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WINTER 2010
POTENTIOMETRIC TITRATIONS
Fill-in, Prelab attached (p 12)
Name
Titrating a strong acid with a strong base, weak acid with a strong base, and a polyprotic acid
with a strong base.
TO EARN YOUR FINAL STAMP: The following items must be completed in lab. You may
complete the entire assignment in the lab; this reflects the minimum required to earn your final
stamp.
Collect and process all data for the titration of HCl with NaOH
Collect and process all data for the titration of H3PO4 with NaOH
Determine the concentration of HCl and H3PO4 from your titration data, and enter the data in
the lab computer for the computation of class averages.
Determine the pKa1 and pKa2 for H3PO4, based on your titration curve.
Introduction
In the experiment today you will be performing a potentiometric titration to determine the unknown
concentrations of two acids. In order to perform this titration you will utilize a pH meter, an
instrument which allows you to directly measure the strength and concentration of an acid.
Discussion
pH meters (see Figure 1) operate by measuring the difference in voltage generated between and
indicator electrode and a reference electrode. The reference electrode or probe is not sensitive to H+
concentration changes and is simply used as a reference point. This electrode produces a constant
voltage (E = +0.2 V) which is provided by the following reaction:
Hg2Cl2 + 2e-
2Hg+1 + 2Cl-
The sensing probe, which is H+ ion sensitive, consists of a glass bulb filled with dilute HCl into
which is inserted a silver or platinum wire. (See Figure 1)
Exp #8 Potentiometric Titrations
Page 1 of 12
Figure 1
The glass bulb is permeable to H+ ions but not to other ions. If the solution into which the electrode
is placed is more concentrated than that in the bulb, H+ ions will move from the solution into the
bulb. The HCl solution inside the bulb will then have an excess of H+ ions and will be positive with
respect to the solution being measured
This potential difference across the glass membrane can be measured then compared to the reference
voltage and a pH determined for the measured solution. Quite often the reference and indicator
electrodes are combined into one probe called a combination probe or electrode. It operates the
same way as the two probes.
Method for Determining Concentration
In this experiment you will be titrating both a strong monoprotic acid and a weak polyprotic acid
with a standardized strong base. You will be adding the standardized base to the acid and measuring
the resulting pH. When the volume of base added is plotted on a graph as a function of pH, a
titration curve is produced. From this curve it is possible to determine the milliliters of base needed
to neutralize the amount of acid present in the solution of unknown concentration. The shape of the
titration curve is dependent on the type of acid being titrated (i.e., strong or weak acid). The two
situations are described below.
Strong Monoprotic Acids
When a strong monoprotic acid, such as HCl, is dissolved in water it totally ionizes into H+ and Clions. As a strong base, such as sodium hydroxide, is added to the acid solution, the available
hydroxide ions combine with some of the available H+ ions to form water. If we continue to add
base and record the resulting pH, we produce, upon graphing a titration curve similar to that shown
in Figure 4.
HCl + H2O H+1 (aq) + Cl-1 (aq)
H+ + OH-
H2 O
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Figure 2
http://img.sparknotes.com/figures/3/3a5994498f24d59f5d5d762b40844a2a/sasb.gif (accessed February 27, 2008)
Notice that until we reach the neutralization or end point, the pH of the solution stays nearly
constant. We know that pH is a measure of H+ ion concentration (pH = log[H+]). Since our strong
acid totally ionizes, we have a large reserve of H+ (actually H3O+) ions available in solution to
instantly react with any added base. Because we have such a large reserve of H+, the addition of a
few milliliters of base will cause only a small change in the total H+ ion concentration. We also
know that pH + pOH = 14. Since any hydroxide ion that is added is immediately neutralized, the
pH remains relatively unchanged.
