Copyright © 2017 Dr N A Lewis. All rights reserved.

Conductimetric Titration & Gravimetric Determination of

BaSO4
The objective of this experiment is to analyze a solution of Ba(OH)2 whose molar concentration
is unknown. We want to find that molar concentration. You will use two different methods to
measure this concentration. One is called a conductimetric titration and the other is called a
gravimetric technique.

Chemical analysis of a compound is often the first step in a wide variety of chemical,
biochemical, and medicinal chemistry applications. When doing a basic analysis experiment
there are two questions that need to be answered. The first is “What is the chemical structure
of the material we are examining?”. The second is “How much of this material do we have?”

Answering the first of these questions (“What do we have?”) is known as qualitative analysis or
“qual”. It usually involves doing an elemental analysis of the material to figure out the per cent
composition of the elements that are there, followed by the use of various instrumental
techniques to determine how these elements combine together to form their unique structure.

Answering the second of these questions (“How much do we have?”) is known as quantitative
analysis or “quant”.

In this experiment, we already know that the solution we are going to analyze contains Ba(OH)2.
So there is no need to do any qualitative analysis experiments. We do not, however, know how
much Ba(OH)2 is in the sample. Specifically, we do not know the molar concentration of the
Ba(OH)2 solution. We will have to do a quantitative analysis of the solution to answer this
question.

Conductimetric Titration Method

You will monitor conductivity during the reaction between sulfuric acid, H2SO4, and barium
hydroxide, Ba(OH)2, in order to determine the equivalence point in this acid/base reaction.
Conductivity measurements depend on the presence of conducting substances such as ions in
the medium. In this experiment, the equivalence point will be the exact point at which all the
Ba(OH)2 that you started with (the soluble reactant containing all the Ba+2 ions) has been
converted to BaSO4 salt (the insoluble product that contains all the Ba+2 ions). From this
information, you can find the molar concentration of the Ba(OH)2 solution. The reaction
between sulfuric acid and barium hydroxide (two water soluble compounds) yields an insoluble
product, barium sulfate, (called a precipitate) and water, as shown in the reaction equation
below. This kind of process is also called a “double displacement” reaction because both
cations present initially (Ba+2 and H+) swap their anions with the other one to produce the
products shown on the next page. For a reaction to be classified as a “double displacement”
process, at least one of the products must be a precipitate. That will not happen for most

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acid/base processes. It is not at all uncommon in Chemistry for one reaction to be classified in
more than one way.

Ba(OH)2(aq) + H2SO4(aq)  Ba(SO4)(s) + 2 H2O(l) (Equation 1)

The subscript (aq) indicates that this species is dissolved in water, the subscript (s) indicates
that this species is a solid (precipitate) and the subscript (l) indicates that this is a liquid which is
also almost always the solvent.

Now, writing the information as shown in Equation 1 above is actually a short-hand way to
write what is really happening in the solution. This is because as soon as any ionic compound is
dissolved in water, it immediately dissociates into its component ions. If we write the
expression this way, we have what is called the complete ionic equation shown in Equation 2
below. Now it is easier to see how the cations in the original reactants are able to swap with
the anions from the original reactants to produce the products.

Ba2+(aq) + 2 OH–(aq) + 2 H+(aq) + SO42–(aq) → BaSO4(s) + 2 H2O(l) (Equation 2)

In this reaction, the total number of dissociated ions in solution (left hand side of equation 2) is
reduced dramatically during the reaction as a precipitate is formed along with water, these
being the products of the reaction (right-hand side of equation 2). As 0.100 M H2SO4 is slowly
added to Ba(OH)2 of unknown concentration, it is clear from Equation 2 that all the ions
(conducting species) that were in the solution at the beginning of the reaction are consumed to
give two products, a BaSO4 solid and H2O both of which are almost completely non-conducting.

The conductivity of the solution (a good measure of the number of ions present) will be
monitored using a Conductivity Probe. When the probe is placed in a solution that contains
ions, and thus has the ability to conduct electricity, an electrical circuit is completed across the
electrodes that are located on either side of the hole near the bottom of the probe body. This
results in a conductivity value that can be read by the interface.

The unit of conductivity used in this experiment is the microsiemens per cm, or µS/cm.

Gravimetric Method

As the reaction progresses, you will see the solid BaSO4 begin to precipitate from solution.
Collecting all this precipitate which is the insoluble barium sulfate salt, drying it, and then
accurately weighing it, will also allow you to calculate the amount of barium ion that was in
your original sample of unknown concentration. From this weight, you can figure out how
many moles of Ba+2 ions are there and then use this to determine the molar concentration of
the original Ba(OH)2 solution. Procedures like this that depend on weighing are called
gravimetric analysis and are among the most accurate and reliable procedures available.

