pH, BUFFERS AND THE DISSOCIATION CONSTANT

INTRODUCTION The pH for a solution is determined from the definition pH = - log [H3O1+]. A simple graphic relationship between the hydronium ion concentration. A buffer is a solution that is resistant to changes in pH. The desired buffer pH determines what compounds are used to make buffer. To make a buffer with an acidic pH, (pH less than 7) the solution is made using a weak acid and a soluble salt of its anion. A buffer with a pH of 4.74 can be made using a equal volumes of 0.10 M acetic acid, HC2H3O2, and 0.10 M sodium acetate, NaC2H3O2. Typically the range for an acid buffer is centered around the value of the dissociation constant for the weak acid. The pH is adjusted by controlling the ratio of the moles of weak acid and the moles of soluble salt. The "recipe" for preparing buffers is illustrated below. A rule of thumb is that an acid buffer can be made using a weak acid and its salt. To make a buffer solution with a basic pH, (pH is more than 7) the solution is typically made using a weak base and a soluble salt of its cation. Buffers have at least two limitations. The natural pH range that matches the properties of the solute acid or base and the capacity of the buffer. One limitation depends on the equilibrium constant for the weak acid or base. The second comes from the limited solubility of the acids, bases or their salts. The amount of dissolved acid, base and salt determines the moles available in the buffer that can react with "added" acids or bases from the outside. BACKGROUND

DEFINITION pH is defined as the negative log of the hydrogen ion concentration of a solution.

pH = -log [H+]

INDICATORS Some common indicators and their color properties are given in the Table below: Indicator Methyl Violet Thymol Blue Methyl Orange pH range 0 to 2 1 to 3 3 to 5 Color Change yellow to violet red to yellow red to orange

Bromophenol Blue 3 to 5 Bromocresol 4 to 6 Green OBJECTIVE The objectives of the experiment are:

yellow to blue yellow to blue

Measure the pH of the unknown solution first with indicators and then with pH paper. Calculate the molecular weight of the unknown acid by titration, to determine its Ka using the pH meter and to measure its concentration in solution independently by stoichiometry and by pH measurement. Measure the pH of the unknown salt solution as obtained and with added Hal and NaOH to determine which of three possible salts it is. In this experiment you will: 1. Use a glass electrode with a meter to 2. Find the pH of a solution using indicators and pH paper a. Carry out pH titration's of a strong acid and a weak acid b. Determine the Ka of some weak acids c. Identify from pH properties a salt in solution 3. Determine the molecular weight of an acid by titration 4. Calculate the concentration of the acid in solution two ways: a. From the titration data. b. From the solution's pH data using Ka.

MATERIALS You will need the following apparatus for the experiment

1. pH meter and glass electrode. Have your instructor show you how to calibrate and use this instrument. 2. Fill your wash bottle with distilled water and use it to rinse the electrode after each use. Then gently blot the excess water off the electrode tip. 3. Small test tubes and a test tube rack

SAFETY ISSUES You are required to wear approved goggles at all times in the lab. Even if you are not working with any chemicals at the time, another student may splash a corrosive material. You may only remove the goggles when you are seated in the classroom part of the laboratory, away from the benches.

PROCEDURE This laboratory exercise can be divided into five experiments. They need not be done in any special order. 1. Measuring the pH of a solution using indicators and confirming your results with pH paper. 2. Doing a drop wise pH titration of HCl with NaOH 3. Doing a drop wise pH titration of acetic acid with NaOH 4. Weighing out an acid, dissolving it and titrating half of the resulting solution. Then measuring the pH of the original acid solution and a half-neutralized solution of the acid made by adding the neutralized solution to the original solution. Finally measuring the pH properties of the resulting buffer. 5. Measuring the pH of a salt solution and observing the pH changes with addition of excess HCl and NaOH. Finding the pH of your pH Unknown

