Kinetics of Malachite Green Fading – Integrated Rate Law Analysis

Malachite Green is a dye whose color depends on pH making it a great acid-base indicator. The major
structural form of malachite green is the monovalent cation, abbreviated MG+, which is shown in
below. MG+ is the predominant form of malachite green in the solid state and in aqueous solution
across a broad range of pH values from pH 1 to 13.

In strongly basic solutions the blue-green MG+ cation slowly combines with hydroxide ions to form a neutral product,
MG-OH, which is colorless. The rate of this reaction (Equation 1) is slower than typical acid–base proton transfer
reactions and depends on the initial concentration of both malachite green and hydroxide ions.

MG+ + OH- à MG-OH (colourless) Equation 1

Exactly how much the rate changes as the reactant concentration is varied depends on the rate law for the reaction. In
the case of the reaction of MG+ with OH– ion, the rate law has the general form:

Rate = k[MG+]x[OH-]y Equation 2

The exponents x and y are defined as the order of reaction for each reactant and k is the rate constant for the reaction
at a particular temperature. As you know, the values of the exponents x and y must be determined experimentally.
OH- is in excesss
Because in the reaction, both would be changing, the reaction is carried out so that the system has an extreme excess of
OH-, so that [OH-]>>[MG+]. This allows the [OH-] to be essentially constant during the reaction unless we change it
between trials on purpose. Since [OH] is essentially a constant, we can rewrite equation #2 as shown in #3.

Rate = k’[MG+]x Equation 3 k’ = k[OH-]y Equation 4

The constant kʹ is a new “pseudo rate constant” incorporating both the “true” rate constant k and the [OH–]y term.
Equation 3 is referred to as a pseudo-rate law because it is a simplification of the actual rate law, Equation 2.
The pseudo-rate law is valid when the concentration of OH− ions is much greater than the concentration of MG+ ions.
Under these conditions the [OH−]y term in Equation 2 will not change much over the course of the reaction and may be
treated as a constant in the rate equation.
Recall that the absorbance for a specific concentration of a solution with a fixed path length varies directly with the
absorptivity coefficient of the solution. This relationship is known as Beer’s law.

A=ebc

where A is absorbance, e is the molar absorptivity, b is the path length in cm, corresponding to the distance light
travels through the solution, and c is the molar concentration of the solution. Beer’s law provides the basis of using
spectroscopy in quantitative analysis. Using this relationship, concentration and absorbance may be calculated if one
variable is known while keeping e and b constant. This relationship is also extremely valuable in kinetics experiments,
making it possible to follow the rate of disappearance of a colored substance by measuring its absorbance as a function
of time.

The visible absorption spectrum for Malachite Green, MG+, is shown in the YouTube video accompanying this lab. The
concentration of the dye was 11 µM. Sketch the spectrum here.

lmax for Malachite Green is _______

616.50 nm so we will use the _______
616 nm wavelength on the colorimeter
*Note: He says the number you should use repeatedly. It is different than what the screen reads by a tiny bit.

Part 1: Create a Beer’s Law plot for Malachite Green.

He begins with a 11 mM stock solution (11 x 10-6 M) and will prepare a series of 6 dilutions in test tubes to measure their
absorbance values with a wavelength at or close to lmax. Test tube 1 will have 1.0 mL of stock solution diluted to 10.0
mL, test tube 2 will have 3.0 mL of stock solution diluted to 10.0 mL, and this will continue to test tube 6 which is NOT
diluted. Perform the dilution calculations to get answers for the third row of the data table. Remember the dilution
equation is M1V1 = M2V2. Then, using the final two rows, you can make your Beer’s Law Plot (directions for how to do
this are found at the end of this document).

Be careful- all of your data will be wrong if you don’t do the dilution math correctly.

Test Tube 1 Test Tube 2 Test Tube 3 Test Tube 4 Test Tube 5 Test Tube 6
Initial Volume of 11 mM 5mL 9mL
1mL 3mL 7mL 10mL
Malchite Green, mL
Added Volume of distilled 7mL 3mL
9mL 5mL 1mL
water, mL

Concentration of 11*10^-7 33*10^-7 55*10^-7 1.1*10^-5

77*10^-7 99*10^-7
Malachite Green, M

Absorbance at _______
616
0.102 0.296 0.472 0.704 0.918 1.042
nm
Take a clear image of your Beer’s Law plot (you can do this by taking a photo) and upload it into the spot below.

Perform linear regression for your Beer’s Law plot and record
the equation y=mx+b equation relating the Absorbance and
the Concentration of malachite green here. Use A for A = 92727.3[MG]-0.0116
absorbance and [MG] for your Malachite Green
Concentration:

Part 2: Trial 1: Reacting the 11 µM Malachite with 0.10 M NaOH.

In the video he mixes 10.0 mL of 11 mM malachite green with 10.0 mL of 0.10 M NaOH in a 50 mL beaker. Record the
absorbance values over time, as the dye fades in the data table below. Then using your Beer’s Law equation, solve for
the concentrations of MG for each time and add that to the table.

Absorbance and time when [MG+] = __________________

0.000011 M and [OH-] = ___________
0.10 M
Absorbance 0.420 0.322 0.244 0.184 0.139 0.104 0.079
(nm)
Time (sec) 0sec. 30 sec. 60 sec. 90sec. 120sec. 150sec. 180sec.

