Acid-Base

Equilibrium


Lab: Determination of the Identity of an Unknown Weak Acid

The Crime:

The attempts on Mr. Boylans life always get more vigorous after the first semester. Students are
generally very angry with Mr. Boylan after getting their semester averages and wish to exact revenge! Despite their
supposed hatred of chemistry, however, they continually attempt to take his life by using chemical means. The
following heinous act represents only the most recent attempt

Mr. Boylan was enjoying a meal after a long day of teaching how to calculate the pH of salt solutions by
putting a lot of salt on his food. As he wondered how he might make the process more enjoyable for his students,
he momentarily considered having them collect their tears so they might measure the pH of those solutionsbut
was unsure of the best way to collect those tears. His thoughts were interrupted, however, as he soon realized that
what he had just shaken onto his food was definitely NOT sodium chloride. He stood up in a panic, but quickly
began to feel dizzy and passed out. As he fainted the last thing he heard was sinister laughing and a voice bellow,
How does that weak, monoprotic acid taste, sucker?! What would Avogadro do NOW!?!?!?! BUHAHAHHAHAHA!

When Mr. Boylan awoke, he discovered his home had been completely vandalized. Some messages had
been written on his walls using phenolphthalein in a basic solution. One of the messages said, Why dont you
buffer this?! and another said, Your Ka value is 1.010!!" because youre so WEAK!

Always looking for a teachable moment, Boylan gathered his strength and collected the remaining weak
monoprotic acid and brought it into class to be identified. Principal Nichols had all of the AP Chemistry students
searched by Round Rock Police Department. The students in the table below were found carrying the respective
weak acids. Your goal is to identify the weak acid from the crime scene so that you can match it to one of the
following suspects and deliver some cold, hard justiceforensic chemistry style.

Suspect
Name

Acid Found with

Suspect

glycolic
acid
potassium dihydrogen
phosphate
potassium hydrogen
sulfate
potassium hydrogen
sulfite
sodium hydrogen
sulfite
sodium hydrogen
tartrate

Formula of
Most
Common
Form

Molar Mass
(g/mol)

Ka

pKa

HC2H3O3

76.05

1.6x10-4

3.80

KH2PO4

136.09

Ka2 of H3PO4 = 6.2x10-8

7.21

KHSO4

136.17

Ka2 of H2SO4 = 1.2x10-2

1.92

KHSO3

120.16

Ka2 of H2SO3 = 6.4x10-8

7.19

NaHSO3

104.07

Ka2 of H2SO3 = 6.4x10-8

7.19

NaHC4H4O6H2O

190.09

Ka2 of H2C4H4O6 = 4.6x10-5

4.34

Acid-Base Equilibrium


Introduction:
A common question chemists have to answer is how much of something is present in a sample or a
product. If the product contains an acid or base, this question is usually answered by a titration. Acidbase titrations can be used to measure the concentration of an acid or base in solution, to calculate the
molar mass of an unknown acid or base, and to determine the equilibrium constant of a weak acid (Ka) or
weak base (Kb).

Concepts:

Weak Acid

Equilibrium Constant, Ka
Titration Curve

Equivalence Point
End Point


Indicator

Background:
Titration is a method of volumetric analysisthe use of volume measurements to analyze an
unknown. In acid-base chemistry, titration is most often used to analyze the amount of acid or base in a
sample or solution. Consider a solution containing an unknown amount of hydrochloric acid. In a
titration experiment, a known volume of the hydrochloric acid solution would be titrated by slowly
adding drop wise a standard solution of a strong base such as sodium hydroxide. (A standard solution is
one whose concentration is accurately known.) The titrant, sodium hydroxide in this case, reacts with
and consumes the acid via a neutralization reaction (Equation 1). The exact volume of base needed to
react completely with the acid is measured. This is called the equivalence point of the titrationthe point
at which stoichiometric amounts of the acid and base have combined.

HCl(aq) + NaOH(aq) NaCl(aq) + H2O(l)


Equation 1


Knowing the exact concentration and volume added of the titrant gives the number of moles of
sodium hydroxide. The latter, in turn, is related by stoichiometry to the number of moles of hydrochloric
acid initially present in the unknown.