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For a gravimetric analysis to work it must meet several requirements (information in bold is
important to remember):

(1) The precipitate formed must be pure and of known stoichiometry.

(2) The precipitation reaction must be virtually complete which means that the product
formed must be very insoluble. The usual standard is that percent yield of the solid
product (precipitate) should be 99.9% or better leaving only a very small amount (0.1%
or less) of the product remaining as soluble ions at the end of the procedure.

(3) The precipitating reagent should be specific for the sample being determined. This is
important if there are contaminants present that could form precipitates with the ions
already present. (In your sample, it is known that there are no contaminating cations
present that will precipitate with sulfate.) The Ba2+ cation is the only one there that will
precipitate with sulfate.

(4) The solid that is precipitated should be in the form of reasonably large, well-formed
crystals. This is necessary so that the precipitate can be easily filtered, and the
compound will have the highest possible purity.

(5) The molecular mass of the precipitated solid should be high enough that a reasonable
weight of precipitate is generated even when the molar amount of precipitate is low.

The gravimetric analysis that you will be performing in this laboratory experiment meets all of
the above requirements. Most common contaminating cations (e.g., sodium, magnesium,
aluminum) do not interfere by producing precipitates with the sulfate anion. Strontium,
mercury (I), and lead (II) ions could interfere with the reaction and co-precipitate, but none of
these cations are present in your sample. In order to know what combinations of cations and
anions will give insoluble products, you need to consult a “Solubility Chart”. You will find one of
these in your BlackBoard site under Documents.

The balanced chemical reaction that you will be performing is shown in equation 1. In order to
accurately determine the concentration of barium hydroxide in your “unknown” (i.e. the BaSO4
solution of unknown concentration) by gravimetric determination, you will need to know two
experimental quantities accurately:

a) The volume of your unknown sample that you started with.

b) The weight of barium sulfate obtained from that sample. Since we are expecting results
accurate to parts per hundred, you must be careful to record your weights to 3 decimal
places as usual from the three-decimal place balance you are using. Avoid sample loss or
contamination.

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Copyright © 2017 Dr N A Lewis. All rights reserved.

A. PROCEDURE FOR CONDUCTIMETRIC ANALYSIS

***At some point after your quiz (at least 30 min into class) one person from
each pair should obtain a filter crucible from the drying oven, place in a
desicooler to cool while you complete part A. ***

1. Connect the Drop Counter (black oblong device just above the beaker in picture
below) to DIG/SONIC 1 (this port is on the RIGHT side of the LabPro interface)
and lower it onto the black retort stand (see Figure 1). Obtain a plastic 60 mL
reagent reservoir (looks like a big syringe) for the drop counter as also shown in
Figure 1 below and attach it also to the retort stand with a utility clamp. Place a
250 mL beaker (for now to collect waste liquids) under the drop counter. Make
sure that the magnetic stirrer device is under the beaker as is shown below
(represented by a box at the bottom of Figure 1).

Lab Pro Check Out

The following materials are
already set up in the lab:
-drop counter
-60 mL reagent reservoir
-stir station
The other Lab Pro materials
must be checked out from the
stockroom and includes a:
-stir bar!! (these are $10
each, do NOT lose!!)
Make sure you return the
proper equipment (the stuff in
the kit) at the end of the
experiment.

Figure 1

3. Connect the Conductivity Sensor to Channel 1 of the LabPro interface. Set the selector
switch on the Conductivity Probe to the 0-20,000 range. Connect the LabPro interface to the
computer with the proper cable. Be sure to plug the LabPro interface AC adapter into the
wall outlet. It should immediately show a green light on the top of the interface if it is
working properly.

4. Start the Logger Pro program on your computer. Open the file (from the file folder icon)
called Advanced Chemistry with Vernier folder, then choose “16b Conductivity Titration
(Drop Count)” from this folder.

