CHE 282 EHp: Titration of a Polyprotic Acid

Objectives • To detennine the equivalence points in the titration of phosphoric acid, a triprotic acid, by a
mathematical analysis of the titration curve with a spreadsheet program

• To use the equivalence point data and detennine the Ka and pKa of the first two ionizations
of phosphoric acid and the concentration of the phosphoric acid used in the titration

Prior Reading Consult your textbook for a discussion of phosphoric acid and other common polyprotic acids
and their titration. Review the infonnation that you can obtain from acid-base titration curves.

Introduction In this experiment, you will titrate the triprotic acid, phosphoric acid (H3P04), with a
standardized solution of NaOH. The ionization of fuP04 occurs in a stepwise manner
represented by these ionic reactions:

fuP04 ;:::: H2P04- + W K aj =7.3 x 10-3 pKaj = 2.14

H2P04-;:::: HP04 - + W
2
Ka.z =6.2 x 10-8 pKa2 =7.21

HP042-+:! P04~ + W Kllj =4.2 X

13
10- pKllj = 12.38

Typical student data for titration of fuP04 with NaOH is shown below. [Note that the curve
represents actual data and is not as smooth as theoretical curves depicted in textbooks.]
Equivalence points, which occur at the midpoints of the vertical portions of the titration
curve, represent conditions in the titration in which the equilibrium positions for the
individual ionizations are greatly shifted toward the products for that ionization. For example,
the graph indicates that first equivalence point was reached by the addition of about 23 mL of
NaOH. At this point in the titration, the equilibrium position of the first ionization reaction
has shifted greatly in favor of H2P04- and W.

I
Titration of Phosphoric Acid I
14

12

10

8
P
H 6

0
0 5 10 15 20 25 30 35 40 45 50
Page 1 of 10 mL NaOH added
 The second equivalence point at about 45 mL represents the conditions where the second
equilibrium has shifted greatly in favor of the products HP04z- and W. Although you would
expect the titration curve to show three equivalence points for a triprotic acid, only two can be
determined for phosphoric acid by titration with concentrations of NaOH typically used. The
third ionization constant is extremely small, and the phosphate ion, pol-, is nearly as basic
as the NaOH used in titrations. Thus in this experiment, you will only obtain data pertaining
to the first two ionizations.

The moles of NaOH used to reach the first equivalence point also equal the moles of IhP04
present at the start of the titration. Combining this value with the volume in liters of the
IhP04 solution taken for the titration leads to the initial concentration of the acid.

The exact volume of NaOH required to reach the equivalence points is difficult to determine
from the titration curve of pH versus volume of NaOH added Applying the principles of
calculus, however, leads to accurate measurements of the equivalence point volumes. Careful
inspection of the titration curve reveals that the equivalence points occur at inflection points
along the curve. An inflection point is where the slope of a curve reaches a maximum and
changes from a positive to a negative value. The slope of the curve represents the change of
the y value divided by the change in the x value. In calculus terms; this ratio is called a f"mt
derivative. When this ratio (i.e., the first derivative) is plotted against the average x value
used in calculating the derivative, the graph appears with peaks at the equivalence points. This
graph is shown below.

I First Derivative Curve I

2.50

2.00

IJ.
P 1.50
H
/
IJ. 1 .00 -t.................................. ., ··f11······························ ,.. ·····1

0.50

0.00 -N~~~~-+----r-~~eC~---l.
o 5 10 15 20 25 30 35 40 45 50
Vmidpoint
Pat:e 2 of 10
 An even more accurate method to detennine the equivalence point volumes than using the first
derivative curve is to determine the second derivative of the data. In this graph, you
detennine the slope of the first derivative plot for each adjacent pair of values. The second
derivative plot shifts from high positive values to low negative values immediately before and
after the equivalence points. An equivalence point occurs where the slope of the second
derivative plot is zero. This graph is shown below. Note again that in all three curves there are
blips where the experimental points do not follow the theoretical curve. The exact volume at

I Second Derivative Curve I

2.50

2.00 -t ;......................................... ·jl····;······································ ; .

