Titrations Revisited

By Drew Rutherford Concordia College

Introduction
The first experiment today will be the titration of acetic acid in vinegar. Vinegar is a solution of acetic acid, an organic acid of formula CH3COOH (MW = 60.0526 g/mole). In order to be sold as vinegar, it needs to meet the FDAs guideline of 5.00% acetic acid by mass. Knowing that the density of vinegar is 1.04 g/mL and analyzing this solution by titration, chemists can determine the mass percentage of acetic acid in a sample of vinegar. The titration reaction is given below: CH3COOH + NaOH CH3COONa + H2O Reaction 1

A customer has purchased a vinegar solution at a local thrift store at a 20% discount and he believes that the sample of vinegar he has purchased does not meet FDA regulations. He is suing the thrift store for the $0.36 he feels that he has been cheated out of. The court has asked you to analyze the sample and render your verdict. Does this sample conform to the FDA guideline? If 2.00 mL of the thrift store vinegar required 9.73 mL of 0.150 M NaOH to reach the endpoint, then 0.00877 g of acetic acid was present. 9.73 mL NaOH x 1 liter NaOH x 0.150 mole NaOH x 1 mole CH3COOH x 60.0526 g CH3COOH 1000 mL 1 liter 1 moles NaOH 1 mole CH3COOH = 0.0876 grams CH3COOH in sample 2.00 mL vinegar x 1.04 g vinegar = 2.08 g vinegar 1 mL 0.0876 g CH3COOH x 100 = 4.21 % CH3COOH by mass 2.08 g vinegar sample You can find the molarity of acetic acid in vinegar by dividing the number of moles of acetic acid in vinegar by the volume of vinegar used. Molarity of CH3COOH = 0.00146 moles CH3COOH 0.00200 L Molarity of CH3COOH = 0.73 M The thrift store vinegar does not meet the FDA guidelines.

The second experiment today will be the determination of the mass percentage of sodium carbonate in a mixture. This procedure will use a powerful variation of titration technique called back-titration. This method is often employed to analyze unknown samples of bases. This technique utilizes a standardized acid to overneutralize the unknown base sample. After the sample of base has been overneutralized, a standardized base is added from the buret to the solution to titrate the excess acid that was added. Since the total number of moles of added acid are known and the excess acid remaining after complete neutralization of the unknown base can determined by titration, one can determine the number of moles of bases present in the analyzed sample by the difference between total number of moles of acid added and the number of moles of acid remaining after neutralization. It is critical to the back titration technique to be certain to add too much standardized acid to the unknown, but not so much that the excess acid remaining cannot be titrated by the total capacity of one buret of standardized base. For example, if 30.00 mL of a 0.200 M HCl solution was added to a 0.225-g sample of a mixture of sodium carbonate and lithium chloride, the acid-base reaction between the HCl and the Na2CO3 results in the production of sodium chloride, water and carbon dioxide (see reaction below). The lithium chloride present in the original sample does not affect the acid/base reaction. Note: Carbonic Acid (H2CO3) is unstable in solution and will spontaneously decompose to water and carbon dioxide. 2 HCl + Na2CO3 2NaCl + H2O + CO2Reaction 2

If the 0.225-g sample was completely sodium carbonate (MW=105.99), the balanced equation indicates that we would need 0.00425 moles of HCl to react with the sodium carbonate. STEP 1: 0.225 g Na2CO3 x 1 mole Na2CO3 x 2 moles HCl = 0.00425 moles HCl 105.99 g Na2CO3 1 mole Na2CO3

How many milliliter of our standardized 0.200 M HCl solution (that we made last week in lab) should we add to the sodium carbonate? STEP 2: molarity = mole Liters 0.200 M = 0.00425 moles HCl liters 0.0213 liters or 21.3 mL However, we added too much HCl to the solution. We added 30.00 mL of HCl. After the reaction is complete, what remains in the flask? 1. 2. 3. 4. Sodium chloride (NaCl) Lithium chloride (LiCl) Water (H2O) Excess HCl that wasnt needed for the reaction

The excess HCl remaining in this solution can then be titrated (back-titration) with a standardized sodium hydroxide solution and the number of moles of excess acid determined. The reaction during the back-titration is

HCl + NaOH NaCl + H2O

Reaction 3

If the solution required 16.22 mL of 0.150 M NaOH to reach the endpoint, there were 0.00240 moles of HCl left in solution (the excess). Step 3: 16.22 mL x 1 liter x 0.150 moles NaOH x 1 mole HCl = 0.00243 moles HCl 1000 mL 1 liter 1 mole NaOH