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5. Close both valves on the reservoir by turning the handles to a horizontal position. Follow
the steps below to set up the reagent reservoir for the titration.

a. Fill the reagent reservoir with water to clean it and to test for leaks. Make sure you still
have a 250 mL beaker under the reservoir to collect the waste water. Start by opening
both valves simultaneously. Look for leaks at the valve attachment positions by putting a
small piece of tissue carefully around each of the valves to see if there is any water
escaping from leaks at this position. Then close first one and then the other valve while
leaving one of them open, checking again with a small piece of tissue to ensure that
there are still no leaks present on either valve attachment position. Now close both
valves again. Treat both the valves very gently. They break easily and this will cause your
experiment to fail. Do not try to force a valve to open or close. If one of your valves is
leaking, report this to the Stockroom (see half-door in the next lab where you got your
LoggerPro Equipment).
g. Now we are going to set the drip rate for this experiment. Open the TOP valve all the
way (vertical). Then, slowly open the BOTTOM valve until you have attained a drop rate
of about one drop per second. Make sure the rate is not MORE than one drop per
second. Once you have set the bottom valve to this drip rate, DO NOT touch it again for
the rest of the experiment. Close the TOP valve (horizontal). At this point, you can use
just the TOP valve to start and stop your liquid flow as needed.

**NOTE: Successful completion of this experiment relies on having the drops from
the reagent reservoir fall directly through the middle of the drop counter AND
KEEPING THE DRIP RATE BELOW ONE DROP PER SECOND!! The drop counter
will “miss” drops if the rate is any faster!!**

7. You must calibrate the volume of the drops that will be delivered from the reagent
reservoir.
a. On the top row of the Logger Pro toolbar, open the Experiment menu and choose
Calibrate
DIG 1: Drop Counter (mL).
b. Select the Automatic button, and continue as follows:
c. Place a clean and dry 10 mL graduated cylinder directly below the slot on the Drop
Counter (where the 250 mL beaker used to be), lining it up with the tip of the reagent
reservoir. Adjust the reservoir so that its tip is just above the Drop Counter slot and
drops will fall directly through the drop counter into the beaker. The drops MUST fall
through the drop counter in the exact center (front to back AND left to right) of the
opening in the drop counter.
d. Click the Start button and at the same time do step e) below.
e. Open the TOP valve on the reagent reservoir (vertical) to start the flow. (Remember,
the BOTTOM valve is set to give the desired flow rate, so don’t touch it!) You should see
the drops being counted on the computer screen.
f. When the volume of the H2SO4 solution in the graduated cylinder is between 5 and
6 mL, close the TOP valve of the reagent reservoir and read the precise mL present.
g. Enter that precise volume of H2SO4 in the graduated cylinder (read to the nearest 0.1
mL) in the edit box. Record the number of Drops/mL displayed on the screen for
possible future use.
h. Click . Discard the H2O from the graduated cylinder and set it aside.

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 Copyright © 2017 Dr N A Lewis. All rights reserved.

8. Assemble the apparatus.

a. Insert the Conductivity Sensor through the large hole in the Drop Counter.
b. Use a clean dry 10 mL graduated cylinder to transfer exactly 10.0 mL of the Ba(OH)2
solution into a clean dry 100 mL beaker. Be sure to put the top back on the reagent
bottle in the fume hood that contains this solution. It is air sensitive and will absorb
CO2 gas and this will change the concentration of this base. Add about 30 mL of
distilled water to the Ba(OH)2 in the 100 mL beaker bringing the total volume of solution
to about 40 mL. CAUTION: The barium hydroxide solution is caustic. Avoid getting it
on your skin or clothing.
b. Adjust the positions of the Drop Counter and reagent reservoir so they are both lined
up with the proper positioning of the apparatus for the 100 mL beaker you are now
using. Adjust the reservoir so that its tip is just above the Drop Counter slot and drops
will fall directly through the drop counter into the beaker. The drops MUST fall through
the drop counter in the exact center (front to back AND left to right) of the opening in
the drop counter.
c. Place the little magnetic stir bar into the 100 mL beaker of barium hydroxide solution,
then lift up the Conductivity Sensor, and slide the 100 mL beaker containing the Ba(OH)2
solution onto the magnetic stirrer. Lower the Conductivity Sensor into the beaker. Turn
the stirrer on so the stir bar spins as fast as possible.

9. Conduct the titration.

a. Click to begin monitoring conductivity. No data will be collected until the first
drop goes through the Drop Counter slot. Fully open only the TOP valve – the bottom
valve should still be adjusted so drops are released at a rate of about 1 drop every
second.
b. Observe your graph; the conductivity will drop to a minimum and then rise again. The
titration curve will be V-shaped. After the conductivity curve shows a good V-shape,
click . Turn the TOP valve of the reagent reservoir to a closed (horizontal)
position.
10. Examine the data on the displayed graph to find the equivalence point; that is, the
volume when the conductivity value reaches a minimum. To do this, highlight the linear
portion of the data where the conductivity is DECREASING only. Once highlighted, click on
the “linear fit” button.

