Detecting a Reaction Intermediate

Objectives

Trap reaction intermediate of hydrogen combustion

Perform a redox titration to detect hydrogen peroxide in water sample
Calculate concentration of hydrogen peroxide reacted during titration

Introduction

Hydrogen is flammable, as you might have figured out from the many warnings in the Safety
section of your lab procedures. The overall reaction of hydrogen with appears very simple:

2 H2 (g) + O2 (g) 2 H2O (l)

Nothing complicated, right? Actually, chemists do not yet fully understand this reactions
mechanism. There are dozens of elementary steps which include over ten different chemical
species. Other combustion processes use different fuels, such as gasoline, candle wax (paraffin),
propane or methane (natural gas), and these reactions are even more complicated.
Understanding these reactions is daunting but important to scientists and engineers designing
more fuel efficient engines and making more effective fire safety equipment.

The first step that occurs when hydrogen burns is the dissociation of the H2 molecule.

H2 (g) 2 H (g)

This reaction occurs very slowly at room temperature that is why it is safe for you to work with
hydrogen in this semesters experiments, as long as you are away from flames. The reaction is
so slow because it takes 436 kJ/mol to break the hydrogen hydrogen bond. That is a lot of
energy. However, at higher temperatures, the reaction rate increases so that hydrogen atoms do
form. They then react with oxygen molecules.

H (g) + O2 (g) HO2 (g)

This product is not stable and therefore is very reactive. It does not live very long before
reacting with other molecules or atoms. Several of these reactions can produce hydrogen
peroxide, H2O2. During combustion, the temperature is high enough that hydrogen peroxide
continues to react, eventually forming water. Chemicals that form during a reaction but then
react are called intermediates. Typically, they are unstable and their concentrations remain low
during the reaction.

However, hydrogen peroxide is stable at room temperature. By quickly cooling the chemicals in
a hydrogen flame, you can trap the hydrogen peroxide. That means you can prevent it from
reacting so that you can study it. Hydrogen peroxide does react slowly in water at room
temperature but it takes months for the reaction to be complete.
 Detecting a Reaction Intermediate

We can trap H2O2 from the flame by placing an ice cube in front of the flame. The ice cube melts
and the hydrogen peroxide that forms during the reaction will dissolve in the water. You will
collect water as it drips off the ice cube. Drippings will contain a small concentration of H 2O2.
The purpose of this experiment is for you to determine how much hydrogen peroxide is in it.

One way to calculate the amount of hydrogen peroxide present in a solution is to measure the
amount of another chemical that reacts with it. This can be done using potassium permanganate
(KMnO4), which forms a bright pink solution when dissolved in water. The permanganate ion
and hydrogen peroxide are converted to Mn2+ and O2 gas, respectively, in a redox reaction. An
acid is necessary in order to ensure that the reaction goes to completion.

As long as the melted ice solution contains hydrogen peroxide, the solution will not turn pink
color as you add KMnO4. A slight pink color of the solution indicates that all the peroxide has
reacted and now you are just adding excess KMnO4. If you know the amount of excess
permanganate that you add, you can calculate the amount of MnO 4- which reacted. Using the
reaction stoichiometry, you can determine the original concentration of hydrogen peroxide in the
drippings from the ice cube.

Safety

Always wear your goggles and lab apron or lab coat.

Sulfuric acid is corrosive and burns your skin. Alert the GSA if you spill any acid. Do not clean
it up yourself. Rinse skin or clothes for at least 10 minutes if you get any acid on you.

While all flames are hot, a hydrogen flame is approximately twice as hot as a candle flame. It
has a faint blue color and does not generate any smoke or ash. Therefore, it is very difficult to
see. The hydrogen flame will extend about 6 inches from the tip of the glass pipette tip.

Only the lab instructor is allowed to operate the hydrogen tank or light the hydrogen flame.
Students who do not behave responsibly around the hydrogen flame will be dismissed from the
lab session.

Experimental Procedure

Setting Up the Experiment

You will be detecting very small amounts of hydrogen peroxide in the melted ice. If your
glassware is not clean, your measurements may be inaccurate due to contaminants. Wash your
stir rod and large test tubes with soap and tap water, then rinse with DI water. Dry them with a
paper towel. Place the test tubes on a test tube rack.

Fill your wash bottle with DI water. You will use DI water to make all solutions in this
experiment.
 Detecting a Reaction Intermediate

Adjust the stopcock valve of the buret so that it is closed (turned perpendicular to the buret).
Place a funnel in the top of the buret. Slowly pour approximately 10 - 20 mL of 1.26 10-4 M
KMnO4 (potassium permanganate) solution into the buret. Attach the buret clamp to the ring
stand then attach the buret to the clamp. Adjust the height of the buret so that you have room to
hold a large test tube beneath the buret tip. Rotate the buret clamp so the buret is above the metal
base of the ring stand.

Place a small beaker beneath the buret tip. Open the stopcock so that a few milliliters of
permanganate solution flows into the beaker. Adjust the buret stopcock so the solution just drips
out. You will be adding KMnO4 solution dropwise to your solutions so this is good practice.
Also practice reading the volumes of liquid in the buret. You should be able to measure volumes
in 0.05 mL increments. See the video 1102 Exp't 8: How to Setup Buret Apparatus for assistance
(http://youtu.be/UOAQR8P4sx0).

Preparing the Solutions

Fill your 10 mL graduated cylinder with 5.0 mL of DI water and pour into a dried test tube. Note
the approximate height of the water line in the test tube.

