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Common-Ion Effect and Buffers The procedures in this experiment make use of pH indicators as gauges of the change in pH of weak

acids and bases and their ability to withstand a change in pH once integrated in a buffer solution. To understand the concept of common-ion effect and buffer solutions, samples of acetic acid, a weak acid, ammonia, a weak base and their respective buffer solutions, were reacted with hydrochloric acid and sodium hydroxide. The indicators phenolphthalein and methyl orange were used to indicate a change in pH effective upon a change in color in a certain range. Also, pH meters were used to gauge the actual experimental value of the pH of each solution. Using this, the experiment enables the researchers to distinguish between a buffer solution and other solutions in their ability to resist visible pH change. The indicators ability to display a change in color upon the reach of a certain pH range is due to the presence of ions with different colors upon reaction with a base or acid. Methyl orange, 4-dimethylaminoazobenzene-4'-sulfonic acid sodium salt, changes color in a color gradient of yellow to red upon changes in pH 4.5 and above to 3.1 and below respectively according to the chemical equation of H-MeOr(aq) H+ + MeOr-(aq), highlighted in the color form. Because of the gradient color change, it is appropriate for use in mid-strength acids and often in acid titration. Because the colors of both solution 1 and 2 were fairly similar, a light salmon-y color between red and yellow, it may be assumed that the pH of both solutions are in the middle of the range, 3.1<pH<4.5. However, because solution 1 appears slightly pinker than solution 2, it is presumably more acidic and possesses a lower pH due to the presence of more H-MeOr than MeOr-. Similarly, phenolphthalein, 3,3-bis(4-hydroxyphenyl)isobenzofuran-1(3H)-one, produces a gradient of a bright pink solution to a clear solution around a range of pH greater than 10 to pH less than 8.3 respectively. This gradient is produced by the reaction H-phph(aq) H+ + phph-(aq). This often allows the researcher to conclude that chemicals which appear clear upon addition of phenolphthalein are acidic and those appearing pink are basic. However, a colorless solution may also result from bases with pH greater 12 and a bright red solution from acids with pH less than 0. Because of this fact, phenolphthalein is more definitely able to distinguish pH ranges from 10 to 8.3 and is used for mid-strength bases like ammonia and in titration. Both solutions 3 and 4 appear bright pink with little difference indicating the presence of more phph- than H-phph. It can then be concluded that both solutions supposedly are of a pH greater than 10 and are basic. However, upon theoretical calculation as well as measurement using pH meters, solution 4 should supposedly have a pH less than 10 and thus a very light pink color. The discrepant results achieved may indicate a deficiency in the indicator, not the solution, as the pH meter readings support the theoretical values given by calculation. The results with respect to pH meter reading as well as computed theoretical values show that there is less of a change in pH upon the addition of a strong acid or base in solutions 2 and 4. Interestingly, the theoretical changes of pH in solutions 1 and 3 are equal, and those of solutions 2 and 4 are equal as well. Although the pH meter readings do not reflect the same numerical changes as the theoretical values, the trends remain the same throughout the solutions. Solutions 2 and 4 are buffer solutions, created to resist changes in pH due to the presence of either a weak acid and its conjugate base in the form of its salt or a weak base and its conjugate acid in the form of its sol. Because of the nature of weak acids or bases and common-ion effect, dissociation of a conjugate ion is negligible and the concentration of the conjugate ion is based purely on the concentration of the salt present. The addition of a common ion in salt form suppressed the dissociation of the ion in acid or base form. Upon the addition of a strong acid or base, the salt or the acid component of the buffer reacts, minimizing the change in pH at equilibria.

This process may be examined by looking at the generalized ionization equilibrium expression of a buffer solution. [ [ ][ ] ]

In an equimolar buffer such as the ones prepared in the experiment, K a = [H+] as the concentrations of the weak acid and its conjugate base cancel out. Looking at the same concept in terms of the Henderson-Hasselbalch equation, [ ]

[ ] it can be observed that unless the concentrations of the conjugate base and acid are unequal, pH = pK a and the pH of a buffer solution is totally dependent of the ratio of conjugate base and acid present at equilibrium. Therefore, as long as the addition of strong base or acid to the buffer solution is in a small amount compared to buffer components existent, the ratio remains close to one, resisting a change in pH. As a direct corollary, the higher the concentration of both the weak base/acid and conjugate base, the more buffering power it has to resist a change in pH. In solution 1, upon addition of a strong acid and base, the solution displayed a theoretical pH change of 0.59 or 0.60 from the control of 2.87, and an experimental pH change of 0.27 from the control of2.55, relatively large. The decrease of pH in 1a upon addition of HCl is accounted for by the increase of H+ ions in the solution due to the complete dissociation of HCl. The increase of pH in 1b upon addition of NaOH is due to the complete reaction of sodium hydroxide with acetic acid to form its conjugate base in the form of sodium acetate salt. This pH can be accounted for using the HH equation for the acetic acid and resulting salt formed. Because they are not equimolar, and are of small ratio, an increase in pH will be perceived. In solution 2, the buffering components react with the strong acid and base to limit the pH change. HCl reacts completely with OAc- to form HOAc and NaOH reacts completely with HOAc to form water and OAc-. Since only 1 drop of each strong component was added, the ratio of OAc- to HOAc stays very close to one, limiting the theoretical change in pH to 0.04 or 0.05 from the control of 4.74, and the experimental pH change to 0.03 or 0.05 from the control of 4.04, much lower than that of solution 1. The reactions are similar with respect to NH3. Like solution 1, solution 3 exhibited a theoretical pH change 0.59 or 0.60 from the control of 11.13, and an experimental pH change of 0.93 or 1.63 from the control of 10.47 upon addition of a strong acid or base. In 3a HCl reacted completely with NH3 forming its conjugate acid in the form of NH4Cl salt. The pH decrease and neutralization can be accounted for using the HH equation as a buffer component was formed. The increase in pH in 3b is accounted for by the increase of OH- ions in the solution. It is interesting to note that the pOH of 3a and 3b are equal to the pH of 1b and 1a respectively. In the NH3 and NH4Cl salt buffer in solution 4, the NH3 component reacts completely with HCl and the NH4+ component completely with NaOH. Like solution 2, because only one drop of a strong acid or base was added, the ratio of NH3 and NH4+ remains very close to 1, limiting the theoretical pH change to 0.04 or 0.05 from the control of 9.26 and the experimental pH change to 0.06 or 0.11 from the control of 9.24, still relatively smaller than its non-buffer solution 3. Theoretically, this buffer has the same buffering capacity as solution 2. From this experiment, the different forms of pH measurement and determination are mere estimates of what a solutions pH may be. Indicators, as stated earlier, estimate pH by the presence of ions which are of different colors. The problem with this method of pH determination lies with the fact that indicators don't change color sharply at one particular pH but rather