Do the same thing for the linear portion of the data where the conductivity is INCREASING
past the equivalence point. Again, click the “linear fit” button. Highlight the area where the
two linear fit lines intersect and zoom in for a better view. Now go to the Analyze menu and
select “Interpolate”. Move the mouse cursor to the volume reading where both linear fit
display boxes show the same conductivity—the volume displayed is the equivalence point
volume for the titration. (You may need to adjust the Y-axis scale to read BELOW zero to
see the intersection of the lines—simply click on the zero for the Y-axis and enter a negative
number.)

11. Make sure that you construct two graphs to turn in for grading. The first graph should show
the entire conductimetric titration. You should have a V in the graph. The bottom of the V
is the equivalence point for this experiment. The second graph should be an expanded
view of only the equivalence point area and your extrapolations to get the exact value of
the equivalence point.

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 Copyright © 2017 Dr N A Lewis. All rights reserved.

B. PROCEDURE FOR GRAVIMETRIC ANALYSIS

Remove the now cool filter crucible from the desicooler and weigh it using the three decimal
place balance. Place the crucible into the black cup of the vacuum filtration apparatus (see
below) securely to form a good seal between the filter crucible and the rubber cup. Obtain an
orange vacuum hose from the front desk.

Note there is a yellow spigot in your work area with the letters VAC on it that will pull a vacuum
on your filtration apparatus. Attach the other end of the orange hose to this spigot. Before
filtering your solution, obtain a squirt bottle of methanol. Then immediately before you are
ready to filter your solution, spray about a milliliter of the methanol into the crucible to wet the
filter disk. Remember that methanol evaporates quickly so there must still be some liquid
methanol in the crucible before opening the spigot to start the vacuum. This step will seal the
filter paper to the crucible and prevent the loss of solid barium sulfate. Now quickly add a little
of your BaSO4 solution to the crucible. The aqueous suspension will maintain this seal for a
much longer time. Before adding more of the barium sulfate, you should use a glass stirring rod
to mix well the solid with the liquid to form a good suspension, and immediately begin filtering
your solution, being careful not overfill the crucible or spill any of the solution. There will be
some solid left in your beaker. You can remove the liquid from the filter flask and put it back
into the original beaker to transfer more of the solid. Do this step as often as needed to make
sure all the solid has been transferred to the crucible. Do not tilt the beaker steeply enough to
allow the magnetic stir bar to enter the crucible—it should stay in the beaker (or you can
remove it with a stir bar retriever so that this is not a concern).

When the majority of the solid is in the crucible and only a few specks remain in the beaker,
you can rinse any barium sulfate remaining in the beaker into the crucible using the methanol
squirt bottle. Again, be careful not to rinse the stir bar into the crucible (if it was not removed
earlier). After all the precipitate has been transferred to the filter crucible, wash the precipitate

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Copyright © 2017 Dr N A Lewis. All rights reserved.

with a small portion of methanol. Allow the crucible to sit on the vacuum apparatus for about
a minute. Get a labelled beaker ready to put your crucible back into the drying oven.

Place the crucible plus precipitate in the drying oven inside a labelled beaker, and dry for 15-20
minutes (or as long as possible before the end of the lab). Make sure that the beaker you use is
not so small that it will fall over). Losing any BaSO4 at this point will ruin any chance of accuracy
in this experiment. At the end of the drying time, carefully remove the beaker with your
crucible from the drying oven and place it in your desicooler to cool. Once cool (about 10
minutes), record the weight of the crucible with the barium sulfate and then determine the
mass of barium sulfate collected. With this information, you can calculate the original
concentration of the barium hydroxide solution.

At the end of the lab, discard your barium sulfate solid in the solid wastes container. Clean the
filter crucible thoroughly to remove all traces of barium sulfate solid, place a new filter disk in
the crucible, and return it to the oven to dry for the next lab section.

Rinse the conductivity probe tip with distilled water and blot dry. Also, thoroughly rinse the
solvent reservoir with distilled water (including the tip). Return the equipment kit that was
checked out including the magnetic stir bar to the stockroom. Leave the drop counter,
reservoir, and stir station set up on the lab bench.

DATA AND CALCULATIONS

Equivalence Point from Titration (mL) _____________

Molarity of H2SO4 solution _____________

Moles of Ba+2 from Titration (mol) _____________

Volume of original Ba(OH)2 soln (mL) _____________

Conc. of Ba(OH)2 from titration (M) _____________

Mass of Crucible and precipitate (g) _____________

Mass of Crucible (g) _____________

Mass of Precipitate (g) _____________

Conc. of Ba(OH)2 from gravimetric (M) _____________