Kinetics Studies of the Bleaching of Food

Dyes
Introduction
Kinetics is the study of how rapidly, or slowly, a reaction occurs. This tutorial applies kinetics to
the bleaching of food dyes, a process that is shown in the following movie:

In this activity, the goal is to determine the "rate law" for the reaction of a food dye with bleach.
The rate law summarizes experimental information in a concise manner: once we have the rate
law, we can predict the rate of the reaction for a wide range of experimental conditions. The rate
law has this form:

and contains two types of information:

 The order of the reaction, n and m above, with respect to the concentrations of the
reactants. The rate is proportional to the concentration raised to the "order". For first
order, the rate is proportional to concentration raised to the first power, so doubling the
concentration doubles the rate. For second order, the rate is proportional to the
concentration raised to the second power, so doubling the concentration increases the rate
by a factor of four.
 The rate constant, k above, is the proportionality constant. We need the rate constant if
we want to calculate the rate instead of just understand how the rate changes when we
change the concentration.

To determine the rate law, we will measure the rate under different conditions.

The conditions we will be changing are the concentrations of the reactants. In particular, we will
run the reaction twice, with the concentration of the bleach being doubled in the second
experiment. Both times, we will start with 10 mL of a Yellow 6 dye solution. The first time, we
will mix in 0.30 mL of 0.090 M NaOCl (household bleach). The second time, we will use 0.30
mL of bleach that is twice as concentrated, i.e. 0.180 M NaOCl. Which reaction do you think
will go faster? Check out the following movie and see if you are correct.

How did you tell which reaction went faster? You probably watched how rapidly the colour
faded. This works because, as the dye reacts with the bleach, its concentration decreases and the
color fades. This can be quantified by using a spectrometer to precisely measure the intensity of
the colour. The quantity that measures "intensity of the colour" is the "absorbance" of the
solution. Using Beer's Law, we can convert absorbance values into concentrations. This is great
for chemical species that impart colour to a solution. But what do we do for the bleach, which is
colourless? We will use stoichiometry to determine the concentration of bleach.

To begin, let's take a look at the overall experimental strategy as it is shown schematically
below. We will then dive in and look at each step in detail.

Step 1: Follow the disappearance of the dye by

measuring the absorbance of the dye during the
reaction.
Making a "kinetic trace": Follow the rate of disappearance of the coloured
reactant by colour spectroscopy.

Step 2: Getting information from a kinetic trace.

 Measuring the absorbance of the dye during its reaction with bleach is expressed graphically on th
spectrophotometer takes a reading of absorbance every second or so. We will learn how the analy
called a kinetic trace) can give us an insight into the rate of reaction.

Step 3: Determine the effect of bleach on the rate of

reaction.
Once we have determined what happens to the dye during the reaction, we need to
find a way to monitor the bleach indirectly, since it is colourless and its
concentration cannot be monitored by the spectrophotometer.

What will happen to the RATE when I make a change?

Step 4: Converting absorbance to concentration
In the last step, we will be assembling the rate law expression. To do this, we will
need to know the concentrations of dye during the reaction. In the laboratory, we
measure absorbance. Beer's Law tells us that absorbance is proportional to
concentration, [dye]. And so if we determine that proportionality, we can convert
from our measured absorbances to [dye].

Beer's Law Calibration

Step 1

Action: We monitor the absorbance of the dye over time as it reacts with bleach.
(This plot of absorbance versus time is called a kinetic trace).

Result: We obtain a kinetic trace for the reaction. We can use this data to
determine the reaction order with respect to the dye.
 Step 2

Action: We consider three different forms for the rate law, corresponding to the
rate being zeroth, first, or second order in the concentration of dye. We use a
graphical approach to determine which rate law applies to our kinetic trace, which
in turn tells us the order of the reaction with respect to dye.

Result: We determine the reaction order in dye.

Step 3

Action: Based on the knowledge gained in the previous steps, we design an

experiment to determine how changes in the concentration of bleach will change
the rate of the reaction.

Result: We perform an experiment which will allow us to determine the reaction

order with respect to bleach.

Step 4

Action: The kinetic traces we obtain in steps 1 through 3 give absorbance of the
solution versus time. To get the rate law, we need to convert from absorbance to
dye concentration. This is not difficult, because absorbance is proportional to dye
concentration, via Beer's Law. All we need to do is determine this relationship. To
do this, we prepare a set of dilutions of the standard dye (its concentration is
written on the bottle). We then measure the absorbance of each diluted solution at
the analytical wavelength.