Once the neutralization point is reached, however, the available reserve of H+ ions is depleted. The
concentration of H+ drops dramatically, while the concentration of hydroxide ion increases. This
causes the pH value to rise. The pH value continues to rise until the pH of the base being added is
reached. Once reached, addition of more base has little effect and the pH again becomes relatively
constant.
It is possible to determine the endpoint for the neutralization reaction, and therefore the base needed
to neutralize the acid, simply by extending a line from the vertical portion of the titration curve to the
x-axis (see Figure 2). Since we are given the normality of the standard base and the volume of acid
used, the normality of the acid can be calculated using the relationship:
Nacid Vacid = Nbase Vbase
Weak Polyprotic Acids
Weak polyprotic acids such as phosphoric acid (H3PO4) do not totally ionize in solution. In fact,
most of the phosphoric acid remains as unionized H3PO4 molecules in solution. The small amount
that does ionize exists as a series of equilibrium equations, each of which produce some H+ ions.
Reaction #1
H3PO4
H+ + H2PO 4
Reaction #2
H2PO 4
H+ + HPO 2
4
Reaction #3
HPO 2
4
H+ + PO 3
4
[H 2PO 4 ][H + ]
= 7.5 10-3
[H 3PO 4 ]
+
[HPO2
4 ][H ]
Ka2 =
= 6.2 10-8
[H 2PO4 ]
+
[PO3
4 ][H ]
Ka3 =
= 3.6 10-13
[HPO2
]
4
Ka1 =
Page 3 of 12
We can also perform a potentiometric titration on H3PO4 (see Figure 3). Note in this graph that the
pH value slowly increases and that the pH transitions through the end points of the acid are not
abrupt but instead are gradual.
The third
equivalence point
is not observed.
Note the volumes
(and relationships)
at the equivalence
points.
Figure 3
equivalence points: the volume
between ( way between each eq. pt)
If the volume to get to the first eq. pt = 10.00 mL then the eq. pt = 5.00 mL.
At this point, pH = pKa1. If the volume to get to the second eq. pt = 20.00 mL
then the eq pt = (10.00 + 20.00 ml)/2 = 15.00 mL. At this point, pH = pKa2.
On this graph, pH = pKa1 = 1.9
and pH = pKa2 = 7.3
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When we titrate H3PO4 with a strong base (i.e., NaOH), the following reactions would occur.
H3PO4 + NaOH
NaH2PO4 + H2O
NaH2PO4 + NaOH
Na2HPO4 + H2O
Na2HPO4 + NaOH
Na3PO4 + H2O
H+ + H2PO 4
NaOH (aq)
NaH2PO4 + H2O
Where there is no large readily available reserve of H+ ions as were present with the totally ionized
strong acid, there are three sources where H+ ions can be obtained as needed. We have shown that
the weak polyprotic acids exist as a series of equilibrium equations. If we shift the equilibrium out
of balance, the systems will adjust to reestablish the equilibrium. When the available H+ is used to
neutralize added base, some unionized acid from each of the three equilibrium equations must ionize
to reestablish the equilibrium of the hydrogen ion to near the original value. Since the [H+] is
changing very little, the pH also changes very little. Mixtures of weak acids and their salts stabilize
hydrogen ion concentration upon addition of small amount of base by shifting the various
equilibrium equations. This is also known as buffering the solution.
The size of the ionization (equilibrium) constant is a measure of the degree of ionization. The larger
the value, the greater the ionization. For this reason, K1 is going to supply more H+ ions than is K2
or K3. Therefore, as the sodium hydroxide is added, reaction #1 will provide more equilibrium
concentrations of H+ than will reaction #3. Reaction #1 will then be used up first (i.e., its endpoint
will be reached first). We do not, however, get a sharp vertical rise at the endpoint as we did with
the strong, monoprotic acid. This is because reactions #2 and #3 are still helping to moderate the
change in [H+] and thus, the pH.
After the H+ from reaction #1 is used, the pH slowly rises to the H+ ion value that can be supplied by
the equilibrium reactions #2 and #3.
