COMMON ION EFFECT AND BUFFERS

M. DELA CRUZ1, M. ESTRADA2 AND J. INSAO1

1National Institute of Molecular Biology and Biotechnology, College of Science
2Instituteof Civil Engineering, College of Engineering
University of the Philippines, Diliman, Quezon City 1101, Philippines
Date Submitted: 19 February 2019
Date Performed: 25 February 2019

ANSWERS TO QUESTIONS

1. Account for the differences in color of Solutions 1, 2, 3, and 4, after adding the appropriate
virtual indicators. Explain in terms of the pKas of phenolphthalein and methyl orange.

It’s important to recall that a buffer solution is described as either a weak acid and its
conjugate base, or a weak base and its conjugate acid. The two components in the buffer solution
allow the solution to neutralize both acids and bases present in the system, further allowing the
solution to resist changes in its pH [1]. Because two components affect the pH of a buffer solution, it
has its own solution, referred to as the Henderson-Hasselbach Equation. The log variable describes the
extent to which the pH of the solution changes, which would be compared to the pKa. Solutions 2 and
4, which are buffer solutions, will have a neutralizing component that will help deliver a minimal
change in the pH of acidic solutions. The minimal change in the pH means that the solution’s pH is still
close to the pKa of the indicator, hence the minimal change in the color of the solutions.

Methyl orange is an indicator for acidic solutions, and it has a pKa of 3.4. Solutions that are
more acidic will appear red, those that are more basic will appear yellow. Solution 1 turned into a red
solution upon the addition of methyl orange, hence it must be more acidic than the indicator, having a
pH lower than 3.4. The buffer solution for acetic acid, solution 2, had minimal changes to its color,
having an orange-yellow color, which is expected when the solution has a pH of more or less 3.4.
Because solution 2 had a conjugate base to neutralize the acid content of the solution, the pH is higher
than that of solution 1, and its pH was closer to the pKa of the indicator than solution 1 which was
completely an acidic solution.

For basic solutions, phenolphthalein is used as an indicator. It has a pKa of 9.4 and turns a
solution colorless when the solution has a pH less than the indicator’s pKa – or more acidic – and turns
into a more intense pink, whenever the solution is more basic. Solutions 3 and 4 were the basic
solutions tested, and solution 3 had an intense pink color because, it had a higher pH than 9.4, due to
the absence of a conjugate acid that would neutralize its basic property. Solution 4 turned into a faint
pink solution because it is more acidic than solution 1 and had a pH closer to the pKa of the indicator,
due to the presence of NH4Cl which helped neutralize the ammonia solution.

2. Describe and rationalize the observed effect of additional acid or base on Solutions 1, 2, 3,
and 4.
An important quality of buffer solutions is its ability to resist changes in pH, which is useful for
industrial purposes such as in the process of making beer, wherein an optimal pH range is requires for
enzymatic activity, and it is also useful for living systems, such as in the case of blood, which must be
maintained at a pH of 7.4 [1]. Adding hydrochloric acid to solutions 1 and 2 turned the solutions into
darker red upon the addition of hydrochloric acid, but solution 1 had a more intense color change, and
solution 2 was only slightly more orange. The result is because solution 2 had a conjugate base to
neutralize the additional H+ added to the solutions, while solution 1 did not. The pH meter also tested
the pH of the solutions, and solution 1 had a much lower pH when HCl was added, and a much higher
pH when NaOH was added. The addition of HCl and NaOH caused a decrease and increase in the pH
creating a pH range of 2.60-4.83. The pH of the buffer solution remained around 4.4 to 4.9.

Similarly for solutions 3 and 4, the buffer solution, 4, had a conjugate acid to react with the
additional OH-, hence it was able to resist an intense color change, unlike solution 3 which had turned
into a very intense pink upon the addition of NaOH. Solution 4 was still a faint pink. The pH meter
readings showed that solution 3 had pH range of 9.56 to 11.31, which was wider and pertained to a
more a basic system than the pH range of solution 4, 8.41-9.05. The buffer solution had acid molecules
to neutralize the basic property of the solution, hence the resistance to pH change and the overall
lower pH value of solution 4.