Result: We obtain a calibration plot of absorbance versus concentration at the

analytical wavelength for the standard dye. We can use the slope of this plot to
convert absorbance readings to concentrations in the kinetic trace.

We use the concentrations in the kinetics experiment to assemble the rate law and
calculate instantaneous reaction rates.

The following pages contain tutors to assist you with performing kinetics experiments and the
calculations required in the above steps.
Experiment 13H
THE REACTION OF RED FOOD COLOR WITH BLEACH
1
LEARNING OBJECTIVES:
By the end of this experiment, the students should be able to demonstrate
the following proficiencies.
1.
Properly make aqueous solutions, given target volumes and molarities.
2.
Relate absorbance measurements to concen
trations, using the Beer-Lambert Law.
3.
Apply the method of comparing initial reaction ra
tes to determine the or
der of reaction with
respect to reactants.
4.
Apply the graphical (integrated rate law) method
to determine the order of reaction with respect
to one reactant.
5.
Control experimental conditions, as needed, to assure proper comparison of rate information
PRE-LAB:
Review Appendix I (Spectrophotometry) for a discussion of spectroscopy and application of
Beer’s Law:
http://www.chemistry.usna.edu/manual/ApdxI.pdf
Complete the pre-lab questions on page E13H-8
prior
to coming to lab.
DISCUSSION:
Most people are familiar with th
e action of bleach on fabrics. If
one has done much laundering of
clothes, one will recall the warning on the side of a Clorox
®
bottle against its use on brightly colored
clothes. This “bleaching” is a chemical
reaction whose kinetics can be easily studied.
Red Dye #3 Hypochlorite Ion Colorless Product
(red dye) (bleach or OCl
-
)
__________________________________________
1
Adapted from Henary, M.M., Russell, A.A.
J. Chem. Educ.
,
2007
, 84, 480-482.
PROBLEM:
Determine the rate law for the chemical
reaction between FD&C Red Dye #3 and
sodium hypochlorite.
E13H-2
The rate of the bleaching reaction is dependent on the
concentration of red dye an
d on the concentration of
bleach. This is expressed in the rate law for the reaction:
rate = k [red dye]
a
[OCl
–
]
b
(1)
Experimental data will allow the values of
the orders with resp
ect to each reactant,
a
and
b
, to be
determined.
Determination of a:
Pseudo Rate Law Method (graphical).
One method for determining reaction or
ders outlined in general chemistr
y textbooks involves determining
whether a reaction follows certain graphical profiles. However, this method can only be applied if the rate
law for the reaction involves only one reactant. Th
is may appear rather limiting, since most chemical
reactions involve at least two reactants
. As shown below, however, there is
a way, in principle, to cause a
reaction involving multiple reactants to appear to include
the change in only one reactant. This method is
known as the Pseudo Rate Law Method. By running
the bleaching reaction with
a large excess of bleach,
OCl
–
, the
Δ
[OCl
–
] will be approximately equal to zero, therefore, k
′
= k[OCl
–
] and the rate law simplifies
to: rate = k
′
[red dye]
a
and the rate of reaction leads directly to the order with respect to red dye,
a
.
Determination of b:
Method of Initial Rates.
The Method of Initial Rates for determ
ining orders of reaction is illustrate
d in Example 13.3 (pp. 567-569)
of the Chang textbook. This method simply involves a comparison of two different trials, the only
difference between the trials being the concentratio
n of one of the reactant
species. The value of
b
in this
experiment will be found by this method through holding the concentration of red dye constant and
changing the concentration of OCl
–
.
Since all of the reactions studied in this experi
ment involve a species (red
dye) that will absorb
visible light a Spectrophotometer (Spec 20) will be used
to collect absorbance (A) data which can then be
related to concentration (c) data using Beer’s Law:
A=

