CHM 2290 Exper iment #1 Deter mination of a Weak Acid in an Unknown Sample

A. Background Discussion Pr inciple of Acid-Base Titr ations. Many inorganic and organic compounds undergo acid-base reactions (i.e., they either contain ionizable hydrogens or can accept hydrogen ions). These acid-base reactions may be used for the purpose of determining the amount of such species in solution. The general reaction may be written in the form (where charges on the various species are omitted): HA + B A + HB (1) In the foregoing reaction, HA and HB are acids and A and B, respectively, are their corresponding conjugate bases. If such a reaction goes essentially completely to the right when exactly stoichiometric (i.e., equivalent) amounts of HA and B have been added to the solution, this "equivalence point" may be determined by observing some change in the solution properties. This is the basic approach utilized for an acid-base titration. If the purpose is to determine the amount of HA in an unknown sample, a known quantity of the sample may be measured out and dissolved it in water. Measured quantities of a solution containing "B" may then be added until the equivalence point is reached. If the reaction lies very far to the right, both HA and B should be entirely consumed at this point. Any further addition of B will result in a slight excess of B remaining in solution. Acid-Base Indicator s. In order to detect this equivalence point, some type of visual "indicator" can be added which is sensitive to the presence of B. Since B is a base, the indicator chosen may be a weak acid, designated below as HIn, which will react with B less strongly than does the substance HA. As long as HA is present in solution, its reaction with B (i.e., reaction 1) will dominate. When all of the HA is converted to A, the addition of a very small amount of excess B will then result in the following reaction with HIn: HIn + B In + HB (2) If the compound HIn exhibits a different color than does species In, one can visually observe the point when this latter reaction occurs. This is called the "end point." The change in the color of the indicator may occur just after the equivalence point is reached. However, by using only a very small amount of indicator, the amount of excess B added at the time the end point is reached may be insignificantly small compared to the total amount of B required to reach the equivalence point. Under such circumstances, the equivalence point and the end point are presumed to be nearly identical. Titr ation of Monohydr ogen Phthalate. As noted above, a major requirement for an acid-base reaction is that reaction 1 lie far to the right at the equivalence point. This will certainly be true if HA and B are strong acids and bases (such as HCl and OH-), respectively. In the current experiment, the acid to be titrated in the unknown sample is the monohydrogen

phthalate ion, HP-, (present in the unknown sample as the potassium salt, abbreviated as KHP). The HP- species is a weak acid (pKa = 5.41). Therefore, to achieve a favorable reaction, we will utilize the strongest possible base, hydroxide ion (introduced as the sodium salt, NaOH). The reactions which take place are illustrated below: dissolution of the sample: KHP K+ + HP(100% ionized) + + OHionization of the titrant solution: NaOH Na (100% ionized)

Titration reaction:
O

HP-

OH-

P2-

+ H2O

Keq = Ka =
Kw

10-5.41 10-14.00

= 10+8.59

OOH
HP- =

OOP2- = O

Since the equilibrium constant for the titration reaction is quite large (108.59), the titration is considered to be quantitative (i.e., lies essentially 100% to the right) at the equivalence point. A suitable indicator is one which will be sensitive to the presence of the first minute excess of OH-. Phenolphthalein Indicator. For this titration, phenolphthalein will be used as the indicator. Phenolphthalein is a large conjugated organic molecule for which the acidic form (HIn) is colorless and the basic form (In-) is purple-red. For this indicator, pKa 9:
HO OH HO O

O O

OO

+ H+

HIn (colorless)

In(purple-red)

Since the initial solution containing HP- is somewhat acidic, the solution will be colorless until the equivalence point is reached. When the first small excess of OH- occurs (just after the equivalence point), the phenolphthalein indicator will react with this excess OH- and will change to the purple-red (deprotonated) form. This indicator color change is very easy to detect.

B. Standar d NaOH Solution From the foregoing introduction, it is clear that you will need to prepare a sodium hydroxide solution of known concentrationcalled a "standard" solution. Satur ated Sodium Hydr oxide Solution. Sodium hydroxide is generally available as solid pellets which dissolve readily in water. If these pellets have been exposed to the air, they will have reacted to some extent with carbon dioxide in the air to form sodium carbonate: 2 NaOH + CO2(g) Na2CO3 + H2O

The carbonate ion is also a base but is not as strong a base as the hydroxide ion. Therefore, if a significant amount of sodium hydroxide has been converted to sodium carbonate, subsequent titrations involving the NaOH solution may be severely compromised. To minimize carbonate contamination, a solution of satur ated sodium hydroxide (approx. 3.5 M) will be available in the laboratory. Sodium carbonate is insoluble in saturated sodium hydroxide and will precipitate out as soon as it forms. By carefully decanting off a sample of the saturated sodium hydroxide solution, you should not have a significant amount of carbonate in your solution. Pr epar ation of NaOH Solutionca. 0.100 M You are to prepare about 1 L of a solution which contains approximately 0.100 mole NaOH per liter. Before you begin, you should calculate the amount of saturated NaOH you will need for this solution. Assume that the saturated NaOH is approximately 3.5 M. Since the number of moles of NaOH will not change upon dilution, your calculation will be of the form: moles NaOH before dilution = moles NaOH after dilution moles NaOH before dilution = 3.5 M x ? L moles NaOH after dilution = 0.10 M x 1.0 L ? L (sat' d NaOH) = 0.100 M x 1 L 3.5 M 1. Carefully decant a sample of the saturated NaOH solution into a beaker. Then use a graduated cylinder to measure out the necessary quantity of NaOH and pour it carefully into a 1-L (32 oz) bottle. {NOTE: Since we do not know the concentration of the saturated NaOH accurately, it is not necessary to measure the volume with great accuracy.} Record the number of milliliters you used in your lab notebook. 2. Add distilled water to the bottle leaving a bit of air space at the top to allow for mixing. Shake the bottle vigorously for about 5 minutes to mix the NaOH solution and the water thoroughly. NOTE: The sodium hydroxide solution will react with CO2 in the air just as the solid pellets do. Therefore, you should open the bottle only when necessary.

