CHEM. 2AP UNIT 3 CH.

4 34
09/26/2003
VOLUMETRIC ANALYSIS - ACID-BASE TITRATIONS

How can we determine the unknown concentration of an acid or base. For instance, you might want to know the
molarity or concentration of acetic acid in vinegar. This is done by using a technique known as a TITRATION. A
titration is a VOLUMETRIC ANALYSIS. This kind of analysis uses precisely measured amounts of liquid to carry
out an analysis. Terms you must be familiar with are:
titration, buret, equivalence point, endpoint, standard solution, analyte, titrant, and indicator. When solving
volumetric analysis problems, the same chemical rules apply as with the neutralization problems:
Write down the reaction.
Convert to moles and relate moles of acid to moles of base.
Dont be frightened by wordy railroad problems.
Ignore superfluous information by listing the necessary information before you do the problem.

A TITRATION is process where the addition of a known amount of solution of known concentration (called a
standard solution) is used to determine the unknown concentration of another solution. The standard solution is
called the titrant; the solution being analyzed is called the analyte.
In a titration, a solution of accurately known concentration called a STANDARD SOLUTION is added gradually
to another solution of unknown concentration until the chemical reaction between the two solutions is complete
(when the acid and base have neutralized each other). A titration is a technique using
the neutralization reaction calculations you did in the previous exercise.
A titration uses the following principle: If you know the volumes of the standard
solution (the titrant) and unknown solution (the analyte) used in the titration, along
with the concentration of the standard solution, you can calculate the concentration of
the unknown solution. For example, you can titrate vinegar (acetic acid) with a
standard solution of NaOH. This will allow you to determine the concentration of the
acetic acid.
In order to titrate an unknown with a standard solution, there must be some way to
determine when the equivalence point of the titration has been reached. In acid-base
titrations, dyes known as acid-base indicators are used for this purpose. For example,
the dye known as phenolphthalein is colorless in acidic solution but is red in basic
solution. If we add phenolphthalein to an unknown solution of acid, the solution will
be colorless. We can then add standard base from a buret until the solution barely
turns from colorless to red. This color change indicates that the acid has been
neutralized and the drop of base that caused the solution to become colored has no
acid to react with. The solution therefore becomes basic, and the dye turns red. The
color change signals the end point of the titration which usually coincides very
nearly with the equivalence point. Care must be taken to choose indicators whose
end points correspond to the equivalence point of the titration.

EQUIVALENCE POINT Neutralization point determined by the stoichiometry of the
acid/base reaction.
END POINT where the indicator first changes color. The equivalence point and end
point may or may not be the same.

If you know:
the measured volume of the acetic acid, V
A

the measured volume of NaOH used to neutralize the acetic acid, V
B

the molarity of the standard solution NaOH, M
B

You can determine the molarity of the unknown acetic acid M
A
by the following reaction and relationship:
HC
2
H
3
O
2
+ NaOH NaC
2
H
3
O
2
+ H
2
O
When neutralized, moles
acid
= moles
base
M
A
V
A
= M
B
V
B

Make sure that you realize that this is only for a 1:1 relationship. The mole relationship is dependent on the acid and
base used. Knowing this, this is how the procedure called a titration is carried out. The lab equipment used is called a
buret. A buret allows you to add very small volumes (less than 1 mL) of a liquid.





CHEM. 2AP UNIT 3 CH. 4 35
09/26/2003
STEPS:
1. A measured amount of an acid of unknown concentration is added to a flask using a buret. An appropriate
indicator such as phenolphthalein is added to the solution. (The indicator will indicate, by a color change, when
the acid and base has been neutralized).
2. Base (standard solution) is slowly added to the acid.
3. The process is continued until the indicator shows that neutralization has occurred. This is called the END
POINT. The end point is usually signaled by a sharp change in the color of the indicator in the acid solution. In
acid-base titrations, indicators are substances that have distinct different colors in acid and base (Phenolphthalein
red in base, colorless in acid).
4. At the equivalence point, both acid and base have been completely neutralized and the solution is still
colorless. However, if we add just one more drop of NaOH solution from the buret, the solution will immediately
turn pink because the solution is now basic. This slight excess of NaOH is not much beyond the end point. The
volume of the base is recorded and used to determine the molarity of the HCl.

The unknown solution can be a base or an acid and the process is the same.

Do these titration problems (same as neutralization). This is just another way to state a neutralization problem!!