1.50

A 1.00
2
P 0.50
H

/ 0.00 ........I'\;;;t....~~.",..~H.........~~Ioif"l,. ...~=-=--+-1f-

A
V
2 -0.50

-1.00

-1.50

-2.00 ........._-'--_..I....-_.l....-_'----'_---'_---l._--'-_........_---'

o 5
10 15 20 25 30 35 40 45 50
Vmidpoint2

the equivalence points can now be determined accurately by using a ruler to measure and
calculate the volume on the x-axis where the curve crosses to zero value on the y-axis. In this
experiment, the equivalence point volumes were calculated to be 22.83 mL and 45.50 mL.

The general description of how you calculate the first and second derivative, and example
fonnulas to be entered into spreadsheet columns follow.

Consider three data points: (V I, pHI), 012. pH2)

ApHI,Z pHz -pH}
and (V3, pRJ). Thefirst derivative for points 1,2 =
is shown at the right. This value is plotted
AVI z . Vz-V I

against the volume halfway between VI and V2

VI + Vz
which is called Vmidpoint" Similar first derivatives Vmidpt = 2
are obtained between points 2,3 and 3,4.

Page 3 of 10
 The second derivative is calculated as
_ ApHlAV2,3 -ApHlAV1,2
shown between first derivatives 1,2 and
- Vmidpt2,3 - V rnidptl,2
2,3 as shown at the right. This value is
plotted against the volume that represents
the average between the midpoint __ V midptl,2 + V rnidpt2,3
V rnidpt2
volumes. 2

Experimental
Procedure

• Your instructor will indicate the size of the buret and other glassware and volumes of
reagents that you will use in this experiment.

• Calibrate a pH meter according to the instructions for the meter you are using.

• Rinse a buret with a few mL of standardized 0.20 M NaOH and then fill the buret with the
standardized 0.20 M NaOH.

• Set up the buret over a small beaker containing a stir bar on a magnetic stirrer. Position the
combination pH electrode in the beaker.

• With a pipet or graduated cylinder, add a measured volume of the phosphoric acid solution to
be titrated to the beaker. Your instructor will indicate the volume to be used. Make certain
that the pH electrode is immersed in the phosphoric acid solution (the porous plug
connecting the outer and inner electrodes must be under the surface of the solution being
titrated) and that the magnetic stir bar is not hitting the electrode.

• Record the initial pH of the solution on your data sheet. Then begin the titration by adding
O.5-mL increments of the NaOH solution with the magnetic stirrer turned on. Record the
pH after each addition.

• Continue adding NaOH and taking pH measurements until the pH has reached 12 to 13.

• Discard the completed titrated solution in the waste containers available.

• Repeat the titration two more times.

Page 4 of 10
Data Analysis

• Enter your data into a spreadsheet and construct the three plots indicated below. An example
of a portion of the spreadsheet follows the description of the graphs. Specific instructions
for use of a spreadsheet program (such as Excel) are not included in these instructions but are
available in computer services, in general books and manuals found in a college library or
on the internet.

• You will select the best set of graphs to submit with your report. For the calculations of
pK's and concentration of lhP04, you may use data from either the graphs submitted or an
average of values obtained from each titration.

• Graph 1 - pH versus mL NaOH Added

Construct a plot of pH on the y-axis versus the volume of NaOH ld:Ied (in mL) on the
x-axis. You will use this graph to determine pKa] and pKll2 after you have accurately
established the equivalence points.

• Graph 2 - First Derivative Plot (ApWAV versus Vmidpoint)

Use the calculation power of the spreadsheet program to determine the value of apWaV for
each pair of data points and the value of Vmidpoint as the average of the two volumes used.
Specific formulas are indicated on the attached format sheet

Construct a plot of apWav on the y-axis versus Vmidpoint on the x-axis. The peaks of this
graph correspond to the volumes of NaOH used to reach the equivalence points for the
titration of the first two hydrogen ion dissociations.

• Graph 3 - Second Derivative Plot(AZpH/AVZ versus VmidpoinU)

Use the spreadsheet to calculate the values of a 2pwaV2 using each pair of values of
apWav from graph 2. This value is plotted on the y-axis. The volume to be plotted on the
x-axis is the midpoint volume (called "midpoint2") between each pair of volumes used from
graph 2.

The volumes of NaOH required to reach the two equivalence points can be determined from
the values on the x-axis where the y value equals zero. Use a ruler to take accurate
measurements and then use the scale of your particular graph to calculate these volumes at
the equivalence points. You should be able to estimate the volumes to ±O.02 mL.