1. Line up five clean 4-inch test tubes or sample tubes in your test tube rack. Add to each about 10 drops of your pH UNKNOWN. Then add to each, one-drop of indicator, a different indicator in each tube. Observe the colors and from the table, determine the approximate whole number pH of your pH UNKNOWN. Keep these tubes for comparison with the colors generated by known. 2. To several clean dry 4-inch test tubes add 10 drops of a solution having a known pH around that estimated for your unknown. Add one drop of one of the indicators that is in its color transition at the pH of the unknown. 3. From the colors of the known and the unknown you should be able to tell if your unknown has a pH higher or lower than the known pH. If the first known pH was slightly higher than the unknown, repeat the procedure with a second known pH that is slightly lower. Continue developing the colors until you can estimate your unknown pH to 0.1 pH units. (you should be within 0.3 units). Write this number on your data sheet and have the instructor circle and initial it. 4. Obtain from an instructor about 1 cm of pH paper in the correct range. With the instructors supervision, place some of your pH UNKNOWN on the paper using a clean stirring rod. 5. Use your 50ml beaker for this part of the experiment. Once you start this experiment, keep the meter continuously reading pH. When adding drops, try to make the size of the drops as even as possible. The drop size can be affected by the angle you hold the dropping bottle and rate of dropping. 6. Put 25 mL (Graduated Cylinder) of distilled water in the beaker. Go to a pH meter and follow the directions given under laboratory techniques to first calibrate the meter, then find the pH of the water. Swirl the solution being measured occasionally to maintain proper solution homogeneity at the electrode. The pH of distilled water may continue to drift but in any case get a reading in 30-60 sec. Read the meter to 0.01 pH units. Now add one drop of 1.0M HCl from the dropping bottle (next to the pH meter). Swirl the solution until the pH stops changing. At this point the meter should not be drifting. If it is, swirl the solution again and then read. Read the meter to 0.01 pH unit and record on your DATA SHEET in ink. Now add an additional 9 drops of the HCl. As before, swirl, read and record. This is the initial reading for your pH titration. 7. In the process of finding the dissociation constant of the ACID UNKNOWN, you will be able to calculate the ACID Unknown's molecular weight if you first weigh the amount of ACID UNKNOWN used to make the original acid solution. You will neutralize half of this original acid solution by titration.

Finding the Ka of the ACID UNKNOWN

Obtain from your instructor an ACID UNKNOWN containing 8-10 mill moles of a pure liquid or solid weak acid. 8. Rapidly weigh the acid on the analytical balance: weigh a clean, dry 125 ml flask. Weigh into it the entire contents of the sample tube. Record the weights to 0. 1 mg. 9. You will now make the original acid solution: dissolve the weighed acid in the 125 ml flask in 50 ml of distilled water. Measure the water in a graduated cylinder. Some of the ACID UNKNOWNS may require heating to get them into solution 10. Pour 25 ml of this solution back into the graduated cylinder for storage. (Note that this is half of the original solution). Add two drops of phenolphthalein indicator to the contents of the 125 ml flask. 11. Take a CLEAN, DRY flask to the stockroom and obtain about 50 ml of 0.2 M NaOH. The exact concentration will be given to you by the instructor. Fill your buret with the 0.2 M NaOH using proper analytical technique and titrate the acid in the flask carefully to a light pink end point. This should take less than one buret-full of base. Record the volume of NaOH used to .01 ml. Note: in steps 13 through 14 Once you start making your pH measurements, do not remove the pH electrode from solution or put the pH meter in standby; keep the meter in the pH mode while you make all your measurements. 12. Pour the 25 ml of original acid solution from the graduated cylinder into a clean, dry 150 ml beaker. (If the acid has crystallized out, you may have to heat it to get it back into solution. Cool it to room temperature to make the pH measurement.) Measure and record its pH. You may have to tip the beaker. Without removing the electrode from the solution, add the neutralized solution from the 125 ml flask to the beaker. Swirl. Recognize that this new solution is half neutralized. Measure and record its pH. 13. Without removing the electrodes from this solution, complete the measurements given on the data sheet in #7. Use the dropping bottles of 1.0M HCl and 1.0 M NaOH next to each pH meter. Recognize that in #7b, you are adding just enough base to neutralize the excess acid added in #7a. 14. Now carry out the measurements in #8 using your 50 ml beaker with 25 mL of a solution obtained from the STOCKROOM. The effect of adding 1M HCI and/or NaOH to this solution should contrast with that observed for the buffer in #7. From its behavior, you are to identify the salt in this solution as: Ammonium Chloride, Sodium Acetate, or Sodium Sulfate.