Titration of a Diprotic Acid

Identifying an Unknown
A diprotic acid is an acid that yields two H+ ions per acid molecule. Examples of diprotic acids are
sulfuric acid, H2SO4, and carbonic acid, H2CO3. A diprotic acid dissociates in water in two stages:
(1) H2X(aq)   H+(aq) + HX–(aq)
(2) HX–(aq) 
 H+(aq) + X2–(aq)

Because of the successive dissociations, titration curves

of diprotic acids have two equivalence points, as shown
in Figure 1. The equations for the acid-base reactions
occurring between a diprotic acid, H2X, and sodium
hydroxide base, NaOH, are from the beginning to the
first equivalence point:
(3) H2X + NaOH   NaHX + H2O

from the first to the second equivalence point:

(4) NaHX + NaOH   Na2X + H2O

from the beginning of the reaction through the second

equivalence point (net reaction):
(5) H2X + 2 NaOH   Na2X + 2 H2O

At the first equivalence point, all H+ ions from the first dissociation have reacted with NaOH base.
At the second equivalence point, all H+ ions from both reactions have reacted (twice as many as at
the first equivalence point). Therefore, the volume of NaOH added at the second equivalence point
is exactly twice that of the first equivalence point (see Equations 3 and 5).

The primary purpose of this experiment is to identify an unknown diprotic acid by finding its
molecular weight. A diprotic acid is titrated with NaOH solution of known concentration. Molecular
weight (or molar mass) is found in g/mole of the diprotic acid. Weighing the original sample of acid
will tell you its mass in grams. Moles can be determined from the volume of NaOH titrant needed to
reach the first equivalence point. The volume and the concentration of NaOH titrant are used to
calculate moles of NaOH. Moles of unknown acid equal moles of NaOH at the first equivalence
point (see Equation 3). Once grams and moles of the diprotic acid are known, molecular weight can
be calculated, in g/mole. Molecular weight determination is a common way of identifying an
unknown substance in chemistry.

You may use either the first or second equivalence point to calculate molecular weight. The first is
somewhat easier, because moles of NaOH are equal to moles of H2X (see Equation 3). If the second
equivalence point is more clearly defined on the titration curve, however, simply divide its NaOH
volume by 2 to confirm the first equivalence point; or from Equation 5, use the ratio:
1 mol H2X / 2 mol NaOH
OBJECTIVE
In this experiment, you will identify an unknown diprotic acid by finding its molecular weight.

MATERIALS
Materials for both Method 1 (buret) and Method 2 (Drop Counter)
LabQuest magnetic stirrer (if available)
LabQuest App stirring bar or Microstirrer (if available)
Vernier pH Sensor wash bottle
unknown diprotic acid, 0.120 g distilled water
Materials required only for Method 1 (buret)
50 mL buret 2nd utility clamp
2nd 250 mL beaker

Materials required only for Method 2 (Drop Counter)

Vernier Drop Counter 100 mL beaker
60 mL reagent reservoir 10 mL graduated cylinder

CHOOSING A METHOD
Method 1 has the student deliver volumes of NaOH titrant from a buret. After titrant is added, and
pH values have stabilized, the student is prompted to enter the buret reading manually and a pH-
volume data pair is stored

Method 2 uses a Vernier Drop Counter to take volume readings. NaOH titrant is delivered drop by
drop from the reagent reservoir through the Drop Counter slot. After the drop reacts with the
reagent in the beaker, the volume of the drop is calculated, and a pH-volume data pair is stored.

METHOD 1: MEASURING VOLUME USING A BURET

1. Obtain and wear goggles.

2. Weigh out about 0.120 g of the unknown diprotic acid on a piece of weighing paper. Record the
mass to the nearest 0.001 g in the Data and Calculations table. Transfer the unknown acid to a
250 mL beaker and dissolve in 100 mL of distilled water. DANGER: Do not eat or drink when
using the solid acid or its solutions—harmful if swallowed. Causes skin and eye irritation.
Avoid breathing dust or fumes. May cause respiratory irritation.

