.4x10-5 mole

Molarity of HCrO4- = Mole of HCrO4- / Volume of HCrO4-

Molarity of HCrO4- = 5.4x10-5 mole / 10x10-3L = 5.4x10-3 M

For 2ml Isopropanol

From TABLE 1

From equation 5,

Molarity of HCrO4- = Mole of HCrO4- / Volume Na2S2O3

But Mole of HCrO4- = 1/3 x 1.62x10-4 mole of Na2S2O3

Molarity of HCrO4- = 1/3 x 1.62x10-4 mole of Na2S2O3 /Volume of HCrO4-

Molarity of HCrO4- = Molarity of Na2S2O3 x vol of Na2S2O3 / 3 x vol HCrO4-

At 10 mins,

Molarity of HCrO4- = 0.02M x 6.8x10-3 /3 x 10x10-3 = 1.62x10-4/3x10x10-3 = 4.5x10-3M

At 20 mins

Molarity of HCrO4- = 0.02 x 5.7x10-3 / 3x10x10-3 = 1.14x10-4 / 0.03 =3.8x10-3M

At 30 mins

Molarity of HCrO4- = 0.02 x 4.8x10-3/ 3x10x10-3 = 9.6x10-4 / 0.03 =3.2x10-3 M

At 40 mins

Molarity of HCrO4- = 0.02 x 3.9x10-3 / 3x10x10-3 =7.8 x10-5 /0.03 = 2.6x10-3M

At 50 mins

Molarity of HCrO4- = 0.02 x 3.3x10-3/ 3x10x10-3 = 6.6x10-3/ 0.03 =2.2x10-3M

At 60 mins

Molarity of HCrO4- = 0.02 x 2.1x10-3 /3x10x10-3 = 4.2x10-5 /0.03 =1.4x10-3 M

At 70 mins

Molarity of HCrO4- = 0.02 x 1.2x10-3 / 3x10x10-3 = 2.4x10-5 / 0.03 =8.0x10-4M

At 80 mins

Molarity of HCrO4- = 0.02 x 0.9x10-3 /3x10x10-3 = 1.8x10-5 / 0.03 = 6.0x10-4 M

Table 3: Table of Values for 2ml Isopropanol

Time (mins) Volume of [HCrO4-](M) log[HCrO4-] 1/[HCrO4-](M-1)

Na2S2O3(ml)
10 6.8 4.5x10-3 -2.347 222.2
20 5.9 3.8x10-3 -2.420 263.2
 30 4.8 3.2x10-3 -2.494 312.5
40 3.9 2.6x10-3 -2.585 384.6
50 3.3 2.2x10-3 -2.658 454.5
60 2.1 1.4x10-3 -2.854 714.3
70 1.2 8.0x10-4 -3.097 1250.0
80 0.9 6.0x10-4 -3.222 1666.7
TABLE 3

CALCULATION

Specific Gravity of Isopropanol 0.79 = 0.79g/mol

1000ml will contain0.79g/ml x 1000ml/1dm3 =790g/dm3

Molar mass of C3H7OH = (3x12) + (7x1) + 16 +1 = 36 + 7 +16 +1 =60g/mol

Molarity of C3H7OH = Mass concentration/ Molar Mass = 790g/dm3/60g/mol = 13.167M

Mole of 2ml Isopropanol = Volume x Molarity = 2x10-3dm3 x 13.167M = 0.0263 mole

Concentration of 2ml Isopropanol in 180ml HCrO4- solution

Mole =0.0263mole

Volume = 180x10-3dm3

Concentration = mole/ volume = 0.0363mole / 180x10-dm3 = 0.146mol/dm3

Calculation using 3ml of Isopropanol solution

Molarity of HCrO4- = Molarity of Na2S2O3 x vol of Na2S2O3 / 3 x vol HCrO4-

At 10 mins

Molarity of HCrO4- = 0.02M x 6.5x10-3dm3/3 x 10x 10-3L = 1.3x10-4/0.03 =4.33x10-3M

At 20 mins

Molarity of HCrO4- = 0.02M x 6.2x10-3dm3 / 3x10x10-3 =1.24x10-4 /0.03 = 4.13x10-3M

At 30 mins
Molarity of HCrO4- = 0.02M x 5.8x10-3dm3 / 3x10x10-3 = 1.16x10-4/0.03 = 3.87x10-3M

At 40 mins

Molarity of HCrO4- = 0.02M x 5.5x10-3dm3 / 3x10x10-3 = 1.1x10-4 / 0.03 = 3.67x10-3M

At 50 mins

Molarity of HCrO4- = 0.02M x 4.8x10-3dm3 / 3x10x10-3 =9.6x10-5 / 0.03 = 3.2x10-3M

At 60 mins

Molarity of HCrO4- = 0.02M x 2.8x10-3dm3 / 3x10x10-3 = 5.6x10-3/0.03 = 1.86x10-3M

At 70 mins

Molarity of HCrO4- = 0.02M x 1.0x10-3dm3 / 3x10x10-3 = 2.0x10-5/0.03 = 6.67x10-4M

At 80 mins

Molarity of HCrO4- = 0.02M x 0.6x10-3dm3/ 3x10x10-3 = 1.2x10-5/0.03 = 4x10-4M

Table 4: Table of Values for 3ml Isopropanol

Time (mins) Volume of [HCrO4-](M) log[HCrO4-](M) 1/[HCrO4-](M-1)

Na2S2O3(ml)
10 6.5 4.33x10-3 -2.36 230.94
20 6.2 4.13x10-3 -2.38 242.13
30 5.8 3.87x10-3 -2.41 258.39
40 5.5 3.67x10-3 -2.44 272.48
50 4.8 3.20x10-3 -2.49 312.50
60 2.8 1.80x10-3 -2.74 555.56
70 1.0 6.67x10-4 -3.18 1499.25
80 0.6 4.00x10-4 -3.39 2500.00

CALCULATION

Specific gravity of Isopropanol is 0.79g/ml

1000ml will contain 0.79/ml x 1000ml/1dm3 = 790g/dm3

Molar mass of C3H7OH = (3x12) + (7x1) + 16 +1 = 36 + 7 +16 +1 =60g/mol

Molarity of C3H7OH = Mass concentration/ Molar Mass = 790g/dm3/60g/mol = 13.167M

Mole of 3ml isopropanol is = volume x molarity

=3x10-3dm3 x 13.167M = 0.0395 mole

Concentration of 3ml Isopropanol in 180ml HCrO4- solution

Mole =0.0395mole

Volume = 180x10-3dm3

Concentration = mole/ volume = 0.0395mole / 180x10-dm3 = 0.219mol/dm3

DISCUSSION

The experiment showed a straight line graph of concentration against time. From the graph it
can be inferred that the reaction is first order with respect to the reactants. The overall order is
: 1+ 1 +1 = 3.

Hence, the oxidation of Isopropanol by Cr3+ in the:

2HCrO4- + 6S2O32- +14H+ → 2Cr3+ + 3S4O62- + 8H2O

Follows a first order reaction with respect to [HCrO4-] and [C3H7OH]

PRECAUTION

1. I ensured that my apparatus were well calibrated

2. I ensured that my readings were taken at exactly 10 minutes interval for all the
experiments