Finally, after all H+ from reaction #2 is used, we see a third rise in pH. However, because of the
very small size of K3 it is often difficult to obtain an accurate measurement for the titration of
reaction #3.
You will be asked to perform a potentiometric titration of both HCl and H3PO4 using the strong
base, NaOH, in this experiment.
Page 5 of 12
Experimental
The standardized base and stir bars can be found on the reagent bench. The magnetic stir plates are
under the middle hood. The unknown acids will be in burets for you to use. Measure out about 20
mL and record the volume to the nearest 0.01 mL. Refill the burets from the bottles/transfer
beakers beside the apparatus. The pH electrodes and interfaces are next to the computers
CAUTION: Do not spill liquids on the computer or interfaces. Put your set-up together
carefully. Place magnetic stir plates as far away from the monitors as possible.
PROCEDURE General description- You will be doing two titrations using a pH electrode as a
sensor and typing in the volumes you read on the buret. For each acid, HCl and H3PO4, you
will determine the volume at each equivalence point and calculate the molarity for that acid.
You must calibrate the electrode before you begin.
Technique Tip: Rinse the electrodes between solutions by dipping them into a beaker of distilled
water or use a wash bottle to rinse the solution on the electrode into a waste beaker.
Setting up the computer:
1. Obtain and wear goggles. Set up the equipment as shown in Figure 4 with the electrode
attached to the pH amplifier. Instead of the pH meter you will have your computer, interface and
pH amplifier.
2. At the computer, open the Vernier/LoggerPro software using the start menu. Then File Open
Experiment Chemistry with Computers 25 Titration dip acid. Make sure the
vertical axis of the graph is pH scaled from 0 to 14 pH units and the horizontal axis reads 0 to
50mL. Change the axes as necessary.
Calibrating the pH electrode:
3. Obtain two buffer solutions, one each of buffer pH 4 and buffer pH 7. Do not contaminate or
dilute these solutions! They can be reused by other groups. Place the pH probe into the pH 4
buffer solution. Go to the menu and under the Experiment open Calibrate. Click Calibrate
now. The electrode will be reading a voltage when this value has stabilized, type in the pH of
your buffer (4.0) into the Enter Value box under Reading 1 and then click Keep. Rinse your
electrode and place it into the pH 7 buffer solution. When the voltage has stabilized again, enter
that pH value (7.0) in the box under Reading 2 and click keep. Click done to return to the graph
and data table screen. Rinse the electrode and place the probe back into the pH 4 buffer to make
sure it is stable. If the electrode is properly calibrated, the pH of the solution should read 4.00
0.05 units. If your pH value is significantly different (0.05 pH units) than the buffer you are
checking, or if the value drifts slowly to a higher or lower number, contact your lab instructor.
Preparing solutions and setting up the titration apparatus:
4. Obtain a MAXIMUM of 100 mL of NaOH in a clean and dry beaker. You will use this NaOH
for both experiments. Record the precise concentration of the NaOH solution in the Data
and Calculations table.
5. Obtain a 50-mL buret and rinse the buret with about 5 mL of the ~0.1 N NaOH solution. Roll
the NaOH in the buret to coat and rinse all sides, and drain the NaOH through the tip into a
waste beaker. Use a buret clamp to attach the buret to the ring stand as shown in Figure 4. Fill
the buret a little above the 0.00-mL level of the buret. Drain a small amount of NaOH solution
so it fills the buret tip and leaves the NaOH at the 0.00-mL level of the buret. You do not need
to start exactly at 0.00-mL- you can record the initial volume and subtract it from the final, to get
your total volume.
Exp #8 Potentiometric Titrations
Page 6 of 12
Figure 4
6. Place about 100 mL of distilled water into a 250 mL beaker. From a buret already set up for you
at the reagent bench, measure to the nearest 0.01 ml, 20 ml of an acid, HCl, of unknown
concentration directly into the beaker.
