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Title

Determination of Reaction Rate Constant and Rate Order For Hydroxylation Between
Methyl Violet IIB solution and Sodium Hydroxide at Ambient Temperature

Author Information

Sheikh Mohammad Faisal Sh. Mohd. Nasir
Chemical Engineer
School of Chemical Engineering
The University of New South Wales
Sydney, NSW 2052
E: z3358227@unsw.edu.au

Abstract

This report presents a method to determine the reaction rate constant for the
hydroxylation reaction between methyl violet IIB solution with sodium hydroxide at
ambient temperature. Using a prepared dye solution with concentration (0.9 0.3) X 10-5
M, the dye solution was reacted with 0.0500 0.0004 M and 0.1000 0.0002 M of sodium
hydroxide separately. The absorbance was recorded within a period of time and the
reaction rate constant was calculated to be 0.009 0.001 !.! !.! !! with rate order 0.8
0.2 with respect to the concentration of sodium hydroxide and rate order 1 with respect
to the concentration of dye solution. The work presented here has profound implication for
controlling water pollution in our environment.

1. Introduction

1.1 Background



One of the wide range of organic compounds that is useful in textile industries is methyl
violet IIB or abbreviated as MV [1]. This three-aromatic-ring compound is used widely as a
fabric dye and printing industries. Typically, the by-products from these industries are
disposed to the environment via water drainage. Methyl violet presents in the effluents
raises a lot of environmental issues due to its toxic property to aquatic organisms. The
existence of this dye in the effluent reduces the transparency of the water even at its low
concentration due to its strong colour [2]. Consequently, the amount of light pass through
the wastewater will be reduced and inhibit the growth of aquatic plant which is the source
of oxygen for aquatic organisms. Besides that, methyl violet IIB can be transferred
indirectly to human being via the uptake by aquatic organisms [3]. Accumulations of
methyl violet IIB in the body, which is known to be mutagenic can harm the physiological
performance of human beings and can even cause death [4]. With such concern, people
start to study the methods to remove MV from the environment. Removal of MV
procedures from the environment includes chemical bleaching, biodegradation, ion
exchange and etc. However, these methods do not necessarily solve this issue. One of the
reasons is the by-products from such reactions produce other negative impacts.
Hydroxylation is proposed and considered to be a better alternative for MV removal
method and the kinetics of this procedure is studied. The rate constant and the reaction
order are crucial to be determined as they govern how fast the reaction happen. By

knowing them, the efficiency of methyl violet removal method can be improved and hence,
reducing the threat to the environment.

1.2 Aim

The aim of this experiment is to develop a theoretical framework that can be used to
determine the rate constant and order of reaction for hydroxylation of methyl violet IIB.
This experiment also is aimed to develop a calibration curve to determine the
concentration of methyl violet IIB from the absorbance obtained from the colorimeter as
well as calculating the reaction rate constant and reaction order at ambient temperature
for the hydroxylation reaction.

1.3 Objectives



The aim of this experiment can be achieved by deriving the overall rate equation from the
theoretical rate equation. This experiment is done to determine the reaction order and
reaction rate constant from the developed theoretical framework. To obtain the
concentration of methyl violet IIB from the colorimeters absorbance, a calibration graph is
plotted. The absorbance of methyl violet standard solution is measured to build the
calibration curve. Graphical approach and linear regression are used to analyze the
calibration curve to obtain the concentration of the MV solution and to determine the
reaction order and reaction constant.

2. Theory

2.1 Mechanism of Hydroxylation Between Methyl Violet IIB and Sodium Hydroxide

Methyl Violet IIB is a compound with three aromatic rings and has an absorbance peak of
575nm [5] and undergoes hydroxylation reaction. An example of hydroxylating agent is
sodium hydroxide. The reaction can be illustrated below in Figure 1:


Figure 1: The hydroxylation reaction between methyl violet IIB molecules with sodium
hydroxide

The hydroxylation is basically governed by nucleophilic addition to the carbon-carbon


double bond. In this reaction, the hydroxide ions act as nucleophiles (a chemical species
that has an electron lone pair that reacts with an electrophile to form a chemical bond).
Aromatic rings can shift the electron density to themselves due to their neuclophilic
properties and thus making the marked carbon in figure 1 to be an electrophile (a chemical
species that lack with electron density). The presence of nucleophilic reagent and
electrophilic carbon make the reaction to be feasible at ambient temperature.

