Preparation and Properties of Buffer Solutions Laboratory #11

Henry Ko AP Chemistry Dulaney High School February 3rd, 2009

Abstract:
In this experiment the pH of water and a number of solutions will be measured, and then acids and bases will be added to see how the pH is affected. Several buffer solutions of different pH values was prepared and tested for their ability to resist change in pH. a pH of 5 was prepared and was tested with strong acids and bases. When HCl was added, the pH did not change. When NaOH was added, the pH increased by 0.1.

Theory:
Buffers are solutions that resist changes in pH when an acid or base is added. In order to accomplish this, a buffer must contain both an acidic and basic component. These two components should not neutralize each other, but be available to neutralize hydrogen or hydroxide ions from other sources. One possible way to carry this out is to combine a weak acid-base conjugate pair. −− HA(aq) −− H+ (aq) + A – (aq) The acid dissociation constant expression for the reaction above would then be [H+ ][A− ] [HA] [HA] [A− ]

Ka =

or

H+ = Ka

(1)

If we take the negative logarithm of both sides, we have [HA] [A− ] [HA] [A− ]

− log[H+ ] = − log Ka − log

or

pH = pKa + log

(2)

Equation (2) is also known as the Henderson-Hasselbalch equation, and is frequently used to calculate the pH of buffers. By applying the Henderson-Hasselbalch equation, the equation for a basic buffer can be written as: [HA] [A− ]

pH

=

14 − pKb + log

(3)

Procedure:
In Part 1, twenty milliliters of distilled water is placed in a 100-mL beaker and its pH tested and recorded. Then, one 0.1 M of HCl is added and the pH is tested and recorded. The procedure is repeated with a second and third drop of 0.1 M HCl. Then, this process is repeated with 20 mL 0.1 M NaCl solution instead of distilled water. After that, the procedure is repeated with NaOH instead of HCl. In Part 2, a 100 mL graduated cylinder is set up with 10 mL of 0.1 M HC2 H3 O2 and 10 mL of 0.1 M NaC2 H3 O2 . The pH is recorded. One drop of 0.1 M HCl is added and then the pH of the mixture is recorded. A second and third drop is added, and the pH values after each drop is recorded. A new acetic acid-acetate buffer is prepared, and three drops of 0.1 M NaOH is added, with the pH recorded after each drop. A new buffer solution is prepared by combining 10 mL of 0.1 M NH3 and 10 mL of 0.1 M NH4 Cl in a 100-mL beaker. The pH values of 3 drops of HCl and NaOH (after each drop) is recorded with the new solution. In Part 3, 2.0 g of the solid acid sample is massed and dissolved in 150 mL of distilled water (in a 250-mL Erlenmeyer flask). Seventy-five mL of this solution is extracted into another 250-mL Erlenmeyer flask, along with 2 drops of phenolphthalein. It is then titrated with 0.2 M NaOH. Add the same volume of distilled water to the acid in flask 1 (weak acid) as the volume of NaOH you use to titrate the solution in flask 2. Combine 10 mL of the weak acid solution in flask 1 with 10mL of the conjugate base solution in flask 2. The pH is recorded and volumes of acid/conjugate base is mixed and tested with twenty mL of buffers with 3 drops of 0.1 M NaOH and HCl. 1

Data Analysis:
Part 1. pH Changes in Non-buffered Solutions Initial pH pH of distilled water 6.9 pH of 0.10 M NaCl 7.1 pH of distilled water 7.0 pH of 0.10 M NaCl 6.9 pH after Addition of Solution 1 drop HCl 2 drops HCl 3 drops HCl 3.9 3.6 3.4 1 drop HCl 3.9 1 drop NaOH 10.2 1 drop NaOH 9.8 2 drops HCl 3.6 2 drops NaOH 10.5 2 drops NaOH 10.2 3 drops HCl 3.4 3 drops NaOH 10.8 3 drops NaOH 10.5

1. 2. 3. 4.

Part 2. pH Changes in Buffered Solutions Initial pH pH of acetate buffer 4.5 pH of acetate buffer 4.4 pH of ammonia buffer 9.4 pH of ammonia buffer 9.3 pH after Addition of Solution 1 drop HCl 2 drops HCl 3 drops HCl 4.4 4.4 4.2 1 drop HCl 4.6 1 drop NaOH 9.3 1 drop NaOH 9.5 2 drops HCl 4.7 2 drops NaOH 9.3 2 drops NaOH 9.6 3 drops HCl 4.8 3 drops NaOH 9.2 3 drops NaOH 9.6

5. 6. 7. 8.

