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COMMON-ION EFFECT AND BUFFERS RESULTS AND DISCUSSION REPORT IN CHEM 26.1 SUBMITTED BY CLARICE MAE B.

DACASIN
C. M. B. DACASIN
DEPARTMENT OF FOOD SCIENCE AND NUTRITION, COLLEGE OF HOME ECONOMICS UNIVERSITY OF THE PHILIPPINES, DILIMAN QUEZON CITY 1101, PHILIPPINES DATE SUBMITTED: 10 DECEMBER 2013 DATE PERFORMED: 28 NOVEMBER 2013

INTRODUCTION Our bodies are able to take in and store strong acids and strong bases (e.g. HCl in stomach). This is because our body provides a way as to not drastically change the pH and damage itself. Bodies use buffer solutions, a combination of compounds, to keep the pH at a narrow range [1]. A buffer solution contains a conjugate acid-base pair with both the acid and base in reasonable concentrations [1]. In this experiment, the difference between a pure solution and a buffer solution according to pH changes would be observed. Concepts of the common-ion effect and buffer solutions would be applied in this experiment. Four solutions were prepared for the first part of the experiment. These solutions were: (Solution 1) 30 mL 0.10 M CH3COOH; (Solution 2) 15 mL 0.20 M CH3COOH 15 mL 0.20 M NaCH3COO; (Solution 3) RESULTS AND DISCUSSION Table 1. pH using Visual Indicators and pH meter. Color of Solution + Methyl Orange 1 2 3 4 Red Yellow + Phenolphthalein Dark Violet/ Fuchsia Faint Violet 3.46 4.58 10.46 9.07 30 mL 0.10 M NH3; and (Solution 4) 15 mL 0.20 M NH3 15 mL 0.20 M NH4Cl. A drop of methyl orange indicator was then added to Solutions 1 and 2. The changes in color were then observed, compared, and recorded. Consequently, for Solutions 3 and 4, a drop of phenolphthalein indicator was added. The changes in color were also observed, compared, and recorded. For the second part of the experiment, each solution from the first part was separated into three equal portions. For the first portion of the solution (a), three drops of 1.0 M HCl solution were added; for the second portion (b), three drops of 1.0 M NaOH were added; and, for the last portion (c), the third portion, nothing was added since it served as a control or basis of change.

Solution

pH Reading

For the first part of the experiment, methyl orange indicator was added to Solutions 1 and 2. Methyl orange indicator is an acid-base indicator that oscillates between colors red to yellow depending on

the pH value [4]. The transition range for this indicator is around 3.1 to 4.4 (acceptable up to 4.5), wherein leaning towards the former (more acidic) would result to a change of color to red while if the pH value is

closer to the latter (more basic), then it would result to a change of color to yellow [5]. According to the results of the actual experiment, there were no discrepancies up to this point. In solution 1, the hydrolysis of the weak acid (HOAc) is given by this equation, CH3COOH + H2O CH3COO- + H3O+ (1)

[2]. To reverse the given reaction, H3O+ ions are used up. By this, the dissociation of CH3COOH is suppressed or inhibited. Upon calculation for the ideal pH of this buffer solution, it is appropriate that the HendersonHasselbalch equation, which is used to calculate the pH of buffer solutions, (3) be used [6], given by the equation, ( ) (3)

By looking at the equation, CH3COOH partially dissociates to produce H3O+ (hydronium) ions. These hydronium ions would account for a certain pH. Due to the production of H3O+ ions being unobstructed, a reaction with the indicator would be shifted to the left, according to this equation, HInd + H2O H3O+ + Ind(2)

The reaction with the indicator is shifted to the left because when the solution exhibits a color, in this case the color is between red, the HInd form predominates (the Ind- predominates if the color is yellow). And since HInd is in the left side of the equation, the reaction would be shifted to the left. The pH reading justifies this, having a pH of 3.46 which is in the range of the indicator. Upon calculation for the ideal pH of this solution, a pH of 2.87 is obtained by the usage of the I.C.E. (InitialChange-Equilibrium) table and the acid dissociation constant of HOAc (Ka = 1.8 x 10-5). Theoretically, the solution should have had a deeper red color than a plain red color (near to salmon pink). On the other hand, Solution 2 is a buffer solution, comprised of a weak acid and its soluble ionic salt. Solutions with weak acids and their soluble ionic salts are always less acidic than a solution containing the weak acid alone [2]. This indicates that, by comparison, solution 2 is expected to have a much higher pH than solution 1. In solution 2, compared to solution 1, there is an additional source of CH3COO- ions from NaCH3COO. Due to the excess amount of ions, equilibrium is shifted to the left since there was a need to overcome stress and re-establish equilibrium as stated by the common-ion effect. When a solution of a weak electrolyte is altered by adding one of its ions from another source, the ionization of the weak electrolyte is suppressed; that behavior is the common-ion effect