Concentration 4.40*10^-6 3.60*10^-6 2.76*10^-6 2.11*10^-6 1.62*10^-6 1.25*10^-6 9.77*10^-6

M M M M M M M
(M)
Using the data above, create plots of [MG], ln[MG], and 1/[MG] vs t. Screen-shot/ share them in the space below.
 Part 3: Reacting the 11 µM Malachite Green with 0.050 M NaOH.
In the video 10.0 mL of 0.050-M NaOH is reacted with 10.0 mL of 11 µM malachite green. Record the absorbance values
over time, as the dye fades. Then using your Beer’s Law equation, solve for the concentrations of MG for each time and
add that to the table.

Absorbance and time when [MG+] = __________________

0.000011 M and [OH-] = ___________
0.050 M
Absorbance 0.451 0.391 0.337 0.290 0.249 0.215 0.186 0.160 0.138 0.118 0.103
(nm)
0 sec. 30 sec. 60 sec. 90 sec. 120 sec. 150 sec. 180 sec. 210 sec. 240 sec. 270 sec. 300 sec.
Time (sec)
Concentration 4.74*^-6 4.34*10^-6 3.76*10^-6 3.25*10^-6 2.81*10^-6 2.44*10^- 2.13*10^-6 1.85*10^-6 1.61*10^-6 1.40*10^-6 1.24*10^-6
M M M M M 6M M M M M M
(M)

Using the data above, create plots of [MG], ln[MG], and 1/[MG] vs t. Screen-shot or share them in the space below.

Part 4: Conclusion Calculations and Questions!

Remember there are ultimately 3 equations you will need to have completed by the end of this lab.

• The graphs will help you solve for equation #3 because they plot [MG] concentrations vs time at constant [OH].
• The two different trials will help you solve for equation #4 because each trial has constant [MG] concentration
and a different value of [OH].
• With both of those solved, you can solve for equation #2 which is our final end goal.

Equation 2: Rate = k[MG+]x[OH-]y Equation 3: R = k’[MG+]x Equation 4: k’ = k[OH-]y

1. Given your graphs of [MG] concentrations, determine the order of the reaction in respect to [MG]. Use this to fill
in “x” in equation #3.

R = k'[MG^+]^1

2. Find k’ by finding the slopes of the appropriate graphs. You should have 2 different k’ values with units.
Trial #1 Trial #2
ln(9.77*10^-7) - ln(4.40*10^-6) / 180 - 0 ln(1.24*10^-6) - ln(4.74*10^-6) / 300 - 0

k' = -0.00836 s^-1 k' = -0.00447 s^-1

 3. Based on your answers to 1 and 2 above you should be able to solve for the rates in M/sec for both trials using
equation #3. Since the first concentration value is the only one that is 100% accurate with no potential errors,
you will get the prettiest for the rate by using [MG] = 11*10-6 M. Calculate the two rates below, and then enter
them into the table.

Trial #1 Trial #2
R = k'[MG^+]^1 R = k'[MG^+]^1
R = -0.00836[11*10^-6]^1 R = -0.00447[*10^-6]^1
R = -9.19*10^-8 M/s R= -4.92*10^-8 M/s

Trial [MG] measured in M [OH] measured in M Rate M/sec

1 11*10-6 M 0.10 M -9.19*10^-8 M/s

2 11*10-6 M 0.050 M -4.92*10^-8 M/s

4. Using this trial table you made, determine the order of the reaction with respect to [OH]. Show the calculation
below. Write the final rate law

Trial 1&2:
0.050M / 0.10M = 0.5
(-4.92*10^-8)M/s / (-9.19*10^-8)M/s = 0.5 R = k[OH]^1
0.5/0.5 = 1

5. Using either equation # 2 or equation #4, determine the actual rate constant k with units.

R = k[MG]^1[OH]^1
-9.19*10^-8 M/s = k[11*10^-6 M]^1[0.10 M]^1
(-9.19*10^-8 M/s) / (1.1*10^-6 M^2) = k

k = -0.0835 M^-1 s^-1

6. Finally!!! Write the final rate law including the rate constant with units. Woohoo you did it!

R = (-0.0835 M^-1 s^-1) [MG]^1[OH]^1

How to Do the Analysis with a TI-8X Graphing Calculator:

1. To get to where you can plot the data points – hit the “stat” button. Then click “enter” to take your to the data
table.

2. Enter the concentrations and absorbance values in L1 and L2 respectively to create your Beer’s Law scatterplot.

3. To view the scatterplot:

a Click “2nd” and then the “y=” button. Hit enter and then turn on plot 1. By moving the curser from “off”
to “on”.
b Then go to “zoom” and scroll down to #9 – “zoom stat” and click on it.

4. Perform Linear Regression and obtain the equation for the Beer’s Law plot. Enter this equation on the data sheet.
You will use it to convert absorbance values to concentrations for the malachite green in the kinetics analysis.

a Go to “stat” then “calc” by scrolling over 1.

b Scroll to the first “linear regression” – it should be item #4 and click it.
c Scroll down to calculate and hit enter.

5. To do the remainder of the graphs repeat with [MG], ln[MG] and 1/[MG] by replacing the Ln1 with the times and
replacing the Ln2 with the various concentration values. Note you would only do a linear regression on the linear
graph.

HOW TO DO THE DATA ON EXCEL

The same analysis can be done with a spreadsheet like Excel or Google Sheets. Excel is really fast when it comes to
changing the values from one type to the other and doing regression.

1. Make your data tables of X vs Y.

a. You can type the initial data and then use =ln() and select the initial data and =1/() and select the initial data
to automatically populate the new values quickly. You can hit copy and select all the other box and choose
“paste formula” and it will do all of the numbers for you.

2. Highlight the columns and select “insert” and choose a scatter plot.
3. Right click or control click the data and select “insert trendline” and choose linear for the linear plot. This will cause
the equation to appear.