Eric Robinson, Section 02

Chem 254
Lab #4

Introduction
This lab is important because it expands upon the method of titrations as a means of
analysing a solution. Acid-base titrations like the one done here are useful for determining the
concentration of a weak acid/base by titrating strong acid/base into a sample.
A number of titrations were done in this experiment. The first set was done to determine
the concentration of the NaOH titrant. With this information, more titrations were done to
determine concentrations of citric or phosphoric acid in soft drinks. Finally, another set of
titrations was done in order to determine the concentration of phosphoric acid in an unknown
sample.
In order to get these concentrations, I titrated NaOH solution into my acid sample and
recorded the pH. A lot of these measurements were taken as I titrated small amounts and results
were graphed. By graphing the derivative of this curve, I found the equivalence points of each
titrations. The number of moles of NaOH added at the equivalence point is stoichiometrically
equal to the number of moles of acid present in the sample.
Considering the strong tastes of phosphoric and citric acid, I do not expect concentrations
of them to be very high in the soft drinks.

Methods.
First, my solution of NaOH was standardized. This was done by weighing by difference
four samples of KHP and adding to them about 25ml of water that was heated to remove CO2. In
each sample, a few drops of phenolphthalein were added. In one of these standardizing titrations,
pH was recorded with a pH meter as titrant was added. These values and their first derivative
values were graphed. Peaks on the first derivative graph indicate an equivalence point where the
moles of KHP and NaOH are equal. In making further calculations, I used the concentration I
determined graphically. This information was used to calculate the concentration of the NaOH
solution.
Now that the concentration of the titrant is known, it can be used to calculate
concentrations of a weak acid in various samples. About 400ml of Coca Cola and 400ml of 7-Up
were brought to a boil in beakers in order to remove as much carbon dioxide as possible. These
soft drinks samples were titrated into with NaOH and equivalence points were calculated by
looking at peaks in the first derivative plot. Three trials using Coca Cola and three trials using 7-
Up were done. Finally, three titrations of an unknown concentrated solution (A) of phosphoric
acid were done in order to determine the concentration of acid in the sample.
 The standard procedure was followed with one exception. I did three titrations to
standardize my NaOH before I remembered to do one using the pH meter. A titration using a pH
meter was done on the fourth sample however.

Results

Table 1. Standardization of NaOH solution by using KHP.

Mass KHP (g) Mol KHP Mol NaOH Vol NaOH (l) M NaOH (mol/l) M NaOH

0.5155 0.0025242 0.00252424 0.02352 0.107323068 (gotten

graphically)

0.8494 0.0041592 0.00415924 0.03865 0.107612938

0.5403 0.0026457 0.00264568 0.02463 0.107416818 I used this one in

further
calculations

0.3407 0.0016683 0.0016683 0.01542 0.10819059 0.1089

Mean M NaOH (using indicator) Standard Deviation %RSD

.1076 M

.0004
M

0.36%

OH Excess

Endpoint

Buffer Region
pH=pKa
Figure 1. Titration of NaOH solution into KHP samples.

Figure 2. First Derivative of NaOH Standardization Plot. Peak at 15.32ml.

The concentration of NaOH I calculated using the graphical method was slightly higher
than what I calculated using phenolphthalein indicator. This makes sense because in the titrations
using an indicator, the equivalence point actually occurs slightly before a color change is visible.
This is due to my limitation of being able to a very pale pink color. The calculated concentration
using indicator was 6.5% lower than the more accurate concentration gotten graphically. This is
a significant error and future titrations I do will probably be done with a pH meter. One reason I
might choose to use an indicator instead of a pH meter is the fact that it takes time to calibrate
the pH meter while using an
indicator is a lot faster.

OH Excess

Buffer Region
Endpoint
Buffer Region
pH=pKa
Figure 3. 7-Up Titrations Curves

Figure 4. First Derivative Plots of 7-Up Titrations. Peaks at 19.05, 17.30, and 17.6ml NaOH.
I noticed that series 1 took more NaOH solution than the others to reach its equivalence
point. I think this is due to the presence of carbonic acid from not boiling the sample enough.
Series 2 and 3 were definitely boiled long enough so they are the more accurate results.
The three pKa values for citric acid are all pretty close to one another, so only one
equivalence point was observable. This is when the following stoichiometric equation is true.
H3C6H5O7(aq) + 3NaOH(aq) 3H2O +Na2C6H5O7

This means the number of moles of citric acid will be a third of the moles of NaOH added
at the equivalence point.
Table 2. Calculated Concentrations of Citric Acid in 7-Up
Vol NaOH (Equ. M NaOH mol NaOH mol Citric Acid M Citric
Point) Acid

0.01905 0.01089 0.000207455 6.91515E-05 0.000692

0.0173 0.01089 0.000188397 0.000062799 0.000628

0.0176 0.01089 0.000191664 0.000063888 0.000639

 Mean Conc. (M) 0.000633

Standard Deviation 8E-06

%RSD 0.012157

I chose to not use the first trial of titration in the mean above because I believe it had a
substantial
amount of CO2
acting as an
acid to give me
a bad result.