3. Place the beaker on a magnetic stirrer and add a stirring bar. If no magnetic stirrer is available,
you need to stir with a stirring rod during the titration.

Figure 2
4. Connect the pH Sensor to LabQuest and choose New from the File menu. If you have an older
sensor that does not auto-ID, manually set up the sensor.

5. Use a utility clamp to suspend a pH Sensor on a ring stand as shown in Figure 2. Position the pH
 6. Obtain a 50 mL buret and rinse the buret with a few mL of the ~0.1 M NaOH solution. Record
the precise concentration of the NaOH solution in the Data and Calculations table. Use a utility
clamp to attach the buret to the ring stand as shown in Figure 2. 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. Dispose of the waste solution in this step as
directed by your teacher. WARNING: Sodium hydroxide solution, NaOH: Causes skin and eye
irritation.

7. Set up the data-collection mode.

a. On the Meter screen, tap Mode. Change the data-collection mode to Events with Entry.
b. Enter the Name (Volume) and Units (mL). Select OK.
8. You are now ready to perform the titration. This process goes faster if one person manipulates
and reads the buret while another person operates enters volumes.
a. Start data collection.
b. Before you have added any drops of NaOH solution, tap Keep and enter 0 as the buret
volume in mL (using the numerical keyboard displayed on the screen). Select OK to store the
first data pair for this experiment.
c. Add the next increment of NaOH titrant (enough to raise the pH about 0.20 units). When the
pH stabilizes, tap Keep and enter the current buret reading (to the nearest 0.01 mL). Select
OK. You have now saved the second data pair for the experiment.
d. Continue adding NaOH solution in increments that raise the pH by about 0.20 units and enter
the buret reading after each increment. Proceed in this manner until the pH is 3.5.
e. When pH 3.5 is reached, change to 2-drop increments. Enter the buret reading after each
increment.
f. After pH 4.5 is reached, again add larger increments that raise the pH by about 0.20 units and
enter the buret reading after each addition. Continue in this manner until a pH of 7.5 is
reached.
g. When pH 7.5 is reached, change to 2-drop increments. Enter the buret reading after each
increment.
h. When pH 10 is reached, again add larger increments that raise the pH by 0.20 units. Enter the
buret reading after each increment. Continue in this manner until you reach a pH of 11 or use
25 mL of NaOH, whichever comes first.
9. Stop data collection.

10. Examine the data on the displayed graph of pH vs. volume to find the equivalence point—that is
the largest increase in pH upon the addition of 1 drop of NaOH solution. To examine the data
pairs on the displayed graph, tap any data point. As you tap each data point, the pH and volume
values are displayed to the right of the graph.
One of the two equivalence points is usually more clearly defined than the other; the two-drop
increments near the equivalence points frequently result in larger increases in pH
(a steeper slope) at one equivalence point than the other. Indicate the more clearly defined
equivalence point (first or second) in Box 1 of the Data and Calculations table. Determine the
volume of NaOH titrant used for the equivalence point you selected. To do so, examine the data
to find the largest increase in pH values during the 2-drop additions of NaOH. Find the NaOH
volume just before this jump. Then find the NaOH volume after the largest pH jump. Record
these values in Box 2 of your data table.
For the alternate equivalence point (the one you did not use in the previous step), examine the
data points on your graph to find the largest increase in pH values during the 2-drop additions of
NaOH. Find the NaOH volume just before and after this jump. Record these values in Box 10 of
your data table. Note: Another method for determining the equivalence-point volume is
described in the Alternate Equivalence Point Method of this experiment.

11. Dispose of the beaker contents as directed by your teacher. Rinse the pH Sensor and return it to
the pH storage solution.

12. Before printing the graph of pH vs. volume, rescale the y axis from 0 to 12 pH units.
 d. Select OK. The y-axis on the displayed graph should now have pH scaled from 0 to 12.
13. Print or sketch a copy of the graph of pH vs. volume.