Part 3. Preparation of a Buffer of a Given pH Weak acid Mass of weak acid Volume of NaOH titrant pH of buffer solution pKa of weak acid Assigned pH Volume of weak acid solution Volume of conjugate base solution Measured pH pH Changes in Prepared Buffer Initial pH pH of prepared buffer 5.0 pH of prepared buffer 5.0 pH after Addition of Solution 1 drop HCl 2 drops HCl 3 drops HCl 5.0 5.0 5.0 1 drop NaOH 2 drops NaOH 3 drops NaOH 5.0 5.1 5.1 KHC8 H4 O4 2.026 g 26.5 mL 5.0 5.0 5 25 mL 25 mL 5.0

2

Conclusion:
In this experiment, the pH of water and a number of solutions will be measured , and then acids and bases will be added to see how the pH is affected. Several buffer solutions of different pH values was prepared and tested for their ability to resist change in pH. For example, a buffer of pH 5 was prepared, and when 3 drops of a strong acid, HCl, and a strong base, NaOH, was introduced, the pH did not change. With HCl, the pH did not change from 5.0. With NaOH, the pH did increase by 0.1 when 2-3 drops were added, but this change is not significant. Contamination was a large source of error in this experiment. Adding the wrong amount of acids or base could have dynamic effects on buffer equlibria. For example, because the pH scale is logarithmic, from one pH to another, there is one-hundred fold difference in the amount of hydrogen ions present. Therefore, this clearly makes a difference on the anions present when a buffer solution is made. Also, the accidental mixture of any solution that is not supposed to be in the buffer solution also changes the pH and the subsequent buffering system. This includes, but not limited to, the contamination of equipment used. For example, many beakers and graduated cylinders were used in this experiment. Therefore, unclean equipment could contain contaminants that could alter the pH. Or, on the other hand, washed equipment with distilled water introduces a neutral compound in the solution, which can also alter pH. This paradox forces the experiment to use consistant equipment, meaning that the entire equipment set must either be cleaned with distilled water, or left dry and risk the contamination of foreign material. Overall, this experiment was not very precise nor accurate. Precision was a problem because of the pH meter used was fluxuated between the measured values. For example, when tested in a sample of distilled water, the pH meter provided two different readings. Although both were within acceptable limits (6.9 and 7.0) this fluxuation can be expand to problems with more complex solutions such as the acetic or ammonium solution used in Part 2. Also, when placing drops of strong acid/base, the drops were not very consistant in terms of volume. This would give a different amount of acid or base in the solution, and the pH could vary depending on the amount added. Accuracy was also not guarenteed in this experiment due to the lack of accurate measuring tools. Most solution measurements were based on beakers or Erlenmeyer flasks, which do not provide an accurage gauge of volume. Also, the pH meter was also not very accurate, as sometimes it displayed clear inaccurate results. For example, the pH of distilled water was meausured at 5 at one point, which makes it very acidic for deionized water, clearly an error. This experiment can be improved by more accurate measuring equipement, like better pH meters or more accurate flasks. This way, more accurate measurements can be taken with a higher degree of confidence. Pre-Lab Questions: 1. The pH of a solution is measured to be 3.50. Calculate the hydrogen ion concentration. 1 × 10−3.5 = 3.16 × 10−4 M 2. Fill in the chart below with the formula of the missing conjugate acid or base. a. b. c. d. Conjugate Acid HC2 H3 O2 HCN – HSO4 – HCO3 Conjugate Base – C2 H 3 O 2 CN – SO4 2− CO3 2−

3. A buffer is prepared using the conjugate acid-base pair acetic acid and acetate ions. Write chemical equations showing the reactions that take place when H+ and when OH – are added to the buffer.

HC2 H3 O2 + OH− HC2 H3 O2

−− −− −− −−

H2 O + C 2 H3 O − 2 C2 H3 O− + H+ 2

4. Acetic acid has a Ka value of 1.8 × 10−5 . How many grams of NaC2 H3 O2 would have to be added to 100 mL of 0.10 M HC2 H3 O2 to prepare a buffer with a pH of 4.50?