First, the hydroxide ions attack the electrophilic carbon atom and form covalent bond
together. The electron density in the pi bonds as well as the negative charges of the
hydroxide ions were shifted to the next carbon, causing it to be a nucleophile or as known
as carboanion. Then, the carboanion attacks any electrophile present, which in this case are
the hydrogen ions. The carboanion loses its negative charge and form a covalent bond with
the hydrogen atom. The mechanism of this nucleophilic addition can be illustrated below in
Figure 2:


Figure 2 The mechanism of nucleophilic addition between hydroxide ion and the methyl
violet IIB molecule
2.2 Rate Equation

In chemical kinetics, reaction rate constant is a quantity that quantifies the speed of a
particular reaction. The rate constant can be found in a rate equation, which is an equation
that governs holistically the speed of a reaction. The rate equation for the hydroxylation of
reaction between sodium hydroxide and methyl violet IIB can be written as follows:

![!"]
= ! [! ]!



(1)
!"

where [MV] is the concentration of the methyl violet IIB solution, [OH-] is the concentration
of sodium hydroxide, k is the rate constant, n and m are the order of reaction with respect
to the dye solution and sodium hydroxide respectively. The negative sign shows that the
concentration of the dye solution is decreasing as time increase since the dye molecules are
being consumed in the reaction.



2.3 Pseudo Rate Law



By using equation (1), each parameter (k, m and n) cannot be figured out since only one
equation is present. Besides that, it is difficult to monitor the changes of concentration of
both chemical species during the chemical reaction at the same time. Therefore, a pseudo
rate constant is invoked to simplify the task by treating one of the reagents to be constant.
To use this pseudo rate law, flooding condition need to be introduced by using a very high
concentration of sodium hydroxide relatively compared to the concentration of the dye
solution ([OH-] >>> [MV]). By applying such condition, equation (1) will be reduced to the
following equation: [6]

![!"]
= !" []!




(2)
!"
where

!" = [! ]!





(3)

and kps is the pseudo rate constant.

2.4 Theoretical Framework For Reaction Rate Law

The pseudo rate equation can be either zero, first and second order with respect to the
concentration of MV i.e. the value of n can be 0, 1 or 2. Then, the rate equation is integrated
both sides with respect to the dye concentration and time respectively for different values
of n. The limit of the left hand side is applied from the initial dye concentration ([MV]0) to
the dye concentration at time equal to t ([MV]t) whereas the limit of the right hand side is
applied from time = 0 to time = t. Since the light travels through the same path length and
the methyl violet molecules are assumed to have a constant molar absorbtivity, according
to Beer-Lamberts Law, the absorbance is directly proportional to the methyl violet IIB
solution i.e. absorbance [MV] and hence, the equation (4) below can be obtained:

[!"]!
[!]!
=





(4)
[!"]
[!]
!


where [A]0 and [A]t is the initial absorbance and absorbance at time = t. Applying the limits
and substituting equation (4) into the integrated equation, the pseudo rate equation will be
as tabulated in Table 1:

Reaction Order

Zero

First


Second

Value of n

0


1


2

Integrated Pseudo Rate Equation


!"

[]!
= 2.3026!"
[]!

1
1
=
+ !"
[]! []!

Table 1: The integrated pseudo rate equation for every possible value of n
where 2.3026 is the conversion factor to convert the natural logarithm to a logarithm with
base 10 and is the conversion factor to convert from concentration to absorbance.
Continuation of this derivation can be referred at the Appendix Section.

3. Materials and Methods

3.1 Determination of Absorbance-Concentration Relationship.

Standard laboratory apparatus were used for the following experimental procedure. A
standard solution with 1 X 10-4 M was prepared with the provided methyl violet powder
(Sigma-Aldrich). Then, the standard solution was diluted to five different concentrations
via the standard dilution procedure. The colorimeter (Orion AQUAfast) was recalibrated
with 10 ml of deionized water and the absorbance of each different concentration of
standard solution was measured and recorded. The data collection procedure was done
thrice to get three sets of absorbance readings. A graph of absorbance against
concentrations was plotted and the gradient of the graph was calculated by using linear
regression approach via Microsoft Excel for Mac 2011.