Buffer solutions also involve the common ion effect, that in which if a strong acid is added to a
weak acid buffer solution, then the reaction pushes to the direction relating to the formation of the
weak acid, thereby inhibiting the production of hydronium ions, which is in the opposite direction. The
same can be s aid for basic buffer solutions, wherein the strong base will push the reaction towards the
formation of the weak base and inhibit the production of hydroxide ions. These inhibitions are
expressed in the manner that the buffer solution would only have a slight change in pH because the
molecules are not dissociating to make acid or basic ions, but to form more of the weak acid or base
[1][2].

3. Compare the different methods of determining pH: visual indicators, pH meter, and
calculations. Compare the accuracy of the three methods.
Visual indicators involve the addition of a small amount of a weak acid or weak base that
change colors over different pH ranges. These indicators react with the acidic analyte or basic analyte
to form molecules that color or decolor the original solution, giving the researcher an idea of the
range of where analyte’s pH is. It usually describes the analyte in terms of it being more acidic or more
basic than the indicator, instead of giving an exact value [3].

The pH meter is a lab equipment that directly gives the value of the analyte’s pH, by
comparing the generated voltage of the analyte with a known generated voltage of a reference
solution contained in the reference electrode of the pH meter. The principle behind the pH meter
involves the exchange of ions through the porous glass membrane, and the generated electricity of the
exchanged ions in the electrodes of the pH meter. The pH meter must be calibrated before each run
and washed between analytes [4].

Calculations are done as a result from titration techniques which still involve the use of a
visual indicator. This method derives concentrations of acids or bases by measuring the volume of a
base or acid titrant that will neutralize the solution, or make it reach its endpoint that should
approximate the equilibrium point. Another way of calculating for the pH does not include external
factors, and just simply plugs values into the Henderson-Hasselbach equation as long as the
concentrations of the acids and bases, and the buffer solutions if needed, are known.

The purely theoretical calculations of plugging into the Henderson-Hasselbach equation is the
most accurate because it measures the pH in an ideal situation. In reality, pH determinations are done
with physical techniques, for which case, the most accurate would be the use of the pH meter because
as long as it is calibrated, then it is not as affected by errors like prejudice involving the color of the
solution and also because of the errors propagated by the additional use of more glassware in
titration.

4. What are the possible sources of errors and their effect on the calculated parameters?
Rationalize.
Dilution greatly affects the pH value of an unbuffered solution because the concentration of H+
ions changes, so if the solutions were improperly diluted then inaccurate measurements may appear.
Buffered solutions are minimally affected by dilution because the ratio of H+ ions to OH- ions is
retained [5]. Not washing the pH meter’s electrode with distilled water between the testing of each of
the analytes, a methodical error, may either decrease the pH value if the analytes are acidic, or
increase it, if the analytes are basic. Since the ions permeate through the glass membrane, some may
latch onto the electrode and stay there even in the next run. The ions that remain on the electrode will
also affect the voltage along with the new ions in the solution, thereby, causing the pH meter to read a
different voltage [4]. Not sealing or improperly sealing the acid-base analytes will also cause a change
in the pH, because carbon dioxide may react with water in the solutions forming acidic an acidic
compound, carbonic acid.

REFERENCES

[1] Petrucci, R. H., Herring, F. G., Madura, J. D., & Bissonnette, C. (2011). In General Chemistry:
Principles and Modern Application (10th ed.). Toronto: Pearson.

[2] Skoog, D. A., West, D. M., Holler, F., & Crouch, S. R. (2014). Fundamentals of Analytical Chemistry
(9th ed.). Belmont, California, United States of America: Brooks/Cole.

[3] Zumdahl, S. S., & Zumdahl, S. A. (2014). Acid-Base Indicators. In Chemistry (pp. 742-747).
Belmont: Brooks Cole.

[4] Bosche, J., & Schleicher, J. (n.d.). Critical Factors Affecting pH Measurement. Retrieved from
http://www.jumo.cn/media/PDFs/Press/whitepaper/JUMO_Critical_Factors_pH_Measure
ment.pdf

[5] Christian, G., Dasgupta, P., & Schug, K. (2013). Acid-Base Equilibria. In Analytical Chemistry (pp.
222-279). Danvers: John Wiley & Sons.