7. Place the beaker with your acid on a magnetic stirrer and add a stirring bar.
Titration
8. Use a three prong utility clamp to suspend a pH electrode on a ring stand as shown in Figure 4.
Position the pH electrode in the HCl (or H3PO4) solution and adjust its position toward the
outside of the beaker so that it is not struck by the stirring bar.
9. You are now ready to begin the titration. This process goes faster if one person manipulates and
reads the buret while another person operates the computer and enters buret readings.
Before adding any NaOH titrant, click on the Collect button and monitor pH for 5-10
seconds. After the pH has stabilized, click on the Keep button. Enter the current buret level,
0.00. You have now stored the first data pair.
Add enough NaOH to raise the pH by about 0.20 units. After the NaOH has been added and
the pH has stabilized, click on the Keep button. Enter the new buret reading, to the nearest
0.01 mL. Be sure that the pH has stabilized! There is a delay between the addition of
NaOH and a stable pH reading.
Continue adding NaOH solution in increments that raise the pH about 0.20 units and enter
the buret reading after each addition. By watching your graph, it will be easy to see when
your pH starts jumping significantly for a small amount of base added. Adjust the amount of
NaOH added to keep the pH changes at 0.20 units. Slow down your titration and collect
data. Eventually you will collect every one or two drops to get good data for the equivalence
point regions. Once again, be sure that the pH has stabilized!
When you have reached a flat region past the equivalence point for HCl or when the pH is
greater than 11 for H3PO4 you may Stop the titration.
10. Change the title of your graph appropriately. Click on the graph and from the File menu choose
Print window and proceed to print the graph. Click on the data table window and again choose
print window and print the data table. You may want to include your name in the title.
11. Double check the electrode with a buffer solution and make sure it is still calibrated. Repeat the
titration with the H3PO4 (using about 20 mL of acid, read and recorded to the nearest 0.01 mL).
****
Dispose of the beaker and buret contents and any other solutions in the collection
bottles.
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Page 8 of 12
Report Sheet
Potentiometric Titrations
Lecturer _________________
Name _____________________
Partner_____________________
Stamp here
Data and Calculations -Attach all data tables and labeled graphs (see previous page)
This table must be completed in lab to earn a final stamp.
HCl Titration.
H3PO4 Titration
Initial volumes of
Acid
Concentration of
NaOH
Volume of NaOH
at Eq.Pt. 1
Volume of NaOH
at Eq.Pt. 2
Molarity of acid.
Show calc. below.
Molarity of acid.
At eq. pt. 2
E.P. 2
pKa1 =
pKa2 =
[H3PO4] =
initials:
Class average for M of HCl __________ Class average for M of H3PO4 ______________
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4. Taking into account the fact that H3PO4 is triprotic, and that youve only examined the first two
equivalence points, use your data to estimate the volume of base that would be required to reach
the third equivalence point.
Page 10 of 12
5. Using the Ka values provided in the lab, calculate pKa1 and pKa2. (report your values to two sf)
6. Calculate the % difference between the calculated pKa values (consider these to be the ideal
values) and the values you read off your graph. (pay attention to sf in this calculation!)
Page 11 of 12
Prelab Assignment
Name _____________________
Stamp here
1. Write the ionic and net ionic equation for the reaction of HNO3(aq) with NaOH(aq).
2. The following graph shows the equivalence points for a diprotic acid. Label the axis and
indicate on the graph the equivalence points and the equivalence points
d. If 21.00 mL of 0.0950 N NaOH solution is used to titrate 28.75 mL of H2SO3(aq) to the first
equivalence point, what is the molarity of the acid? (hints: review your acids and bases lab!
And at the first eq. pt. how many H+ ions have reacted? )
e. What total volume of NaOH solution would be needed to get to the second equivalence
point?
__________________ mL
f. Use your answer to part d to compute the normality of the H2SO3.
Page 12 of 12