over a narrow range of pH, over a color gradient. As a reaction progresses, the presence of the ions which determine one color from another increase or decrease, creating conditions wherein there is no exact way of telling at which point a particular pH change actually occurs. Thus the pH determination of indicators like methyl orange and phenolphthalein are limited to a range of values and may thus be precise, but not entirely accurate. The quality of the indicator is also a factor, as seen by the discrepant experimental results of solution 4 with phenolphthalein. PH meters on the other hand, use voltage as estimates of pH. Operational amplifiers and inverting amplifiers similar to those found in ECGs are used to calibrate a voltage output to a certain pH reading based on the activity brought about by the ionization of different substances into hydrogen ions. The accuracy of a pH meter is based mostly on the accuracy of its calibration in the gain and offset of the voltage amplifier and inverting amplifier. In simple terms, the it is important that the voltage output of 0 is assigned to a true neutral calibration substance, or a substance of pH 7 and a separate voltage output to a pH of accurate known value as all subsequent readings are based on the offset specified by the calibration. The pH meter may be a potentially accurate determinant of pH given exact and accurate calibration and may yield values close to theoretic values if determinate errors are avoided in all other aspects. In the case of the conducted experiment however, values were somewhat skewed in the measurements, but were relatively close to the theoretical values attained by calculation. These discrepancies may be accounted for in the calibration of the pH meter. The neutral solution may not have been a true pH 7 solution, or determinate errors may have occurred in the calibration. The only values which were justifiably questionable were those of solution 3. Determinate errors in the preparation of solution 3 may have contributed to the discrepant readings. Theoretic values computed using the ICE table and Henderson-Hasselbalch equation give an accurate gauge of pH, provided that there are no determinate and errors. Because of the uncertainty present with regards to methodical errors, computed values should be treated as they are: theoretical. This means these should be used as comparative values to determine whether or not errors in experimental methodology or procedural discrepancies occur to account for deviations from theoretic computations. On the topic of errors, it has been discussed how errors in calibration may account for values other than those of the theoretically computed. If the neutral calibration was actually somewhat acidic, the pH meter records a lower pH as 7 in the voltage output and thus all readings are based on a neutral that is acidic, making readings more basic with a higher pH. If the neutral was somewhat basic, the opposite happens as well. Errors in solution preparation may also yield discrepant values. If the concentrations of acetic acid and ammonia are mistakenly higher than listed, pH and pOH are higher than theoretically calculated. The opposite occurs if the concentrations are lower. HCl and NaOH only contribute a significant discrepancy if the solution preparation was grossly misconducted as only 0.05 mL of each was used. In conclusion, indicators display changes in pH over a narrow range of pH values by means of a color gradient which is based off the amount of different colored ions which react with hydrogen ions present. Buffers effectively resist pH change because of the presence of a weak acid or base and their conjugate ions which react with strong acids or bases. In this case, the NH3 - NH4Cl salt buffer and the HOAc NaOAc salt buffer have equal buffering capacity. PH determination using indicators and pH meters are estimates of the true pH of a solution which may be taken as the theoretically computed values in the absence of determinate errors.

References: Chemguide (2009). ACID-BASE INDICATORS. Retrieved from http://www.chemguide.co.uk/physical/acidbaseeqia/indicators.html. Chemguide (2009). BUFFER SOLUTIONS. Retrieved from http://www.chemguide.co.uk/physical/acidbaseeqia/buffers.html. Chemtutor (2009). Acids and Bases. Retrieved from http://www.chemtutor.com/acid.htm. Masteron, W. L., Slowinski, E. J., Walford, E. T. (1980). Chemistry. New York: Holt, Rinehart and Winstron Publishers Morris, H. (1982). Foundations of College Chemistry (5th ed.). Monterey, California: Brookes/Cole Publishing Company. Roberts, J. L., Hollenberg, J. L., Postma, J. M. (1996). General Chemistry in the Laboratory (3rd ed.). New York: W. H. Freeman and Company.