OH Excess
Buffer Region
pH=pKa
Buffer Region Endpoint
H3PO4 pH=pKa
- H2PO4-
BufferHRegion
2PO4 Endpoint H1PO42-

pH=pKa

Figure 5. Titration of Phosphoric Acid in Cola

Figure 6. First Derivative of Phosphoric Acid Titration Curve

Table 3. Calculated Concentrations of Phosphoric Acid in Cola
NaOH Conc. Vol Eq. NaOH Mol NaOH Mol H3PO4 M H3PO4 Avg. M RSD

0.108 0.00685 0.000740 0.000740 0.0296 0.0296 0.015

0.108 0.00695 0.000751 0.000751 0.0300 Stdev. %RSD.

0.108 0.00675 0.000729 0.000729 0.0292 0.0004 1.5

My results indicate Veq22Veq1 which makes sense. At the first equivalence point, the first form
of phosphoric acid was in equilibrium with the singly deprotonated form, so it makes sense that
it would take twice as much volume to hit the second endpoint. It is only possible for Veq2<2Veq1
if there were deprotonated species before the titration began. If I were to titrate to the third
endpoint, Veq33Veq1 .

OH Excess

Buffer Region
Endpoint H3PO4
H2PO4-
Buffer Region

pH=pKa

Figure 7. Titration
Curve of an
Unknown
Concentration of
Phosphoric Acid
Figure 8. First Derivative Plots of Unknown A Titration. Peaks at 1.9, 1.85, and 1.9ml
NaOH.
Figures 7 and 8 are the results of the titrations of the unknown concentration of
phosphoric acid with NaOH.

Table 4. Calculated Concentrations of Unknown A Phosphoric Acid

Vol NaOH (Equ. M NaOH mol NaOH mol H3PO4 M H3PO4 Mean M RSD
Point)

0.00190 0.1089 0.000207 0.0000690 0.00276 0.00274 0.0153

0.00185 0.1089 0.000201 0.0000672 0.00269 Stdev %RSD.

0.00190 0.1089 0.000207 0.0000690 0.00276 .00004 1.53

Discussion
In terms of accuracy, using a well calibrated pH meter and graphing the results is the
better method of finding equivalence points. Because of the limitations of perceiving a color
change of the human eye, the observed endpoint of a indicator titration is after the equivalence
point of a titration. This is consistent with my results because the volume of NaOH delivered to
the endpoint calculated graphically is slightly but significant less than the volume delivered to a
visual endpoint. Another reason a pH meter is better than an indicator is in the case of titrating
into cola. It is not possible to see a color change in a dark liquid like cola so a pH meter is
necessary. However, a benefit of using an indicator like phenolphthalein is that it is much faster
than the graphical method. Also, if a pH meter is not correctly calibrated (which is sometimes
hard to do), the results could be wildly incorrect.
Another graphical method of determining the equivalence points would be to make a
second derivative plot. Points on this plot where the Y value is equal to zero would be
equivalence points. Using this method increases the accuracy of the results if many
measurements were taken.
 The following calibration curve was used to correct for measurements reported by the
buret and various volumes.
I reported the standard deviation of my sets of measurements to one significant figure.
This same decimal place of figure was the last digit I reported my averages to. When multiplying
volumes and molarities, I reported my answers to the same number as the least precise value.

Figure 9. The Calibration Curve Used to Correct for Buret Error

Conclusion
I calculated the concentration of my NaOH standard using the pH meter to be 0.1089
mol/L. This is slightly higher than the average concentration by using an indicator.
I found the calculated the concentration of citric acid in 7-Up to be 0.000633.000008
mol/L. This means in a 12 fl. Oz. can, there is approximately 43mg of citric acid.
I calculated the concentration of phosphoric acid in the cola sample to be 0.0296.0004
mol/L.
I found my Unknown A to have a concentration of 0.00274.00004 mol/L.
Evaluate and Expand
For the most part, I was happy with my results. However, I should have done another
titration for the 7-Up analysis because the first run was contaminated with carbon dioxide and
could not be used. I also could have been more careful around the equivalence points of my
unknown phosphoric acid samples and taken measurements at smaller increments. Regardless,
my results still hold up.