Analysis of the MnO2 and Zn Content of New and Used

Super-Heavy-Duty Batteries:
Safety Concerns: In this lab you will work with the paste inside a Heavy Duty
battery, as well as concentrated hydrochloric acid, dilute Potassium iodide, and
dilute sodium thiosulfate solutions. Only the hydrochloric acid poses significant
hazards it can be an irritant on your skin or by any form of ingestion. The other
materials pose fewer hazards at the concentrations used but are still irritants. The
battery paste can be difficult to wash off, so it is smart to wear gloves when
handling it. As in any lab exercise, you must take precautions to keep splashes
away from your eyes by wearing safety glasses at all times in the lab.
The material from inside the battery will be obtained by cutting the
battery open with a hack saw. This poses no undo risks with the Heavy
Duty Battery, but it should never be attempted with other types of
batteries.
Introduction:
A battery is an electrochemical device. It contains the reactants (and products) of a
redox reaction, and it is organized in such a way that the two half-reactions occur in
different regions so that the electrons given off in the oxidation half-reaction have to
leave the battery through some external circuit (like your flashlight) before they can
return to be used in the reduction half-reaction.
The battery, however, has a limited capacity. It depends on the amount of reactants
inside the battery. A D-size battery has more capacity than a C-size or AAs or
AAAs, so long as they use the same battery chemistry. This is simply because D is
bigger than the other sizes and can hold more reactants. In actuality, one of the
reactants is the limiting reagent (you can figure that out in todays lab). The battery
is dead when it has used up the limiting reagent.
There are a variety of battery chemistries available commercially. The most
common ones in use today are listed below along with the half-reactions and the
overall reaction:

LithiumIon batteries
(x is a small non-integer number)
Reduction: Li1-xCoO2 + x Li+ + x e- LiCoO2
Oxidation: LixC6 xLi+ + C6 + xeOverall: LixC6 + Li1-xCoCO2 LiCoO2 + C6
Nickel Cadmium Batteries
Reduction: NiO(OH) + H2O + e- Ni(OH)2 + OHOxidation: Cd + 2 OH- Cd(OH)2 + 2eOverall: 2 NiO(OH) + Cd + 2 H2O Cd(OH)2 + 2 Ni(OH)2
Lead Acid Batteries
Reduction: PbO2 + 2 H+ + H2SO4 + 2e- PbSO4 + 2 H2O

Oxidation: Pb + H2SO4 PbSO4 + 2 H+ + 2eOverall: PbO2 + Pb + 2 H2SO4 2 PbSO4 + 2 H2O

Alkaline Batteries
Reduction: 2 MnO2 + H2O + 2e- Mn2O3 + 2 OHOxidation: Zn + 2 OH- ZnO + H2O + 2eOverall: 2 MnO2 + Zn Mn2O3 + ZnO
Heavy Duty Batteries

Reduction: 2 MnO2 + 2 NH4Cl + 2 e- Mn2O3 + 2 NH3 + 2 Cl- + H2O

Oxidation: Zn Zn2+ + 2 eOverall: 2 MnO2 + Zn + 2 NH4Cl Mn2O3 + Zn(NH3)2Cl2 + H2O
The one we care about today is the Heavy Duty Battery. We will take samples of the
material from inside an unused and a used battery and compare how much of the
oxidizing agent (MnO2) is present in each. One presumes that the used battery
should have less than the unused battery.

Figure 1. Diagram of a Super Heavy Duty Battery. (from Eveready Carbon Zinc
Application Manual,
http://data.energizer.com/PDFs/carbonzinc_appman.pdf)
In todays lab you will analyze for MnO2 in the used and unused batteries.
Since MnO2 is a good oxidizing agent, we will react it with a good reducing agent (I -)
to make something that is fairly easy to analyze for (I 2).
MnO2(s) + 4 H+(aq) + 2 I-(aq) Mn2+(aq) + 2 H2O + I2(aq)
The Mn2O3 which is a product in the Heavy Duty Battery reaction, is also an oxidizing
agent, but not as good as MnO2.
Mn2O3(s) + 6 H+(aq) + 2 I-(aq) 2 Mn2+(aq) + 3 H2O + I2(aq)
[Notice that there is only half as much I2 formed per Mn atom of Mn2O3 as
in the reduction of MnO2. We will make note of that difference to deduce
how much of the MnO2 had been converted to Mn2O3.]