14. (optional) Print a copy of the NaOH volume and pH data for the titration.
METHOD 2: MEASURING VOLUME WITH A DROP COUNTER
1. Obtain and wear goggles.

2. Weigh out about 0.120 g of the unknown diprotic acid on a piece of weighing paper. Record the
mass to the nearest 0.001 g in the Data and Calculations table. Transfer the unknown acid to a
250 mL beaker and dissolve in 100 mL of distilled water. CAUTION: Handle the solid acid
and its solution with care. Acids can harm your eyes, skin, and respiratory tract.

3. Obtain the plastic 60 mL reagent reservoir. Note: The bottom valve will be used to open or
close the reservoir, while the top valve will be used to finely adjust the flow rate. For now, close
both valves by turning the handles to a horizontal position.
Rinse it with a few mL of the ~0.1 M NaOH solution. Record the precise concentration of the
NaOH solution in the Data and Calculations table. Use a utility clamp to attach the reagent
reservoir to the ring stand. Add the remainder of the NaOH solution to the reagent reservoir.
WARNING: Sodium hydroxide solution, NaOH: Causes skin and eye irritation.
Drain a small amount of NaOH solution into the 250 mL beaker so it fills the reservoir’s tip. To
do this, turn both valve handles to the vertical position for a moment, then turn them both back
to horizontal.

4. Connect the pH Sensor to CH 1 of LabQuest. Lower the Drop Counter onto a ring stand and
connect it to DIG 1. Choose New from the File menu. If both sensors are identified, proceed to
Step 5.
If you have older sensors that do not auto-ID, manually set them up:

a. Choose Sensor Setup from the Sensors menu.

b. Select Drop Counter from the DIG 1 sensor list, or pH Sensor from the CH 1 sensor list.
c. Select OK.
5. Calibrate the Drop Counter so that a precise volume of titrant is recorded in units of milliliters.
a. Choose Calibrate ► Drop Counter from the Sensors menu.
 If you have previously calibrated the drop size of your reagent reservoir and want to
continue with the same drop size, tap Equation. Enter the value for Drops/mL. Select Apply to make
the changes take effect. Select OK and proceed directly to Step 6.
 If you want to perform a new calibration, select Calibrate Now, and continue with this step.
b. Select Calibrate Now.
c. Place a 10 mL graduated cylinder directly below the slot on the Drop Counter, lining it up
with the tip of the reagent reservoir.
d. Open the bottom valve on the reagent reservoir (vertical). Keep the top valve closed
(horizontal).
e. Slowly open the top valve of the reagent reservoir so that drops are released at a slow rate
(~1 drop every two seconds). You should see the drops being counted on the screen.
f. When the volume of NaOH solution in the graduated cylinder is between 9 and 10 mL, close
the bottom valve of the reagent reservoir.
g. Enter the precise Volume of NaOH. Select Stop. Record the
number of drops/mL displayed on the screen for possible future
use. Select OK.
6. Assemble the apparatus.
a. Place the magnetic stirrer on the base of the ring stand.
b. Insert the pH Sensor through the large hole in the Drop
Counter.
c. Attach the Microstirrer to the bottom of the pH Sensor,
as shown in the small picture. Rotate the paddle wheel of the
Microstirrer and make sure that it does not touch the bulb of the
pH Sensor.
d. Adjust the positions of the Drop Counter and reagent reservoir so
 f. Adjust the position of the Drop Counter so that the Microstirrer on the pH Sensor is just
touching the bottom of the beaker.
g. Adjust the reagent reservoir so its tip is just above the Drop Counter slot.
7. Turn on the magnetic stirrer so that the Microstirrer is stirring at a fast rate.

8. You are now ready to begin collecting data. Check to see that the pH value is between 1.5 and
2.5. Start data collection. No data will be collected until the first drop goes through the Drop
Counter slot. Fully open the bottom valve—the top valve should still be adjusted so drops are
released at a rate of about 1 drop every 2 seconds. When the first drop passes through the Drop
Counter slot, check the data table to see that the first data pair was recorded.