l
c
(2)
where
l
= pathlength of the cuvette (1.00 cm in this experiment) and

= molar absorptivity for red dye.
MATERIALS:
100 mL volumetric flask (3), 50 mL beaker (2), 5 mL pipet (1), 2 mL pipet (3), 1 mL
pipet (2), Spec-20 (1), cuvette (2), rubber st
opper for cuvette (1), plastic droppers (2).
PROCEDURE:
SAFETY:
ALWAYS wear safety goggles and an apron, and handle the intensely colored dye carefully to
avoid stains on clothing.
Sodium hypochlorite, househol
d bleach, is a bronchial irr
itant. Keep solutions in
the hood, and avoid breathing the
vapors. Immediately wipe-up any
spills of the red dye or bleach.
Part A. Prepare two red dye solutions from an initial stock solution, using serial-dilution method
(See PRELAB) & determine absorbance
1. On data sheet, record
the concentration of the stock
solution to four decimal places
2. Obtain about 10 mL of red dye stock solution, in 50 mL beaker.
3. Rinse inside walls of pipet with a small amount of the red dye stock solution, then fill pipet and
transfer 5.00 mL of the red dye
into a volumetric flask. Carefully fill the flask up to the 100.0 mL
mark with distilled water. Cap the flask and i
nvert the solution several times to mix well.
Transcription
1 Experiment 13H FV 1/25/2011(2-run) THE REACTION OF RED FOOD COLOR WITH
BLEACH 1 PROBLEM: Determine the rate law for the chemical reaction between FD&C Red
Dye #3 and sodium hypochlorite. LEARNING OBJECTIVES: By the end of this experiment, the
students should be able to demonstrate the following proficiencies. 1. Properly make aqueous
solutions, given target volumes and molarities. 2. Relate absorbance measurements to
concentrations, using the Beer-Lambert Law. 3. Apply the method of comparing initial reaction
rates to determine the order of reaction with respect to reactants. 4. Apply the graphical
(integrated rate law) method to determine the order of reaction with respect to one reactant. 5.
Control experimental conditions, as needed, to assure proper comparison of rate information
PRE-LAB: Review Appendix I (Spectrophotometry) for a discussion of spectroscopy and
application of Beer s Law: Complete the pre-lab questions on page E13H-8 prior to coming to
lab. DISCUSSION: Most people are familiar with the action of bleach on fabrics. If one has done
much laundering of clothes, one will recall the warning on the side of a Clorox bottle against its
use on brightly colored clothes. This bleaching is a chemical reaction whose kinetics can be
easily studied. Red Dye #3 Hypochlorite Ion Colorless Product (red dye) (bleach or OCl - ) 1
Adapted from Henary, M.M., Russell, A.A.J. Chem. Educ., 2007, 84, E13H-1

2 The rate of the bleaching reaction is dependent on the concentration of red dye and on the
concentration of bleach. This is expressed in the rate law for the reaction: rate = k [red dye] a
[OCl ] b (1) Experimental data will allow the values of the orders with respect to each reactant, a
and b, to be determined. Determination of a: Pseudo Rate Law Method (graphical). One method
for determining reaction orders outlined in general chemistry textbooks involves determining
whether a reaction follows certain graphical profiles. However, this method can only be applied
if the rate law for the reaction involves only one reactant. This may appear rather limiting, since
most chemical reactions involve at least two reactants. As shown below, however, there is a way,
in principle, to cause a reaction involving multiple reactants to appear to include the change in
only one reactant. This method is known as the Pseudo Rate Law Method. By running the
bleaching reaction with a large excess of bleach, OCl, the Δ[OCl ] will be approximately equal to
zero, therefore, k = k[ocl ] and the rate law simplifies to: rate = k [red dye] a and the rate of
reaction leads directly to the order with respect to red dye, a. Determination of b: Method of
Initial Rates. The Method of Initial Rates for determining orders of reaction is illustrated in
Example 13.3 (pp ) of the Chang textbook. This method simply involves a comparison of two
different trials, the only difference between the trials being the concentration of one of the
reactant species. The value of b in this experiment will be found by this method through holding
the concentration of red dye constant and changing the concentration of OCl. Since all of the
reactions studied in this experiment involve a species (red dye) that will absorb visible light a
Spectrophotometer (Spec 20) will be used to collect absorbance (A) data which can then be
related to concentration (c) data using Beer s Law: A = lc (2) where l = pathlength of the cuvette
(1.00 cm in this experiment) and = molar absorptivity for red dye. MATERIALS: 100 ml
volumetric flask (3), 50 ml beaker (2), 5 ml pipet (1), 2 ml pipet (3), 1 ml pipet (2), Spec-20 (1),
cuvette (2), rubber stopper for cuvette (1), plastic droppers (2). PROCEDURE: SAFETY:
ALWAYS wear safety goggles and an apron, and handle the intensely colored dye carefully to
avoid stains on clothing. Sodium hypochlorite, household bleach, is a bronchial irritant. Keep
solutions in the hood, and avoid breathing the vapors. Immediately wipe-up any spills of the red
dye or bleach. Part A. Prepare two red dye solutions from an initial stock solution, using serial-
dilution method (See PRELAB) & determine absorbance 1. On data sheet, record the
concentration of the stock solution to four decimal places 2. Obtain about 10 ml of red dye stock
solution, in 50 ml beaker. 3. Rinse inside walls of pipet with a small amount of the red dye stock
solution, then fill pipet and transfer 5.00 ml of the red dye into a volumetric flask. Carefully fill
the flask up to the ml mark with distilled water. Cap the flask and invert the solution several
times to mix well. E13H-2