To determine the difference between the MnO 2 content of unused and used Heavy
Duty Batteries we will carry out the above reactions with iodide ion and will then
titrate the I2 with another reducing agent (thiosulfate ion, S 2O32-) until all the I2 has
been reacted.
I2 + 2 S2O32- 2 I- + S4O62The I2 makes a blue-black complex with starch, so the titration will involve adding a
known concentration of S2O32- until the blue-black color disappears. The color
change will be quite sudden.
Your analyses of the amount of I2 formed will indicate the amount MnO2 plus Mn2O3
in the black paste in the battery.

moles I 2 moles MnO 2 moles Mn 2 O3

The difference in the amounts of I 2 formed from tests on unused vs used batteries
will reflect the difference in the amounts of MnO 2 and Mn2O3 in the unused vs the
used battery. But since the amount of Mn doesnt change when the battery is used,
and all the Mn comes as MnO2 in the new battery
Moles MnO2 + 2 x moles Mn2O3 = constant
So,

MnO2 + 2 Mn2O3 = 0

Where the quantities represent the difference in moles in the used minus
the new batteries, and the MnO2 will be negative, and the Mn2O3 will be positive.

So,

MnO2 2 Mn2O3

or

1
Mn2O3 MnO2
2

So the difference in moles of I2 between the new and used batteries will be

I 2 MnO2 Mn 2O3
I 2 MnO2

I 2

1
MnO2
2

1
MnO2
2
or

MnO2 2 I 2

So, the decrease in the moles I2 found in the tests on the new vs used batteries will
be half the loss of the MnO2.

Figure 2 attempts to show the relationships among the numbers of moles as

electrons are passed through a battery. It clearly shows how the change in the
amount of I2 measured in the new vs used battery is half as much as the depletion
in MnO2.

Figure 2. Changes in the moles of MnO2, Mn2O3, Zn, and the amounts of I2
potentially made from the reaction of battery paste with HCl as a function of battery
use.

The amounts of I2 you will measure will actually be the amounts per gram of battery
paste. In order to know an absolute amount of MnO 2, you will need to multiply the
amount you determine by the total mass of the black paste. This is about 50g in
the new D-sized Heavy Duty batteries, and about 54g in the used batteries. The
mass of the paste in the used battery actually depends on the extent of use, but
this value of 54g will get us suitably close.
It is important to point out that not all of the black paste in a new battery is MnO 2.
The manufacturers put in some additional carbon powder to improve the
conductivity of the battery. It may be as little as 30%MnO 2.
So far we have only talked about the reduction of the Mn as the battery is used, but
we can also talk about the oxidation of the Zn. The change in the number of
moles of MnO2 in the new vs used battery should be the twice the change
in number of moles of Zn.
[This follows from the equation : 2 MnO 2 + Zn + 2 NH4Cl + 2 e- Mn2O3 +
Zn(NH3)2Cl2 + H2O.]
Zn = MnO2
Determining the number of moles of Zn is much easier than the MnO 2
determination. One can simply rinse the Zn can and weigh it. Any soluble Zn salts
which havent passed through the separator into the black paste will be easily
rinsed away, and weight will reflect the mass of Zn.
Looking at this electrically, one should be able to predict the amount of MnO 2 that
has been used up in a battery by keeping track of the electrons it has put out. For
every mole of electrons leaving the Zn side of the battery and reentering the MnO 2containing paste, one half mole of Zn should have be converted to Zn 2+, and one
mole of MnO2 should have been converted to half a mole of Mn 2O3.

MnO 2 ne
where ne is the number of electrons and the units on each side are
moles.
The total number of electrons will be the integral of the current i, over time t, that
the battery is used.
t

ne

1
i dt
F 0

Where F is called the Farday constant and is the proportionality between

moles of electronic
charge and the SI unit of charge, the Coulomb.

You wont make the current and time measurements today, but you will be given
the resulting number of electrons, and you will compare that number to your
determination of MnO2 and Zn.

Procedure:
The battery paste is difficult to wash off, so you may want to wear gloves in parts of
the lab. They are available in the stockroom window.
You and your lab partner will analyze the MnO 2 content of either a fresh or a used
Heavy Duty battery. When you are done, you will compare your result with the class
results and make some deduction about how the MnO 2 content changes on use. You
will also compare the change in MnO 2 with the change predicted from the amount of
charge that passed through the battery.
-Accurately weigh out about 0.1g of the black powder from the battery.
-Add the black powder to a small Erlenmeyer flask containing 5mL of concentrated
HCl (you figure out if you need to be precise) and 5mL of 1.0M KI (again, you figure
out if you need to be precise). Heat the mixture on a hot plate with stirring. Do not
let it boil. If you see a purple vapor form, take the flask off the hot plate. There is
no need to heat more than 5 minutes.
- Add about 20mL of distilled water to the flask. Filter the solution into a clean (but
not necessarily dry filter flask. Rinse the collected powder with a few mL of distilled
water . Collect the filtrate(thoroughly) in a 100mL volumetric flask. Do not dilute
yet.
- Take the filter paper from the filter flask and put it in a small beaker with 5mL of
concentrated HCl and 5mL of 1M KI. Heat again, below boiling, with stirring until
you either see purple vapor or 5 minutes whichever comes first. Add 20mL
distilled water then filter as above, being sure to rinse with a few mL of distilled
water. Collect the filtrate (thoroughly) in the 100mL volumetric flask. Dilute to
100.0mL, and mix well.
- Carry out the titration with the 0.050M S 2O32- .
- Fill the buret with 0.050M NaS 2O3.
- Put 20.00mL of the diluted reaction mixture in a small beaker or flask along
with a few drops of
starch indicator. Water can be added to make things more easily seen.
- Titrate until the solution just barely becomes colorless (from the blue-black
starch-I2 color)
- Repeat the titration on another 20.00mL portion of the diluted reaction
mixture until you get
the same result to within 0.1mL
- Put the remaining solution in the waste container and rinse the volumetric flask
well.
-You need to record the following common data:
-the number of moles of electrons that passed through the used battery.
-the masses of the Zn in the new and used batteries.