By using the given equation, it yields an ideal pH of 4.75. Because H3O+ ions were used up, there was a lack of it and causes a rightward shift in equation (2). Having a rightward shift makes the Ind- form to predominate, thus, resulting to a yellow color (in this part of the experiment). In the actual experiment, the pH was less than the ideal (4.58) but was still in the range wherein yellow color is exhibited. Phenolphthalein is known to be the most common acid-base indicator used [3]. It has a range of transition between 8.3 and 10.0, wherein a pH value closer to the former value would yield a colorless solution while a pH value nearing the latter would exhibit a fuchsia/ violet color of the solution. The chemical equation for Solution 3 is as follows, NH3 + H2O NH4+ + OH(4)

The hydrolysis of NH3, which is a weak base, produces OH- ions, which correspond to a specific pH value given by this equation, pH = 14 pOH (5)

The calculated pH value (considered as ideal pH), by manipulation of the I.C.E. table, the base dissociation constant for NH3 and equation (5), is found to be 11.13. Since this value is near 10.0, the color of the solution should have a fuchsia or dark violet color. This is supported by the actual experiment, which had a dark violet colored solution. Solution 4, like Solution 2, is a buffer solution comprised of a weak base and its soluble ionic salt. Solutions containing weak bases and their ionic soluble salts are always less basic than solutions with

weak bases alone. By that fact, a pH value lower than that of solution 3 is expected. A modified version of the Henderson-Hasselbalch equation (3) suitable for a solution comprised of a weak base is to be used to find the pH of this solution,

(6)

Using both equation (6) and equation (5), the calculated ideal pH value of the solution is 9.25. The solution is expected to have a light violet color. Experimentally, the solution also had a light violet color which verifies with theoretical expectations.

Table 2. Effect of Strong Acid and Strong Base on Buffers. Estimated pH range pH Reading Solution a b c a 2 b c a 3 b c a 4 b c c is the control 1 + Methyl Orange pH < 3.1 pH > 4.5 3.1 < pH < 4.5 pH < 4.5 pH > 4.5 pH > 4.5 + Phenolphthalein pH < 10.00 pH > 10.00 pH > 10.00 8.3 < pH < 10.00 8.3 < pH < 10.00 8.3 < pH < 10.00 pH meter 2.35 3.87 3.46 4.40 4.70 4.58 9.89 11.56 10.46 8.97 9.28 9.07 Calculated 2.30 3.47 2.87 4.70 4.80 4.75 10.53 11.70 11.13 9.23 9.30 9.25

In the second part of the experiment, for solutions 1 and 3, it is expected that the pH would drastically change (rise or fall) from the addition of drops of strong acids and bases since they are not buffer solutions. They are pure solutions of weak acids and bases without much capacity to counteract additional stresses, unlike solutions 2 and 4 which are buffer solutions that are expected to negate or minimize pH changes. In solution 1a, the addition of HCl follows a special case of Le Chateliers principle, the Common-ion effect. This is when a weak electrolytes dissociation is suppressed by the addition of one of its ions from another source [5]. In this solution, the common ion is H3O+. Suppression would cause the formation of hydronium ions from the acid source, CH3COOH, to be negligible. Because of this, majority of the hydronium ions would come from the addition of 1.0 M HCl, CH3COOH + HCl CH3COO- + H3O+ (7)

For solution 1b, a neutralization reaction occurred given by the following chemical equation, CH3COOH + NaOH NaCH3COO + H2O (8) The neutralization would cause some CH3COOH to be consumed in the production of a salt, NaCH3COO. Ideally, this would cause a lowered hydronium ion concentration due to the presence of the common ion, CH3COO-, from NaCH3COO, causing a leftward shift in the equilibrium. Equation (3) can then be used to calculate for the new pH. The changes in pH for solutions 1a and 1b are -0.57 and +0.60 respectively. Solutions 2a and 2b follow a similar course as that of the divisions of solution 1. But because this is a buffer solution, the change in pH level is different, or lowered to some extent. NaCH3COO completely dissociates into Na+ and CH3COO- but CH3COOH undergoes partial ionization only. Because of the common ion CH3COO-, there will be minimal change of pH in the solution compared to solutions 1a and 1b. CH3COO- will react with HCl, a strong acid, for

solution 2a while CH3COOH will react with NaOH, a strong base, for solution 2b. For solution 3a, it is a neutralization reaction with the following expression, NH3 + HCl NH4Cl (9)