3.2 Experimental Set Up

The standard solution was diluted to 1 X 10-5 M. 5 ml of this diluted standard solution was
pipetted into the colorimeters vial. Another 5 ml of 0.1 M sodium hydroxide (Ajax) was
pipetted in to the same vial. The vial was capped and placed inside the colorimeter for
absorbance reading. The absorbance and the instantaneous time when the reading was
shown by the colorimeter were recorded. This procedure was repeated thrice to obtain
three sets of absorbance data for the reaction of methyl violet IIB with 0.1 M sodium
hydroxide.

The 0.1 M sodium hydroxide was diluted to 0.05 M sodium hydroxide and the experimental
procedure was repeated by replacing 0.1 M sodium hydroxide with 0.05 M sodium
hydroxide.

3.3 Determination of Rate Constant and Order of Reaction

Required graphs to be plotted and the calculation to find the pseudo rate constant was
shown in Table 2 below:


Reaction
Order

Zero

First

Second

Value of n Graph To Be
Plotted



0
[]!




1
log !





1
2

[]!

Gradient, m
!" =

!" =


2.3026

!" =

Table 2: The required graph to be plotted and calculations to find the pseudo rate
constant.
Since two different and known concentrations of sodium hydroxide were used, these
produced two distinct pseudo rate equations, which were solved simultaneously to obtain
the reaction rate constant and the order of reaction with respect to the concentration of
sodium hydroxide.



4. Results

The order of reaction with respect to the concentration iof OH- ions is 0.8 0.2. The
reaction rate constant at ambient temperature for the hydroxylation reaction, which was
obtained from the experiment, was 0.009 0.001 !.! !.! !! , with 95% confidence. This
was calculated from the mean of 3 kps values from 3 trials taken with the corresponding
uncertainty, which was calculated using the t-value from Crawshaw et. al. [8]

From the plotted calibration curve, it can be concluded that the relationship between
absorbance and concentration of the dye solution is directly proportional, i.e. Absorbance
[MV], and thus, it is valid to use the Beer-Lamberts Law. The calibration graph can be
found in the Appendix section

5. Discussions

5.1 Selection of n=1

The results obtained above was done by taking the value of n equal to 1 i.e. the order of
reaction with respect to the concentration of methyl violet is first order. The selection was
was made based on the regression coefficient value (R2). Every graph mentioned in Table 2
was plotted and the R2 values were calculated by using the Trendline option in Microsoft
Excel 2011 for Mac. Then, the values were compared. The closer the R2 values to 1, the
better the correlation. The comparison of R2 values can be seen at the Appendix section.

4.2 Error in Mixing The Reactants

The resulted rate constant has an error, which cannot be avoided. When adding both
reactants in a vial, the vial cannot be shaken to mix the solution. This was done so that no

air bubbles were trapped in the vial, which can cause interference and result in inaccurate
absorbance data. This caused the rate of reaction at the upper part of the vial to be higher
than the lower part as when the solutions were mixed, the upper part had a higher
concentration of reactants compare to lower part that leaded to a difference in rate of
reaction.

4.3 Reviews on The Results

From the experimental results, which are 0.8 0.2 for the order of reaction with respect to
the concentration of OH- seems acceptable since the order of reaction ranged from 0.6 to 1.
There is a chance that the order of reaction to be an integer 1, which theoretically, the
order of reaction is typically an integer. The reaction rate constant is
0.009 0.001 !.! !.! !! and seems to be acceptable as well, since this parameter is
expected to have a low value. Besides that, the error is small too.


5. Conclusion

The reaction rate constant for the hydroxylation between methyl violet IIB and sodium
hydroxide can be determined by using a colorimeter as long as it satisfies the Beer-
Lamberts law. In this experiment, the order of reaction with respect to the concentration
iof OH- ions is 0.8 0.2. The reaction rate constant at ambient temperature for the
hydroxylation reaction, which was obtained from the experiment, was
0.009 0.001 !.! !.! !!

This experiment can be improved by increasing the concentration of methyl violet IIB up to
1 X 10-4 M so that the change of absorption can be seen much clearly. The samples of
methyl violet IIB used for plotting the calibration curve can be increased to improve the
accuracy of the absorption-concentration relationship.

6. Acknowledgement

The author would like to acknowledge the School of Chemical Engineering of University of
New South Wales for providing necessary infrastructural facilities to run the experiment.
The author also gratefully thanks Dr. May Lim, Ayu Liana and Mitchell Grierson for an
outstanding advices and guidance throughout the experiment and report writing period.
Not to forget, fellow collogues for their useful discussions.