DISCARD filter paper waste in the small HAZARDOUS WASTE-Research Solids

CONTAINERS on the back bench. [They look like little white plastic trash cans.]
DISCARD solution in the AQUEOUS WASTE containers.

Sample MnO2 Calculation: Your goal is to figure out how much MnO 2 and Zn was
used up when a battery was used, then compare those values to the charge that
has passed through the battery. To do this you will calculate the moles of I 2 per
gram associated with the battery paste of new vs used batteries. Twice that
difference will equal the change in moles of MnO 2.
Presume you weigh out 0.0985g of the 50g of battery paste of a used battery, then
react it as directed, diluting to 100.0mL and titrating 20.00mL portions with 0.050M
S2O32- . In this case, the titration required 5.12mL.

moles I 2

g paste

0.050

moles S 2 O3
L

1 mole I 2
2

100.00mL Total Sample

0.00512 L
20.00mL used

2 mole S 2 O3
0.0985 g

0.0065 moles I 2
g paste

The amount of I2 that could have been produced if the reaction had been carried out
with all 54g:

total moles I 2 (used ) 54 g paste

0.0065 moles I 2
0.35 moles I 2
g paste

Next, presume you weigh out 0.1114g of the 54g of battery paste of an new
battery, then react it as directed, diluting to 100.0mL and titrating 20.00mL portions
with 0.050M S2O32- . In this case, the titration required 8.02mL respectively.

moles I 2

g paste

0.050

moles S 2 O3
L

1 mole I 2
100.00mL Total Sample

0.00802 L
2
20.00mL used
2 mole S 2 O3
0.0090 moles I 2

0.1114 g
g paste

The amount of I2 that could have been produced if the reaction had been carried out
with all 50g:

total moles I 2 (new) 50 g paste

0.0090 moles I 2
0.45 moles I 2
g paste

I 2 0.45 moles I 2 0.35 moles I 2 0.10 moles I 2

MnO2 2 I 2 0.20 moles MnO2
You are told that 0.191 moles of electrons have gone through the battery. This
accounts for 105% of the calculated change in MnO 2. Considering the nature of the
reaction and measurements, this isnt bad.

Be sure your lab report includes

...an abstract including an objective, a brief mention of the technique involved and
the final results.
tables of the data from your sampling and titrations.
tables of the class data for the moles of II2 in the new and used batteries,
(including moles MnO2 in new battery, moles MnO2+Mn2O3 in used battery, MnO2.
comparison (table or list) of MnO2, Zn, and moles of electrons through used
battery,
a sample calculation of the moles I2 per gram of paste.
a sample calculation of the change in moles of I2 and MnO2 for the unused and
used batteries.
a sample calculation of the change in moles of Zn for the unused and used
batteries.
answers to the following questions:
1) Assuming that the unused battery had no Mn 2O3 in it, use your knowledge
of
- the mass of battery paste in the new battery, and
- the amount of I2 made from the reaction with HCl with the new
battery paste,
to determine the fraction of the paste was MnO 2? Explain.
2) If the Zn can had a mass of 17.0g and the 50g of paste was 50% MnO 2,
what is the limiting
reagent for the batterys life time of operation?

Prelab Assignment:
The battery chemistry we are exploring today is described by the reaction:
2 MnO2 + Zn + 2 NH4Cl Mn2O3 + Zn(NH3)2Cl2 + H2O.
This reaction suggests that 2 moles of electrons pass (through an external circuit
like a flashlight) from one mole Zn to 2 moles MnO 2.
1) If, in using a battery in your flashlight, 0.2 moles of electrons are
passed
how many moles MnO2 must have been used?

how many moles of Zn must have been used?

2) Fill in the following blanks with chemical formulas:

In todays lab, a standard solution of 0.05M Na 2S2O3 is used to titrate the
_____________ made in a
reaction of the battery paste with ______________ and ________________.

With the paste from a new battery, the I2 found in the titration is equivalent to the
number of
moles of __________________________ in the sample.

With the paste from a used battery, the I2 found in the titration is equivalent to the
number of moles of
______________________ plus the number of moles of _______________________ in the
sample.
The difference in the moles of I 2 found in the titrations of the new and used battery
paste is

equivalent to half the number of moles of ____________________________ that reacted

in the use of
the battery.