9. Continue watching your graph to see when a pH of 11. When this occurs, stop data collection to
view a graph of pH vs. volume Turn the bottom 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 largest
increase in pH upon the addition of 1 drop of NaOH solution. To examine the data pairs on the
displayed graph, tap any data point. As you tap each data point, the pH and volume values are
displayed to the right of the graph.
One of the two equivalence points is usually more clearly defined than the other; the two-drop
increments near the equivalence points frequently result in larger increases in pH
(a steeper slope) at one equivalence point than the other. Indicate the more clearly defined
equivalence point (first or second) in Box 1 of the Data and Calculations table. Determine the
volume of NaOH titrant used for the equivalence point you selected. To do so, examine the data
to find the largest increase in pH values during the 2-drop additions of NaOH. Find the NaOH
volume just before this jump. Then find the NaOH volume after the largest pH jump. Record
these values in Box 2 of your data table.
For the alternate equivalence point (the one you did not use in the previous step), examine the
data points on your graph to find the largest increase in pH values during the 2-drop additions of
NaOH. Find the NaOH volume just before and after this jump. Record these values in Box 10 of
your data table. Note: Another method for determining the equivalence-point volume is
described in the Alternate Equivalence Point Method of this experiment.

11. Dispose of the beaker contents as directed by your teacher. Rinse the pH Sensor and return it to
the pH storage solution.

12. Before printing the graph of pH vs. volume, manually scale the y-axis from 0 to 12 pH units.
a. Choose Graph Options from the Graph menu.
b. Select Manual.
c. Enter 12 as the Graph 1 Y-Axis Top value (the maximum pH value).
d. Enter 0 as the Graph 1 Y-Axis Bottom value (the minimum pH value).
e. Select OK. The y-axis on the displayed graph should now have pH scaled from 0 to 12.
13. Print or sketch a copy of the graph of pH vs. volume.

14. Print or sketch a copy of the NaOH volume and pH data for the titration.

ALTERNATE EQUIVALENCE POINT METHOD

An alternate way of determining the precise equivalence point of the titration is to take the first and
second derivatives of the pH-volume data.

1. Determine the peak value on the first derivative vs. volume plot.

a. Tap the Table tab. Choose New Calculated Column from the Table menu.
b. Enter d1 as the Calculated Column Name. Select the equation, 1st derivative (Y,X). Use
Volume as the Column for X, and pH as the Column for Y. Select OK.
c. On the displayed plot of d1 vs. volume, examine the graph to determine the volume at the
 a. Tap the Table tab. Choose New Calculated Column from the Table menu.
b. Enter d2 as the Calculated Column Name. Select the equation, 2nd derivative (Y,X). Use
Volume as the Column for X, and pH as the Column for Y. Select OK.
c. On the displayed plot of d2 vs. volume, examine the graph to determine the volume when the
2nd derivative equals approximately zero.

PROCESSING THE DATA

1. Use your graph and data table to confirm the volumes you recorded in Box 2 of the Data and
Calculations table (volumes of NaOH titrant before and after the largest increase in pH values).
Underline both of these data pairs on the printed data table.

2. Determine the volume of NaOH added at the equivalence point you selected in Step 1. To do
this, add the two NaOH volumes determined in Step 1. Find the NaOH volume just before the
jump. Then find the NaOH volume after the jump and record them in the data table.

3. Determine the volume of NaOH added at the equivalence point you selected in Step 1. To do
this, add the two NaOH volumes determined in Step 2 and divide by two.

4. Calculate the number of moles of NaOH used at the equivalence point you selected in Step 1.

5. Determine the number of moles of the diprotic acid, H2X. Use Equation 3 or Equation 5 to
obtain the ratio of moles of H2X to moles of NaOH, depending on which equivalence point you
selected in Step 1.

6. Using the mass of diprotic acid you measured in Step 1 of the procedure, calculate the molecular
weight of the diprotic acid, in g/mol.