1. A 25.00 mL solution of HCl is titrated with a standard solution of 0.750M NaOH. Phenolphthalein was used as an
indicator. The equivalence point was reached after the addition of 18.00 mL of NaOH. What is the concentration
of the acid solution? (0.540 M)
2. What volume of 0.139M phosphoric acid is used to reach the equivalence point when 38.5 mL of 0.500 M NaOH
is titrated with the phosphoric acid in which phenolpthalein is used as the indicator? (15.0 mL)
3. What volume of 0.900 M HCl is required to completely neutralize 25.0 g of calcium hydroxide. (749 mL)
4. A volume of 128 mL of 0.650 M Ba(OH)
2
was required to completely neutralize 50.0 mL of nitric acid solution
HNO
3
. what was the concentration of the acid solution? (3.33 M)
5. How many mL of 1.00 M H
2
SO
4
solution are required to neutralize 2.10 g of KOH? (18.7 mL)
6. What volume of 0.210 M H
2
SO
4
solution is needed to exactly neutralize 50.0 mL of 0.082 M NaOH? (9.8 mL)
7. What volume of 0.0824 M NaOH solution is needed to titrate 9.8 mL of 0.210 M H
2
SO
4
to the equivalence point?
(50. mL)
8. What is the molarity of an oxalic acid H
2
C
2
O
4
solution if 22.50 mL of this solution requires 35.72 mL of 0.198 M
NaOH for complete neutralization? (0.157 M)

STANDARDIZING A SOLUTION

Typically, to be considered a standard solution, the concentration of the solute in the solution must be known to
four significant figures. In many cases (especially with solid solutes) it is possible to prepare a standard solution
by accurate weighing of the solute, followed by precise dilution to an exactly known volume in a volumetric flask.
One of the most common standard solutions used in acid-base titration analyses, however, cannot be prepared in
this manner.

Sodium hydroxide is one of the bases commonly used in the laboratory and is one of the most used standard
solutions in a titration Sodium hydroxide is stored in flake (solid form) and a standard solution made with it would
involve weighing out the solid NaOH and then making the solution by adding water. For instance, a 1.00 molar
solution of NaOH would be made by dissolving 40.00 grams of solid NaOH in enough water to make 1.00 L of
solution. This method of preparation would not yield an accurate molarity of standard solution. It is not possible
to prepare standard sodium hydroxide solutions by mass. It is difficult to obtain solid sodium hydroxide in a
pure form because it has a tendency to absorb water from air, and its solution reacts with carbon dioxide. For these
reasons a solution of sodium hydroxide must be standardized before it can be used in accurate analytical work. We
can standardize the NaOH solution by titrating it against an acid solution of accurately known concentration.
The acid often chosen for this task is a monoprotic acid called potassium hydrogen phthalate (KHP) molecular
formula KHC
8
H
4
O
4
. (M. W. = 204.22 g/mole). KHP is a white soluble solid that is commercially available in
highly pure form.

First, a known amount of KHP is transferred to an Erlenmeyer flask and an accurately measured amount of water
is added to make up a solution. Next, NaOH solution is carefully added to the KHP solution from a buret until we
reach the equivalence point. At the equivalence point, all the KHP present has been neutralized by the added
NaOH and the solution is still colorless. However, if we add just one more drop of NaOH solution from the buret,
the solution will immediately turn pink because the solution is now basic.

CHEM. 2AP UNIT 3 CH. 4 36
09/26/2003
By using the neutralization calculations previously done, you can accurately determine the concentration of the
standard NaOH accurately. If the standard solution is accurate, then you can accurately determine the
concentration of your unknown sample of acid.

Ex. 1: A student carries out an experiment to standardize (determine the exact concentration of) a sodium
hydroxide solution. To do this, the student weights out a 1.3009-g sample of potassium hydrogen phthalate
(KHC
8
H
4
O
4
, often abbreviated KHP). KHP (molar mass 204.22 g/mole) has one acidic hydrogen. The student
dissolves the KHP in distilled water, adds phenolphthalein as an indicator and titrates the resulting solution with
the sodium hydroxide solution to the phenolphthalein endpoint. The difference between the final and initial
buret readings indicates that 41.20 mL of the sodium hydroxide solution is required to react exactly with the
1.3009g KHP. Calculate the concentration of the sodium hydroxide solution. (0.1546 M)













Ex. 2 An environmental chemist analyzed the effluent (the released waste material) from an industrial process
known to produce the compounds carbon tetrachloride (CCl
4
) and benzoic acid (HC
7
H
5
O
2
), a weak acid that has
one acidic hydrogen atom per molecule. A sample of this effluent weighing 0.3518 g was shaken with water, and
the resulting aqueous solution required 10.59 mL of 0.1546 M NaOH for neutralization. Calculate the mass
percent of HC
7
H
5
O
2
in the original sample. (56.82%)













Ex. 3: You want to determine the molar mass of an acid. The acid contains one acidic hydrogen per molecule.
You weigh out a 2.879 g sample of the pure acid and dissolve it, along with 3 drops of phenolphthalein indicator,
in distilled water. You titrate the sample with 0.1704 M NaOH. The pink endpoint is reached after addition of
42.55 mL of the base. Calculate the molar mass of the acid. (397.1 g/mole)














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