Place the other large test tube in your 400 mL beaker and weigh both of them. It is important
that your test tube and beaker are dry before weighing. Record this mass value. Fill this large
test tube with melted ice drippings so that both test tubes contain approximately the same
volume, though it does not need to be exactly equal. (Your laboratory instructor will operate the
hydrogen tank, light the flame and melt the ice.) Weigh the test tube with melted ice in the 400
mL beaker again and record this mass.

Use the 10 mL graduated cylinder to add 5.0 mL of 2.0 M H 2SO4 (sulfuric acid) solution to each
test tube. Mix both solutions with your stirring rod, rinsing the rod with DI water and drying it
after stirring each solution.

Record the initial volume of KMnO 4 solution in the buret. Add 10 drops of KMnO 4 solution into
your test tube containing the DI water and H2SO4 (not containing the melted ice). Note that the
top layer of the solution in the test tube appears bright pink while the rest of the solution is
colorless. Stir this solution with your stirring rod so that it is mixed. Rinse your stirring rod with
DI water so it is clean when you use it later. See the video 1102 Exp't 8: How to Prepare H2O2
Test Tube for assistance (http://youtu.be/BmWpUt8YtgQ).

Record the final volume of KMnO 4 solution in the buret. The solution in the test tube will be a
very light shade of pink. Place this test tube on the test tube rack. You will use this test tube as a
comparison sample later.

Performing the Chemical Reaction

Record the volume of KMnO4 solution in the buret before adding any to the test tube containing
the solution of melted ice and H2SO4. Open the stopcock so that the KMnO4 drips down into the
large test tube containing the melted ice. Add 5 to 10 drops, close the stopcock and stir the
solution in the test tube with the stirring rod. Unlike the solution containing DI water, the pink
 Detecting a Reaction Intermediate

color from the added permanganate will disappear as it reacts with the hydrogen peroxide.
Continue adding KMnO4 in 5 10 drop aliquots (portions) with stirring after each addition.

As you add more KMnO4, you will need to stir for a longer period of time before the pink color
disappears. You will also notice that when you add drops of permanganate, the pink color at the
top of the solution becomes a brighter shade of pink. This indicates that you are approaching the
end of the reaction (almost all the hydrogen peroxide is consumed). Continue to add drops of
permanganate solution until the test tubes solution appears to be the same light shade of pink
that you observed in the other test tube containing DI water. To best compare the colors, hold the
test tubes side by side and look through them at a fluorescent light. Record the final volume of
KMnO4 solution in the buret. See the video 1102 Exp't 8: How to Prepare H2O2 Test Tube for
assistance (http://youtu.be/BmWpUt8YtgQ).

After verifying that the two solutions are a similar shade of pink, you may dispose of them in the
waste container. Rinse both test tubes and stirring rod with DI water.

Cleaning Up
Dispose of all chemical waste, including unused KMnO4 solution in your buret, in the proper
container. Rinse all glassware and the funnel with DI water. To rinse the buret, place the 400
mL beaker below the buret and pour in DI water. Allow approximately 50 mL of DI water to
flow through the buret. Dispose of the rinse water in the beaker.
 Detecting a Reaction Intermediate

Data Sheet

Name______________________________ Section__________ Date__________

Test tube with DI water

Initial volume of buret: Final volume of buret:

Volume of KMnO4 added: Total volume of solution:

Calculate the concentration of KMnO4 in test tube. Show your work.

Balance the reaction between MnO4- and H2O2. Show your work.
 Detecting a Reaction Intermediate

Data Sheet (continued)

Name______________________________ Section__________ Date__________

Test tube with melted ice

Mass of test tube and beaker:

Mass of test tube and beaker with melted ice:

Mass of melted ice: Volume of melted ice:

Initial volume of buret: Final volume of buret:

Volume of KMnO4 added: Total volume of solution:

Calculate the moles of MnO4- added. Show your work.

Calculate the moles of excess MnO4- present. Show your work.

Calculate the moles of MnO4- which reacted.

Calculate the moles of H2O2 which reacted.

Calculate the concentration of H2O2 in the original melted ice solution.

 Detecting a Reaction Intermediate

Report
Each student will write a short report for this two-week experiment. Write everything in your
own words. Do not copy or rephrase what somebody else writes. Type the report using double
spacing and 12 point font. It should include the sections described below. Lengths for each
section are just suggestions.

Procedure (< 1/2 page)

Explain any changes that you made, either intentionally or unintentionally, to the experimental
procedure that was provided to you. This includes using different equipment (e.g. 50 mL
graduated cylinder instead of 10 mL) or amounts of chemicals. If you followed the procedure
without any changes, simply state that you followed the procedure that was given to you.

Data and Results (length varies)

Include your data sheet and calculations in this section.

State the concentration of hydrogen peroxide that you measured.

Why might the reaction between hydrogen peroxide and MnO4- proceed more slowly towards the
end of the reaction?

Calculate the free energy of the reaction: H2 (g) + O2 (g) H2O2 (g)
and the reaction: H2O2 (g) + H2 (g) 2 H2O (g)
How do the free energy values for these two reactions compare the free energy of the combustion
of hydrogen gas?

Based on your calculations in the previous question and your understanding of reaction
mechanisms, draw a qualitative energy diagram of the reactions progress.

Reflection (< 1/2 page)

What improvements could be made to this experiment? What did you like about it? Please be
honest.

References
Provide references for any sources of data or information that you used in your report. Do not
use Wikipedia, Yahoo Answers or other unreliable sources as your references.

A grading checklist (called a rubric) is posted on Canvas so that you know how your lab
instructor will grade your report. Remember to write your own report and do not copy or
paraphrase from another source.