7. From the following list of five diprotic acids, identify your unknown diprotic acid.
Diprotic Acid Formula Molecular weight

Oxalic Acid H2C2O4 90

Malonic Acid H2C3H2O4 104
Maleic Acid H2C4H2O4 116
Malic Acid H2C4H4O5 134
Tartaric Acid H2C4H4O6 150

8. Determine the percent error for your molecular weight value in Step 5.

9. Use your graph (and data table, if you printed one) to confirm the volumes you recorded in Box
10 of the Data and Calculations table (volumes of NaOH titrant before and after the largest
increase in pH values at the alternate equivalence point). Underline both of these data pairs on
the printed data table. Note: Dividing or multiplying the other equivalence point volume by two
may help you confirm that you have selected the correct two data pairs in this step.

10. Determine the volume of NaOH added at the alternative equivalence point, using the same
method you used in Step 2 of Processing the Data.

11. On your printed graph, clearly specify the position of the equivalence point volumes you
determined in Steps 2 and 9, using dotted reference lines like those in Figure 1. Specify the
NaOH volume of each equivalence point on the horizontal axis of the graph.
DATA TABLE
Mass of diprotic acid g

Concentration of NaOH mL

first equivalence point ——

1. Equivalence point (indicate which one you will use
or  
you will use in the calculations below)
second equivalence point ——

2. NaOH volume added before and after the largest

pH increase ______ mL ______mL    

3. Volume of NaOH added at the equivalence point

mL

4. Moles of NaOH
mol

5. Moles of diprotic acid, H2X

mol

6. Molecular weight of diprotic acid

g/mol

7. Name, formula, and accepted molecular weight of

the diprotic acid ___________ ___________ _______ g/mol

8. Percent error
%

first equivalence point ——

9. Alternate equivalence point (indicate the one used
or  
in the calculations below)
second equivalence point ——

10. NaOH volume added before and after the largest

pH increase
______ mL ______mL    

11. Volume of NaOH added at the alternate

equivalence point
mL

EXTENSION
Using a half-titration method, it is possible to determine the acid dissociation constants, Ka1 and
Ka2, for the two dissociations of the diprotic acid in this experiment. The Ka expressions for the first
and second dissociations, from Equations 1 and 2, are:
Ka1 = Ka2 =
The first half-titration point occurs when one-half of the H+ ions in the first dissociation have been
titrated with NaOH, so that [H2X] = [HX–]. Similarly, the second half-titration point occurs when
+
 Ka1 = [H+] Ka2 = [H+]

Taking the base-ten log of both sides of each equation,

logKa1 = log[H+] logKa2 = log[H+]

Thus, the pH value at the first half-titration volume,

Point 1 in Figure 3, is equal to the pKa1 value. The first
half-titration point volume can be found by dividing the
first equivalence point volume by two.

Similarly, the pH value at the second titration point, is

equal to the pKa2 value. The second half-titration
volume (Point 2 in Figure 3) is midway between the
first and second equivalence point volumes (1st EP and
2nd EP). Use the method described below to determine
the Ka1 and Ka2 values for the diprotic acid you
identified in this experiment.

1. Determine the precise NaOH volume for the first

half-titration point using one-half of the first equivalence point volume (determined in Step 2 or
Step 9 of Processing the Data). Then determine the precise NaOH volume of the second
half-titration point halfway between the first and second equivalence points.

2. On your graph of the titration curve, draw reference lines similar to those shown in Figure 3.
Start with the first half-titration point volume (Point 1) and the second half-titration point
volume (Point 2). Determine the pH values on the vertical axis that correspond to each of these
volumes. Estimate these two pH values to the nearest 0.1 pH unit. These values are the pKa1 and
pKa2 values, respectively. (Note: See if there are volume values in your data table similar to
either of the half-titration volumes in Step 1. If so, use their pH values to confirm your estimates
of pKa1 and pKa2 from the graph.)

3. From the pKa1 and pKa2 values you obtained in the previous step, calculate the Ka1 and Ka2
values for the two dissociations of the diprotic acid.