Standar dization of NaOH Solution It is desired to determine the actual concentration of your NaOH solution to four significant figures. This is accomplished by titrating the NaOH against a solution containing a known quantity of acid. The best approach is to use a pr imar y standar d, a species which is known to be 100% pure and is in a form which can be conveniently weighed out. There are two principal primary standard acids: benzoic acid and potassium hydrogen phthalate. 1. Obtain a sample of primary standard potassium hydrogen phthalate (KHP) from your lab instructor. Pour it into a clean weighing bottle and place the bottle (with the top removed) in a beaker. Mark the beaker with your name and place it in the oven for at least 1 hour to dry. Then place the weighing bottle in your desiccator to cool. 2. When your KHP is cooled to room temperature, weigh out (by difference) at least three samples into Erlenmeyer flasks which are numbered. Record the weights in your notebook. The size of the weights should be calculated to require about 35 mL of a 0.100 M NaOH solution. moles of KHP per sample = moles of 0.100 M NaOH in 35 mL g of KHP = (0.100 M NaOH) x (0.035 L) [MW KHP = 204.23] MW KHP 3. Take a 50 mL buret and fill it with distilled water. Let it drain slowly and inspect the inside surface to make certain that the water does not form drops at any point. If you can see liquid

on the inside walls of the buret after it has drained, the buret is not clean. Consult your lab instructor for cleaning procedures. 4. When the buret is clean, carefully fill the buret with your 0.10 M NaOH solution. (Use a glass rod to direct the solution into the top opening of the buret.) Drain the buret until the
top of the solution is slightly below the 0.00 line. Read the meniscus of the solution to two decimal places. [NOTE: Have your instructor check the accuracy of your reading. Avoid parallax errors.] 5. TRIAL TITRATION: Take a small sample of KHP (about 1/10 the size of your carefully weighed samples) in an Erlenmeyer flask. Add about 50 mL of water. Add 3-4 drops of phenolphthalein solution. Slowly add NaOH solution from the buret into the flask, swirling at all times. As you come close to the end point, you will observe a color change at the point where the NaOH solution hits the surface. This will disappear upon swirling the solution. When the first pink color persists after continued swirling, you have reached the end point. Record the final buret reading to two decimal places. 6. Refill the buret to just below the 0.00 line. Read the meniscus to two decimal places and record this reading in your notebook under "standard #1." Take the Erlenmeyer containing your carefully weighed sample #1 and add approximately 50 mL of distilled water. Swirl until the sample is completely dissolved. Add 3-4 drops of phenolphthalein solution and commence the titration with the NaOH solution. When you approach the end point, wash off

the tip of the buret each time and record the buret readings on the left hand page of your notebook. When you reach the final end point, read the buret accurately to two decimal places and record on the right hand page in your notebook. REPEAT FOR STANDARD SAMPLES #2 AND #3, refilling the buret each time and reading the initial meniscus level

before commencing the titration.

7. For each of the three standard samples, calculate the molar ity of your NaOH. If your three standard samples are not in close agreement (e.g., within 0.0005 M), you should probably carry out about three more titrations with newly weighed standard samples. Use the mean or median molarity for your subsequent determinations. g of KHP = (M NaOH) x (L of NaOH) MW KHP

Deter mination of KHP in an Unknown Sample From your lab instructor, obtain an unknown sample containing potassium hydrogen phthalate (KHP). RECORD YOUR UNKNOWN NUMBER IN YOUR NOTEBOOK. Pour the contents of the envelope into a clean weighing bottle, dry, cool and weigh out three samples by difference into Erlenmeyer flasks. Label each flask with a sample number corresponding to the sample weights recorded in your notebook. 1. Weigh out a trial sample of your unknown of the size which would require about 15 mL of your NaOH solution if it were pure KHP. Record the weight of this sample. Do a very quick titration of this sample and note the amount of NaOH solution required. Then weigh out three samples of a size that would require about 35 mL each of your NaOH solution. 2. Repeat steps 3-4 and 6-7 as described under the standardization procedure. 3. Calculate the %KHP in each of your three samples. If the results are not in close agreement, you may wish to weigh out additional samples (if you have a sufficient amount of sample) and carry out additional titrations. g of KHP (mols KHP) (MW KHP) x 100% % KHP = x 100% = g sample g sample %KHP = (mols NaOH) (MW KHP) x 100% g sample