Indicators are usually added to acid-base titrations to detect the equivalence point. The endpoint
of the titration is the point at which the indicator changes color and signals that the equivalence point has
indeed been reached. For example, in the case of the neutralization reaction shown in Equation 1, the pH
of the solution would be acidic (< 7) before the equivalence point and basic (> 7) after the equivalence
point. The pH at the equivalence point should be exactly 7, corresponding to the neutral products
(sodium chloride and water). An indicator that changes color around pH 7 is therefore a suitable
indicator for the titration of a strong acid with a strong base.


The progress of an acid-base titration can also be followed by measuring the pH of the solution
being analyzed as a function of the volume of titrant added. A plot of the resulting data is called a pH
curve or titration curve. Titration curves allow a precise determination of the equivalence point of the
titration without the use of an indicator.

Acid-Base Equilibrium

In this experiment, the pH of the titration solution will be monitored using a pH meter; the
obtained titration plot will then be used to determine the molar mass and equilibrium constant (Ka) of
the unknown. These values will then let you decide the identity of the weak acid.




The molar mass is determined by titrating an acid with a standard solution of NaOH. Since one
mole of NaOH reacts with one mole of hydrogen ion, at the equivalence point the following relation holds:

Vb Mb = moles base = moles H+


Equation 2

!"#!" !"#$
MM! = !"#$% ! !



Equation 3

where Vb is the volume of the base added at the endpoint, Mb is the molarity of the base, grams acid is the
mass of acid used, and MMa is the molar mass of the acid.


A graph of pH versus volume of NaOH added (See Figure 1) for the titration of a weak acid with
NaOH is obtained by carefully following the titration with a pH meter. There is a significant change in pH
in the vicinity of the equivalence point. Note that when a weak acid is titrated with a strong base, the
equivalence point is NOT at pH 7, but is on the basic side. The value of the equilibrium constant for the
dissociation of the acid is determined from a titration curve by considering the pH when the acid is halfneutralized.


If the dissociation of the acid is represented as:

+ ! ! ! + !


Equation 4

the equilibrium constant expression is:

! =

!! ! ! [!! ]
[!"]

Equation 5

When the acid is half neutralized, [HA] = [! ], these terms cancel in Equation 5 above, and
Ka = [H3O+]. Therefore, when the acid is half-neutralized, the pH = pKa. The point where pH is equal to
pKa can be determined from the graph. (See Figure 1)

Acid-Base Equilibrium

1.
2.
3.
4.

Initial pH is in acidic range, though not as low as strong acid.
pH stays relatively constant through this buffer region.
There is a jump in pH from pH 7 to pH 11. pH at equivalence is > 7.
After equivalence, pH flattens out at high value (pH of a strong base).

Materials:
Chemicals
Equipment
Phenolphthalein indicator solution, 1.0%, 1mL
Balance
Sodium hydroxide solution, NaOH, 0.1M
Beaker, 250mL
Unknown weak acid
Buret, 50mL
Distilled Water
Erlenmeyer Flask, 125mL or 250mL

Funnel

Magnetic Stirrer and Stir Bar

pH Probe

Data Collection Device

Wash Bottle

Safety Precautions:

Dilute sodium hydroxide solutions are irritating to skin and eyes. Phenolphthalein is an alcoholbased solution and is flammable. It is moderately toxid by ingestion. Keep away from flames and other
ignition sources. Avoid contact of all chemicals with eyes and skin and wash hands thoroughly with soap
and water before leaving the laboratory. Wear chemical splash goggles and chemical resistant gloves and
apron.

IT IS IMPORTANT THAT YOU ARE CAREFUL WITH THE TIP OF THE pH PROBE! THEY EASILY BREAK!!
When you are not using the pH probe, gently rest it in a beaker of tap water.
Be sure to rinse the pH probe with distilled water EACH TIME before using!

Acid-Base Equilibrium


Procedure:
1. Prepare for data collection by connecting your pH probe to your data collection device as directed by your
instructor.