3 4. Rinse the pipet again, this time with some of the dilute solution you just made. Pipet 5.00 ml
of the dilute red dye solution (prepared in step 3), into another clean volumetric flask. Carefully
fill the flask up to the ml mark with distilled water. Cap the flask and invert the solution several
times to mix well. Rinse the pipet with some of the more dilute solution you just made. It is
THIS SOLUTION that will be used in all reaction mixtures described in Part B. 5. Set the
wavelength of the Spec-20 to 530 nm. Set the instrument to %T mode. Adjust the zero with no
sample in the instrument. Next, fill a cuvette ~2/3 full with deionized water, wipe with a lab
tissue, insert into the instrument and set 100% transmittance. 6. Switch the Spec-20 to
Absorbance mode. 7. Transfer a sample of your dilute solution from Part A (4.) into a clean
cuvette, wipe with a lab tissue and insert into the sample compartment. Record the absorbance on
the data sheet. Note: From this you will be able to calculate the molar absorptivity,, of the red
dye solution. Part B. Absorbance measurements of reaction mixtures 1. Obtain about 15 ml of
hypocholorite solution, in 50 ml beaker. Record the weight percent on data sheet. 2. Using pre-
rinsed volumetric pipets, fill the cuvette with appropriate amounts of dilute dye solution and
water for Reaction #1 as specified in the table below. Note: Because this reaction will begin as
soon as you mix the red dye and bleach solutions, you must start timing as soon as the bleach is
added. 3. Using a pipet, add 2.00 ml of the bleach solution (begin timing), stopper the cuvette,
invert once to mix, then quickly wipe the cuvette with a lab tissue and insert into the Spec-20.
Record a data point immediately, and then remove the cuvette. Take a second absorbance
measurement 30 seconds after the bleach was originally added, and then record the absorbance
every 30 seconds thereafter for 15 minutes. To maintain constant temperature, REMOVE the
cuvette from the sample compartment between readings. Record time vs. absorbance on data
sheet. 4. For reaction #2, a modified procedure will be used: First, fill a cuvette with appropriate
amounts of dye solution and water. Next, using 1- and 2-mL pipets, pipet 3.00 ml of bleach
solution into a second clean test tube. To initiate reaction, pour the bleach solution quickly and
carefully from the test tube into the cuvette containing the dye-water mixture. Stopper, mix and
begin recording data immediately as previously described. Remember to remove the cuvette
between readings. Clean up: Reaction # dye solution (ml) deionized water (ml) bleach solution
(ml) Be sure to remove the sample from the Spec-20! Discard all solutions in the sink. Wash and
rinse glassware thoroughly to remove red dye and bleach residue. Shut down Spec-20 as
instructed E13H-3