• Indicate these calculated volumes at the equivalence points on Graph 1. On the Graph 1 plot,
determine pKa] from the pH at one--half the volume required to reach the first equivalence
point. Determine pKll2 from the pH at the volume halfway between the two equivalence
points on the graph.

Page 5 of 10
 • Below is a recommended fonnat for your spreadsheetwith the formulas and axes indicated for
the three graphs. Also included are 15 typical data points with the calculated first and second
derivatives.

Example Titration

of

Phosphoric Acid with NaOH

... A- . . .
-_ ...• _.. B
-.,.- .- -- ". ~- ..... -- -_.-0
,- .. , ",_ .. ,_ .. , -.-._- .. -- E ",'",
F G H
Data First Derivative . Second Derivative
Vol NaOH (mL) . pH Vmidpt dpHIdV Vmidpt2 d2 pH/dV2
"X" "V" "X" II V" "X" "V"
(A6+A5)/2 (B6-B5)/(A6-A5) (07+06)/2 (E7-E6)/(07-06)
a 1.55
1 1.6 0.5 0.05
2 1.6 1.5 0.00 1 -0.05
3 1.65 2.5 0.05 2 0.05
4 1.7 3.5 0.05 3 0.00
5 1.75 4.5 0.05 4 0.00
.. "
6 1.85 5.5 0.10 5 0.05
7 1.88 6.5 0.03 6 -0.07
8 1.92 7.5 0.04 7 0.01
10 2 8.95 0.04 8 0.00
11 2.1 10.4 0.10 10 0.04
12 . 2.15 11.4 0.05 11 -0.05
13 2.2 12.4 0.05 12 0.00
14 2.3 13.4 0.10 13 0.05
15 2.38 14.45 0.07 14 -0.03

Page 6 of 10
 Titration of a Polyprotic Acid
Pre-Laboratory

Questions: Name:

Date:

1. Titration of 25.0 mL of a solution of citric acid (fuC6Hs07) required 15.3 mL of 0.150 M

NaOH to reach the first equivalence point of the titration. What is the concentration of the
citric acid solution?

2. If the pH at one half the first and second equivalence points of a diprotic acid is 4.20 and 7.34,
respectively, what are the values for K a ] and K a2?

.3. How many millimoles of NaOH would be needed to react completely with 50.0 mL of a
1.50 M solution of HZCZ04 (oxalic acid)?

Page 7 of 10
Data & Results
Name: _

Date: _ Lab Partner: ~~_

Titration ofPhosphoric Acid

Data Volume IhP04 taken: _ Molarity of NaOH used: _

Titration I Titration II Titration III

mLNaOH pH mLNaOH pH mLNaOH pH

Page 8 of 10
Data taken from Titration Graphs

A Volumes from second derivative graph:

volume in mL at first equivalence point

volume in mL at second equivalence point

B. pH values read on pH versus mL NaOH added graph

pH at first equivalence point

pH at second equivalence point

pH at Jh volume to first equivalence point

pH at Jh volume between equivalence points

Calculated K and pK values for ILP04 compared to literature values

Kat pKat Ka2 pKa2

Your Value

Literature Value

Calculated Concentration of ILP04 Solution

Molarity of lbP04
Graphs
Attach computer-drawn graphs of (1) pH versus mL NaOH added; (2) ApH/AV versus Vmdpt;
and (3) A2pH/AV2 versus Vmdpt2. Indicate equivalence points, pK values, and relevant volume
measurements used in caclulating the ionization constants.
 Titration of a Polyprotic Acid
Post-Laboratory
Questlons~ Name:

Date:

1. After a student determined the pK values of a H3P04 by titration, she realized that she had
recorded on her data sheet that the concentration of NaOH used in the titration was 0.25 M,
but her partner had filled the buret with 0.20 MNaOH. Would you expect the calculatedpK
values to be correct or incorrect? Explain your reasoning.

2. If you had made the same mistake as the student in question 1 above, what part of your
laboratory report, if any, would you expect to be incorrect? Explain your reasoning.

3. The volumes between successive equivalence-points in the titration of a polyprotic acid are
theoretically equal. Consider again the titration of citric acid (lhC6Hs07) as in question 1 of
the Pre-Laboratory Questions where a titration required 15.3 mL of 0.150 M NaOH to reach
the first equivalence point. How many mL of this base would be required so that the titration
solution was essentially a solution of sodium citrate (N~C6Hs07)1

Page 10 of 10