Lab experiment 3 Ka determination through pH titration.

Titrations to determine the concentration of an acid or base in solution are a well known analytical technique. This technique traditionally uses a visual indicator to determine the stoichiometric endpoint of analysis. The use of indicators, however, requires knowledge of the pH at the endpoint of the reaction, and thus knowledge of the acid being used. The traditional strong acid/strong base titration is quite simple and the salt solution formed is neutral. If a plot of the pH of a strong acid solute (e.g. HCl) titrated with a strong base (e.g. NaOH) were plotted as pH vs. volume of base added it would look like figure 1.

Figure 1 Titration curve of strong acid with strong base.

The endpoint is found half way up from where the graph curves up and where it curves to level out in this case at pH 7. The use of phenolphthalein for these titrations is possible because the color change occurs near this pH. For weak acid/strong base titrations the final pH will not be at a pH of 7, due to the formation of a conjugate base of a weak acid Figure 2. The salt formed can act like a base, and in the case of a diprotic system it could act like an acid itself Figure 2.

HA (aq) + NaOH (aq) A- (aq) + H2O (aq) HA- (aq) + H2O (aq) HA- (aq) + H2O (aq)
Figure 2 Weak acid/base equilibria

H2O (l) + A- (aq) OH- (aq) + HA (aq) OH- (aq) + HA (aq) H3O+(aq) + H2A (aq)

This being true knowledge of the Ka of the acid is needed to predict the pH of the solution at the endpoint if an indicator is to be used. However, if the titration is tracked by graphing pH vs. volume of the base added we can determine the endpoint in the same manner as with a strong acid/strong base system.

Figure 3 Titration curve of a weak acid strong base

Figure 3 shows a graph of the pH of a weak acid/strong base titration as you can see the half way point is now at around pH of 8.5 this is caused by the formation of the conjugate base which has a significant contribution of hydroxide from the equilibrium eq. 4. The expected pH can be calculated using the Kb expression assuming we know the concentration of the conjugate base, and the value of Kb.

Knowing the total volume of the system, the initial concentration of the acid, the amount of acid that has reacted with the base, and the Ka we can use the buffer equation (eq. 1) to calculate the expected pH up to the endpoint of the titration.

pH = pK a + log

[ A ] [ HA]

eq. 1

It is important to realize that if the base [A-] concentration is equal to the acid [HA] concentration then pH = pKa. This equation tells us that we can determine the pKa or Ka of an acid by finding the pH when half way to the endpoint of the titration! The same technique can be used when titrating bases with acids. In todays experiment we will determine the identity of an unknown diprotic acid. Diprotic acids have two deprotonation steps and thus will have two sigmoidal curves. The first curve will find the endpoint for the first deprotonation and the second endpoint for the second step. Using the half way point for each step Ka1 and Ka2 can be determined. Procedure 1. All experiments will be done with partners. 2. Obtain around 15 mLs, recording the actual volume, of the approximately 0.1 M unknown acid solution, and add it into a 100 mL beaker. Clean the pH probe and make sure the probe is under the surface of the solution. If not add 10.0 mL of distilled water and test again. 3. Obtain 100 mL of the approximately 0.1 M solution of NaOH. Make sure to note the exact molarity. 4. Rinse your burette with a small portion of the NaOH solution. Your TA will show you how to do this. Fill your burette to approximately zero noting the exact volume. 5. Place the pH probe into the unknown acid solution. Measure and record the pH. Your TA will demonstrate how to use the pH meter properly. 6. Using the burette add approximately 0.5 mL of the NaOH solution, recording the actual volume added, into the unknown acid solution. 7. Using your pH meter probe gently stir the solution, allow the system to settle and record the pH of the solution. 8. Repeat steps 5 and 6 until the pH starts to rise quickly. 9. When the pH starts to rise more rapidly reduce the volume added to approximately 0.2 mL, recording the actual volume added. Stir with pH probe and recording the pH of the solution. 10. When the pH levels off you may increase the volume addition to 0.5 mL recording the actual volumes and pH until the recorded pHs rise quickly. 11. When the pH again starts to rise quickly, reduce the additions to 0.2 mL recording the actual volumes and pH. 12. When the pH levels out again add three more 0.5 mL aliquots recording the volume and pH. 13. This should be repeated with another sample of the acid. Waste disposal: All of the titrated solution are should be collected into a properly marked waste bottle. Any excess NaOH solution should be neutralized with an equal volume of 0.1 M HCl, check using Litmus paper, and discarded down the sink.

Calculations: 1. Plot the pH vs. volume of base added 2. Determine the endpoint for the first and second deprotonations 3. Determine the concentration of the unknown acid solution 4. Using your graph determine Ka1 and Ka2 of the unknown acid 5. Your unknown acid can be 1 of 4 different acids. Oxalic, Malonic, Succinic, or Glutaric Acid. Using your Ka1 and Ka2 and the chemical literature, your TA could be very helpful, determine which acid you have. References are required, online references are not acceptable. Questions: 1. Using the Kas you determined experimentally, calculate the pH of a 0.055 M solution of your unknown acid dissolved in 175 mL of water.(assume the second ionization does not matter)

2. Using the Kas you determined experimentally, calculate the concentration of all the species present in solution( H2A, HA-, A-2, and H3O+) in a 0.055 M solution of your unknown acid dissolved in 175 mL of water. Is the assumption in question 1 valid?

3. The structure of the 4 possible acids is given below. pKa1 and pKa2 of Oxalic acid and Malonic acid are quite different from each other differing by ~3 or more pK units. While Succinic acid and glutaric acid have pKa values that only differ by ~1 pK unit. Give a reasonable explanation for this.
O O O O

HO

OH

OH

OH

oxalic acid
O

malonic acid
O

O O OH OH OH OH

succinic acid

glutaric acid