4 Name Name Section Date DATA SECTION Experiment 13H Part A. Concentration and
Absorbance of red dye solutions & mass percent of bleach Note: Use proper significant figures
and units. 1. Initial concentration of red dye stock solution: mol/l 2. Record the Absorbance of
the solution prepared in Part A (4.): (no units) 3. Mass percent of sodium hypochlorite in the
bleach: Part B. Absorbance data for each reaction mixture Time (sec) Absorbance Reaction #1
Time (sec) Absorbance Reaction #2 E13H-4
5 Name Name Section Date CALCULATIONS & DATA TREATMENT Experiment 13H Part
A. Determining concentrations & molar absorptivity Note: Use proper significant figures and
units. (A.1) Using M (conc) V (conc) = M (dilute) V (dilute) and the initial concentration of the
stock solution recorded in Part A, calculate the concentration of the red dye solutions you made
in Part A (3.) and Part A (4.). [red dye] Part A (3.) [red dye] Part A (4.) (A.2) Use Beer s Law
and the absorbance recorded in Part A to calculate the molar absorptivity of the red dye solution.
Molar absorptivity (A.3) Mass percent of sodium hypochlorite in the bleach: (A.4) Assuming
that the density of bleach solution is 1 g/ml, calculate the molarity of the sodium hypochlorite in
the stock bleach solution provided. (A.5) Using M (conc) V (conc) = M (dilute) V (dilute),
calculate the molarity of the sodium hypocholorite in reaction mixtures #1 and #2: [bleach]
Reaction #1 [bleach] Reaction #2 E13H-5

6 Part B: Data analysis For a refresher on using Excel to perform calculations and graph data,
check out the tutorials on the Chemistry Department website: (B.1) Enter your time and
absorbance data for Reaction #1 into an Excel spreadsheet. (B.2) Create new columns for [red
dye], ln[red dye], and 1/[red dye]. Do not use your calculator - ENTER FUNCTIONS into the
spreadsheet to perform each calculation! Abs Recall that: red dye (B.3) Prepare three plots using
your data from Reaction #1: [red dye] vs. time, ln[red dye] vs. time, and 1/[red dye] vs. time. The
plot that visually appears the most linear tells you the order of the reaction, with respect to [red
dye]. Perform linear regressions on each plot. The plot with the R 2 value closest to 1.0 is the
most linear. Note: Record which plot has an R 2 value closest to 1.0: Record the order with
respect to [red dye], a: (B.4) Enter time and absorbance data for Reaction #2 in the same Excel
worksheet. Refer to your record of which plot was most linear (B.3) and construct this same plot
for Reaction #2. Perform a linear regression on the plot, making sure to include the equation of
the trend-line and R 2 value on each graph. Note: Use the slope of each trend-line to solve for the
order in bleach Slope of trend-line Reaction #2: (B.5) By comparing the slopes of the trend-lines
for Reactions #1 and #2 and the initial bleach concentrations calculated in (A.5), determine b, the
order of the reaction with respect to bleach (i.e. OCl - ). Remember, the slopes of your graphs
equal k in each case, and k is constant for all cases. k' k' EXP#2 EXP#1 k [ OCl k [ OCl ] ] b
EXP#2 b EXP#1 (B.6) Write the experimental rate law based on the order of the red dye and the
order of the OCl - that you obtained in your analysis (B.7) Calculate the rate constant for this
reaction (remember to include proper units) E13H-6

7 QUESTIONS Experiment 13H 1. For Reaction #1, determine the initial (time = 0 minutes) and
final (time = 15 minutes) concentrations of the hypochlorite ion. Does this justify the assumption
that the rate law depends only on the red dye concentration for this reaction? Explain. 2. What
does the rate law determined from this experiment tell us about the overall mechanism for this
reaction? Specifically, based upon the observed rate law, what is the correct stoichiometry for the
reactants in the rate-determining step? Explain. E13H-7

8 Name Section Date PRE-LAB EXERCISES Experiment 13H BRING YOUR NETBOOKS
TO LAB 1. Calculate how many grams of sodium hypochlorite (NaOCl) solution were dissolved
in 1.00 L of distilled water to give a 0.81 M stock solution. 2. Calculate the molarity of a solution
of red dye #3 (MW g/mol) if a g sample is diluted with distilled water to ml in a volumetric
flask. 3. An example of a serial dilution that you will perform in lab is: if you put a 5.00 ml
aliquot of the solution from Question 2, into another ml volumetric flask, and dilute it with
distilled water to the ml mark. That is the first dilution in a serial dilution. Then, if you put 5.00
ml of THIS new dilute solution into another ml volumetric flask, and dilute with distilled water
to the ml mark, this is the second dilution in the series of serial dilutions. The intensity of the
color (and concentration of solute) will decrease with each dilution, as illustrated below ml 5.00
ml Use the molarity you calculated in Question 2, and the data in the description, to calculate the
molarities of the first dilution and second dilution. E13H-8
Purpose:

The purpose of this lab is to