3

4.5 −0.245 x x

= = = =

4.745 + log log

0.01 x

x 0.01 0.01 × 10−.245

0.00569

0.00569 × 82 ≈ 0.47 g Post-Lab Calculations and Analysis: 1. In step 1, how did the strong acid affect the pH of the distilled water? The strong acid lowered the pH of the distilled water because the concentration of H+ ions increased when HCl dissociates in H2 O. 2. Compare the pH values of steps 1 and 2. Did the addition of NaCl, a salt of a strong-acid-strong base, buffer the pH changes? Explain. No, the addition of the NaCl solution did not buffer the changes because NaCl is a salt, and is therefore, neutral in solution. In the experiment, the pH after 3 drops on HCl for both solutions was measured to be at 3.4, and therefore, did not buffer pH changes. 3. Compare the pH values of steps 1 and 3. How did the strong base affect the pH of distilled water? A strong base increased the pH of distilled water. For example, after 3 drops of NaOH, the pH of the water went from 7.0 (neutral) to 10.8 (basic). Compared to step 1, where a strong acid was used instead of a strong base, the pH decreased significantly to 3.4. 4. Compare the pH values of steps 1 and 4. Did NaCl, the salt of a strong acid-strong base, buffer the pH changes? Explain. The final pH measurement in step 1 after the addition of HCl was 3.4 while the final pH reading in step 4 after the addition of NaOH was 10.5. No, NaCl did not buffer the pH changes because the final pH of the distilled water solution and NaOH was 10.8. Since the pH of the distilled water and NaCl after the addition of the NaOH was approximately the same, it can be concluded that the NaCl did not buffer the pH changes. 5. Compare the pH values of steps 1 and 5. How did the acetic acid-acetate ion buffer affect the pH changes with HCl? Explain. Write a chemical equation to show the reaction of HCl with the buffer.
– −− H+ (aq) + C2 H3 O2 (aq) −− HC2 H3 O2 (aq)

The final pH in step 1 after the addition of HCl was 3.4 while the final pH in step 5 after the addition of HCl was 4.2, making the pH of step 5 to be higher than the pH of step 1. The acetic acid-acetate ion buffer affected the pH changes with the HCl by reacting the extra hydrogen ions from the HCl, which dissociated in solution, with the acetate ions present in solution at equilibrium to form acetic acid. This causes the total concentration of hydrogen ions, which was disturbed from equilibrium due to the addition of HCl, to establish a new equilibrium concentration in relation with the other ions/reactants in solution while keeping the overall pH of the solution constant by remaining constant concentration itself. 6. Compare the pH values of steps 1 and 6. How did the acetic acid-acetate ion buffer affect the pH changes with NaOH? Explain. Write a chemical equation to show the reaction of NaOH with the buffer. 4

– −− H+ (aq) + OH – (aq) + HC2 H3 O2 (aq) −− H2 O + C2 H3 O2 (aq) + H+ (aq)

The final pH in step 1 after the addition of HCl was 3.4 while the final pH in step 6 after the addition of NaOH was 4.8, making the pH in step 6 to be higher than that in step 1. The acetic acid-acetate ion buffer affected the pH changes with NaOH by reacting the hydroxide ions from NaOH with hydrogen ions already present in solution to form water, a neutral solution, However, the pH is kept constant due to acetic acid dissociating into acetate ion and hydrogen ion in order to compensate for the change of hydrogen ion caused by hydrogen ions reacting with the hydroxide ion. This keeps the overall hydrogen concentration of the solution, causing the pH to stay constant as well. 7. Compare the pH values of steps 1 and 7. How did the ammonia-ammonium ion buffer affect the pH changes with HCl? Explain. Write a chemical equation to show the reaction with HCl with the buffer. −− H+ (aq) + NH3 (aq) −− NH+ (aq) 4 The final pH in step 1 after the addition of HCl was 3.4 while the final pH in step 7 after the addition of HCl was 9.2, making the pH of step 7 to be higher than the pH of step 1. The ammonia-ammonium ion buffer affect pH changes with HCl by ammonia reacting with the extra hydrogen ions from the HCl, forming the ammonium ion, keeping the hydrogen ion concentration in solution the same as it was at equilibrium, resulting in the pH not changing drastically. 8. Compare the pH values of steps 1 and 8. How did the ammonia-ammonium ion buffer affect the pH changes with NaOH? Explain. Write a chemical equation to show the reaction with NaOH with the buffer. −− NH+ (aq) + OH – (aq) −− H2 O + NH3 (aq) 4 The final pH in step 1 after the addition of HCl was 3.4 while the final pH in step 8 after the addition of NaOH was 9.6, making the pH in step 6 to be higher than that in step 1. The ammonia- ammonium ion buffer affected the pH changes with the NaOH by forming water, a neutral solution. Water forms by having the hydroxide ions from the NaOH react with a hydrogen ion from the ammonium ion, resulting in ammonia and water. Since this effectively neutralizes the extra hydroxide ions from the NaOH without affecting the hydrogen ion concentration in the solution overall, the pH remains relatively constant. 9. Did your prepared buffer match your assigned pH value? Explain. Yes, the prepared buffer had a measured pH value of 5.0, which matched exactly with the assigned value of 5. 10. Comment on the ability of your prepared buffer to resist the change of pH when HCl and NaOH were added in step 25. Explain. The prepared buffer was able to resist changes in pH relatively well when HCl and NaOH were added. That is the case because the initial pH of the prepared buffer for both tests was 5.0. In the HCl test, the final pH of the solution was 5.0. Since the pH did not change upon the addition of hydrogen ions from the HCl, the buffer resisted change in pH well. In the NaOH test, the final pH of the solution was 5.1. Since the pH only increase by 0.1 by the addition of hydroxide ion from the NaOH, it can be said that the prepared buffer resisted change in pH well in this scenario as well.

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