The formation of NH4Cl, a salt of the neutralization reaction, would add a source for common ions in the hydrolysis reaction given by equation (4). This would lead to a decrease in OH- ions due to the leftward shift of the reaction. Solution 3b is another case of the common-ion effect, this time with OH- as the common ion. Its addition would increase the pH due to the reformation of the base by the leftward shift. The change in pH solutions SUMMARY AND CONCLUSIONS For the results, pure solutions of weak acids and bases have shown to have no resistance in change of pH level when a strong acid or base is added, with a change in pH level almost nearing 1.0. Buffer solutions, on the other hand, have proven to be effective at resisting the change of pH, even avoiding drastic changes to pH. Having a buffer solution which resists the change in pH, the pH level is changed to at most 10-1 of the change in pH level of the pure solution. Due to experimental errors in solution preparation, there might have been slight inconsistencies with pH level change but it is not at all extreme. The experimental pH values might have been deviated due to the inconsistency in molarity produced and volume added of the solutions. Depending on molarity and volume change, this would have led to an increase or decrease in pH level. REFERENCES [1] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole, Cengage Learning. 742. [2] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole, Cengage Learning. 743.

3a and 3b are -0.60 and +0.57 respectively. Solutions 4a and 4b follow a similar course as that of the divisions for solution 3. Again, change in pH level is minimal compared to solutions 3a and 3b because solution 4 is a buffer solution. For solution 4a, the H+ ions from adding HCl reacts with NH3 producing more NH4+. And for solution 4b, the OH- ions from adding NaOH reacts with NH4+ to form NH3. From the results in table 2, pH meter results and calculated pH results are slightly different. This is due to experimental errors and the accuracy of the used pH meter. Even so, when adding an acid, it should lower the pH level and when adding a base, it should increase the pH level. For the results in the experiment, there were no abnormalities in the trend and the said trend was followed.

Aside from that, the pH level could be also altered when the pH meter was used. The pH meter, a sensing mechanism, may have been contaminated. By contaminated, it may not have been thoroughly washed or cleansed with distilled water thus, leading to slight inaccuracy. If contaminated with an acid, it might have led to a lower reading and if it was with a base, a higher reading. Overall, the experiment was a success. There were slight errors but since three methods in calculating for the pH level were used (calculations, visual indicators, and pH meter), the results from these methods were compared and each result verified each other. It is recommended that, if this experiment were to be repeated, careful solution preparation and thorough cleaning of containers and the pH meter should be advised.

[3] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole, Cengage Learning. 755. [4] Whitten, K.; Davis, R; Peck, M.; Stanley, G. Chemistry 8th ed. 2010. Belmont, CA: Brooks/Cole, Cengage Learning. 757.

[5] Harris, D. Quantitative Chemical Analysis 8th ed. 2010. Madison Avenue, NY: W.H. Freeman and Company. 221. APPENDIX A Sample calculations: pH of Solution 1 : 0.10 M HOAc Initial Change Equilibrium CH3COOH 0.10 -x 0.10 - x CH3COO0 +x x +

[6] Skoog, D.; West, D.; Holler F.J.; Crouch, S.R. Fundamentals of Analytical Chemistry 8th ed. 2004. Belmont, CA: Brooks/Cole, Thomson Learning. 252.

H+ 0 +x x

H+ is from H3O+ = H2O + H+ (MH2O is negligible) [ ][ ] [ ] [ ]

pH of Solution 2 : 0.20 M HOAc 0.20 M NaOAc ( ( pH = 4.75 pH of Solution 3 : 0.10 M NH3 Initial Change Equilibrium NH3 0.10 -x 0.10 - x [ [ [ ] ][ ] NH4+ 0 +x x ] + OH0 +x x ) )

pH for Solution 4 : 0.20 M NH3 0.20 M NH4Cl ( ( pOH = 4.744727495 pH = 14 4.744727495 pH = 9.25 ) )

APPENDIX B Guide for Discussion Compare the different methods of determining pH: visual indicators, pH meter, and calculations. Compare the accuracy of the three methods. Calculations are generally the most reliable out of the three methods. The values used and the equations are widely accepted by the scientific community. The results of these equations should, therefore, yield the ideal pH values. Even so, experimental results are still encouraged to be done as to verify the calculations. A pH meter is more dependable than a visual indicator in terms of finding the definite quantitative value of the pH. The pH meter is calibrated enough to find an accurate pH value for a solution of substance. Visual indicators are unreliable because color interpretation is subjective and differs from person to person. pH cannot be accurately determined under a subjective basis. Even so, the pH meter could also have deviating pH values. These deviant values or extremes could be brought about by contamination by the atmosphere that surrounds the device.