7. Reference

1. Ou, X., Wang, C., Zhang, F., Sun, H., Wuyunna, (2013). Degradation of Methyl Violet
by Fentons Reagent: Kinetic Modelling and Effects of Parameters, Desalination and
Water Treatment, 51:13-15, p. 2536-2542.
2. Nidheesh, P. V., Gandhimathi, R., Ramesh, S. T., Singh, T. S. A., (2012). Adsorption and
Desorption Characteristics of Crystal Violet In Bottom Ash Column, Journal of Urban
and Environmental Engineering, 6:1, p. 18-29
3. Nidheesh, P. V., Gandhimathi, R., Ramesh, S. T., Singh, T. S. A., (2012). Adsorption and
Desorption Characteristics of Crystal Violet In Bottom Ash Column, Journal of Urban
and Environmental Engineering, 6:1, p. 18-29
4. Duxbury, D. F., (1993). The Photochemistry and Photophysics of Triphenylmethane
Dyes in Solid and Liquid Media, American Chemical Society, 93, p. 381-433

5. Ou, X., Wang, C., Zhang, F., Sun, H., Wuyunna, (2013). Degradation of Methyl Violet
by Fentons Reagent: Kinetic Modelling and Effects of Parameters, Desalination and
Water Treatment, 51:13-15, p. 2536-2542.
6. Corsaro, G., (1964). A Colorimetric Chemical Kinetics Experiment, Journal of
Chemical Education, 41:1, p. 48-50.
7. Ricci, R. W., Ditzler, M. A., Nestor, L. P. (1994). Discovering the Beer-Lambert Law,
College of the Holy Cross, 71:11, p. 983-985
8. Corsaro, G., (1964). A Colorimetric Chemical Kinetics Experiment, Journal of
Chemical Education, 41:1, p. 48-50.
9. Crawshaw, J., Chambers, J. S., (2001), A Concise Course in A-Level Statistics, 4th
edition, Nelson Thornes, Cheltenham, 650.


9. Appendix

9.1 Derivation of Theoretical Framework For Reaction Rate Law

The full derivation for integrated rate equations for every value of n can be seen in
Table 3 below:

n
Derivation
[]
0
= !" []!


[] = !"

[!"]!

[!"]!

[]!
[]!

[!"]!

= !"
= !"

!"

[!"]!

1
[] =
[]

!
!

!"

[]!
= 2.3026!"
[]!

!"

[]
= !! []!

[] =

[]!
= 2.3026!"
[]!

[]
= !" []!

[!"]!
[!"]!

1
[] =
[]!
1
1
+
!

!
!

!"

= !"

1
1

= !"
[]! []!

1
1

= !"
[]! []!

1
1
=
+ !"
[]! []!

Table 3: The full derivation of integrated rate equations for every value of n

9.2 Raw Experimental Data and Calibration Curve


Mass of methyl violet IIB dissolved = 0.0034 0.0001 g
Concentration of standard solution= (0.86 0.03) X 10-4 M

The data values that were used to pot the calibration can be seen in Table 4 below:
Amount of
Standard
Solution
Diluted (ml)
0
5
10
15
20
25

Concentration, (M)
(X 10-5)

[A]1

0 0
0.43 0.01
0.86 0.03
1.30 0.04
1.73 0.05
2.16 0.06

0
216
478
701
1017
1165

Absorption Reading
[A]2
[A]3
[A]average
0
225
482
719
986
1226

0
228
479
718
1008
1213

Table 4: The raw data values used to plot the calibration curve

0 0
223 16
479 5
712 25
1003 40
1201 80

Figure 3: The calibration curve. A graph of absorption against concentration of methyl


violet IIB

9.2 Comparison of R2 Values


The closer the R2 values with 1, the better the correlation is. Based on Table 5
below, it can be seen that for first order, the value of R2 shows the best correlation.

Data Set
1
2
3

Zero Order
0.1 M NaOH 0.05 M NaOH
0.9334
0.9884
0.9540
0.9839
0.9430
0.9822

First Order
0.1 M NaOH 0.05 M NaOH
0.9992
0.9955
0.9998
0.9998
0.9956
0.9996

Second Order
0.1 M NaOH 0.05 M NaOH
0.9725
0.9824
0.9594
0.9880
0.9741
0.9878


Table 5: Comparison of R2 Values for Different Values of n