2. The burets have been prepared for you. If not, complete the following steps to ensure the concentration of
the standardized sodium hydroxide solution remains unchanged:

a. Clean your buret using distilled water, then rinse it with three small portions (about 7mL each) of
the known NaOH solution as indicated by your instructor.

b. After rinsing, carefully fill the buret to above the zero mark with the known solution.

c. Open the buret stopcock to allow any air bubbles to escape from the tip. Close the stopcock when
the liquid level has reached the graduated part of the buret.

3. Based on the assignment provided by your instructor, weigh about

Group A
Group B
0.1-0.2g
0.2-0.3g
of a sample of the unknown acid in a weighing dish using an analytical balance. Record the precise
mass in the appropriate Data Table.

4. Transfer the unknown acid into an Erlenmeyer flask. Use distilled water from a wash bottle to
rinse all of the remaining solid from the weighing dish or funnel into the flask as well.

5. Add about 50mL of distilled water to the Erlenmeyer flask and swirl until all of the unknown acid
is dissolved. STOP. THINK. Does adding distilled water change the amount of moles of acid in your flask?

6. You will be provided with various indicators. Add three drops of the indicator that your group
determines to be the appropriate indicator for the titration to the unknown acid solution in the
flask.

7. If available, carefully add a magnetic stir bar to the flask and thoroughly stir your solution before
continuing. If you do not have a stir bar available, swirl your flask as indicated by your instructor.

8. You are now ready to begin the titration. This process goes faster if one person manipulates and reads the
buret while another person operates the data collection device and enters volumes.

a. Rinse the pH probe with distilled water and then insert the pH probe into the Erlenmeyer flask to
record the initial pH as indicated by your instructor.

b. Remove the pH probe and return to its storage beaker.

c. Add a 1.00mL increment of NaOH titrant (enough to raise the pH about 0.15 units).

d. Swirl the Erlenmeyer flask to ensure good mixing.

e. Rinse the pH probe with distilled water and then insert the pH probe into the Erlenmeyer flask and
obtain the new pH value as indicated by your instructor.

Acid-Base Equilibrium


f.

Record the pH and volume added in your data table and on the data collection device as indicated
by your instructor.

g. Continue adding NaOH solution in 1.00mL increments (increments that raise the pH by about 0.15
units) and record the pH and volume readings after each addition. You will know you are
approaching the equivalence point when it takes longer for the pink color of the phenolphthalein to
fade.

h. Continue adding NaOH solution in 1.00mL increments until the pH levels off in the distinctly basic
range to complete your titration curve.

9. Repeat Step 8 with a second trial. However, this time try to more closely determine the equivalence point
by adding NaOH solution in one-drop increments when you are close to the equivalence point. A convenient
way to do this is to turn the stopcock 180 quickly and smoothly.

10. Take a screen shot of your graph and your data table and upload to your Drive account. Share with group
members as indicated by your instructor.

11. Clean up and dispose of chemicals as directed by your instructor. Wash your hands before leaving the lab.

Data:

Trial 1

Trial 2
Initial Volume of Buret:
Volume
NaOH
Added
(mL)

0.00

pH

Initial Volume of Buret:

Volume

NaOH
pH
Added
Continued
(mL)
Continued

Volume
NaOH
Added
(mL)

0.00

pH

Volume
NaOH
pH
Added
Continued
(mL)
Continued

Acid-Base Equilibrium


Make a sketch of your titration curve on the graph below. Indicate the half-equivalence and equivalence points.

Mass of Unknown Acid

Trial 1

Trial 2
g

NaOH Volume Added BEFORE the largest pH increase

mL

mL

NaOH Volume Added AFTER the largest pH increase

mL

mL

Volume of NaOH Added at Equivalence Point

mL

mL

Moles NaOH

mol

mol

Moles Unknown Acid

mol

mol

g/mol

g/mol

Molarity of NaOH

Volume of NaOH Added at Equivalence Point in LITERS

Molar Mass of Unknown Acid

Class Average Molar Mass of Unknown Acid
Identity of Acid AND Suspect

g/mol