How many moles of HCl did we add to the solution? We added 30.00 ml of 0.200 M HCl. Step 4: 0.200 M HCl = moles HCl 0.03000 L 0.00600 moles HCl A total of 0.00600 moles of HCl was added at the beginning. The excess amount of HCl (the amount not used in the reaction of HCl with Na2CO3) was 0.00243 moles HCl. Step 5: HCl 0.00357 moles HCl used in reaction with Na2CO3 Reaction 2 shows the stoichiometry of the reaction of HCl with sodium carbonate. Step 6: 0.00357 moles HCl x 1 moles Na2CO3 x 105.99 g Na2CO3 = 0.189 g Na2CO3 2 moles HCl 1 moles Na2CO3 total moles HCl = moles HCl used in reaction with Na2CO3 + excess HCl 0.00600 moles = moles HCl used in reaction with Na3CO3
+

0.00243 moles

The amount of sodium carbonate in the 0.225 g mixture was only 0.189 g. The remaining mass was lithium chloride. Step 7: % Na2CO3 = 0.189 g Na2CO3 in sample x 100 0.225 g total sample mass % Na2CO3 = 84.0 %

Experiment
General Comments Use only deionized (DI) water for this (and any titration) lab. Once a titration is started, it is important that the volume of titrant in the buret is sufficient to determine the endpoint for the trial without refilling the buret. Refilling a buret in the middle of a titration will introduce significant errors in measurement. Be sure to completely close the KHP container to prevent KHP from prolonged contact with the air. The endpoint of phenolphthalein is colorless to light pink (acidic solution to basic solution). The endpoint of 2:3 methyl red:bromocresol indicator is light pink to light green. The complete transition is from light pink (sometimes tannish) to light green to light blue (acidic solution to basic solution). It is sometimes difficult to see the green endpoint since one-half a drop over will give the blue color without observation of the light green intermediate. Methyl red indicator changes from red to yellow (pKa = 5.4) while bromocresol green indicator changes from yellow to blue (pKa = 4.7). The combination of methyl red/bromocresol green indicators gives pink (red plus yellow in acidic solution) to green (yellow plus blue basic solution) at the endpoint. In the back titration, in order to ensure complete reaction between the HCl and the sodium carbonate and to drive off all carbon dioxide, the reaction solution is heated to boiling on a hot plate for 3 minutes and cooled to room temperature before the titration is conducted. Sodium hydroxide solutions react with carbon dioxide from the air over time. This reaction changes the concentration of standardized solutions of NaOH slightly. In order to obtain the most accuracy, your sodium hydroxide solution should be restandardized against KHP.

Restandardize your NaOH solution: Follow the method from last week to restandardize your NaOH solution against KHP. Titration of Vinegar: Obtain 10-15 mL of vinegar sample in clean, dry 50-mL beaker. Transfer 2.00 mL of vinegar sample to a 125-mL Erlenmeyer using a volumetric pipette. Dilute with 30-40 mL of DI water. Use 3 drops of phenolphthalein indicator and titrate with your standardized sodium hydroxide solution from last week. Repeat at least three times. Calculate the molarity of acetic acid in the vinegar and the mass percentage of acetic acid. Comment on whether the vinegar sample conforms to FDA standards.

Back Titration of Na2CO3/LiCl Mixture: Weigh out 0.200-0.250-g of the Na2CO3/LiCl unknown mixture and transfer completely to a dry, 125-mL Erlenmeyer flask. Calculate the amount of your standardized HCl solution you would need to neutralize the sample if it was completely sodium carbonate and add 2 extra milliliters of HCl to ensure that you have an excess of HCl. Round up to a whole number. If it would take 22.3 mL, add 2 mL of HCl for a total of 24.3 mL and round up to 25.00 mL. Add that quantity of your standardized HCl solution to the solid sample with a volumetric pipette. Add 5 drops of 2:3 methyl red:bromocresol green indicator. Heat solution on hot plate for 3 minute. Let the solution cool to room temperature. Titrate excess HCl in solution with your standardized sodium hydroxide solution. Repeat at least three times. If you had a large excess of HCl, on subsequent titrations, reduce the amount of HCl that you add. Calculate the percentage of sodium carbonate in unknown sample.