Experiment No.

2
Acid-Base Titrations

I. Preparation of Standard Acid and Base solutions

Objectives

1. To learn how to prepare acid and base titrant solutions

2. To know how to standardize titrant solution using primary standard
3. To know how to standardize titrant solution using secondary standard
4. To be familiar with the concepts of the double indicator method
5. To analyze qualitatively and quantitatively the components of a base
solution

Background

Standard solutions (titrant solution) are reagents of known concentration and

play an important role in all titrimetric methods of analysis. Thus, the following
properties of these solutions must be considered:
1. Sufficiently stable so that it is only necessary to determine its
concentration once;
2. React rapidly with the analyte so that the time required between additions
of reagent is minimized;
3. React more or less completely with the analyte so that satisfactory end
points are observed; and
4. Undergo a selective reaction with the analyte that can be described by a
simple balanced equation.

The accuracy of a titrimetric method can be no better than the accuracy of the
concentration of the standard solution used in the titration.

The standard solutions used in neutralization titrations are strong acids or strong
bases because these substances react more completely with an analyte. Standard
solutions of acids are prepared by diluting concentrated hydrochloric, perchloric,
or sulfuric acid. Nitric acid is seldom used because its oxidizing properties
offer the undesirable side reactions. Standard solutions of bases are prepared
from solid sodium, potassium and barium hydroxides.

Determining the concentration of a standard solution can be done in either of

these two methods:

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 1. Direct Method. The weighed quantity of a primary standard is dissolved in a
suitable solvent and is diluted to an exactly known volume in a
volumetric flask.
2. Standardization. The solution to be standardized is used to titrate (a) a
weighed quantity of a primary standard, (b) a weighed quantity of a
secondary standard, or (c) a measured volume of another standard
solution.

A primary standard is a highly purified compound that serves as a reference

material in all volumetric and mass titrimetic methods. The accuracy of a method is
critically dependent on the following properties of a primary standard:
1. High purity
2. Stability toward air
3. Absence of water of hydration so that the composition of the solid does
not change with variations in relative humidity.
4. Availability at modest cost
5. Reasonable solubility in the titration medium
6. Large molar mass so that the relative error associated with weighing the
standard is minimized.

The standard base solution in the experiment was standardized against Potassium
Hydrogen Phthalate (KHP) as the primary standard. KHP is a nonhygroscopic
crystalline solid. The standardization of the base may be illustrated by the equation:

KHC8H4O4 + NaOH NaKC8H4O4 + H2O

Neutralization titrations can also be employed to analyze qualitatively and

quantitatively the constituents of a solution containing sodium carbonate, sodium
bicarbonate and sodium hydroxide, either alone or mixed. No more than two of
these three constituents can exist in an appreciable amount in any solution
because any reaction will eliminate the third. Thus, mixing sodium hydroxide
with sodium bicarbonate results in the formation of sodium carbonate until one or
the other (or both), of the original reactants is exhausted. If the sodium
hydroxide is used up, the solution will contain sodium carbonate and sodium
bicarbonate; if sodium bicarbonate is depleted, sodium carbonate and sodium
hydroxide will remain; if equimolar amounts of sodium bicarbonate and sodium
hydroxide are mixed, the principal solute species will be sodium carbonate.

The analysis of this kind of mixture requires two titrations:

(1) using an alkaline-range indicator like phenolphthalein, and
(2) using an acid-range indicator like methyl orange.

The composition of the solution can be deduced from the relative volumes of

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 acid needed to titrate equal volumes of the sample. From the deduced composition
of the solution, the volume data can be used to determine the concentration
of each component in the sample

Reagents

50% NaOH solution

Concentrated HCl solution
Distilled water (previously boiled and cooled)
Phenolphthalein indicator
Potassium Hydrogen Phthalate (KHP)
Methyl orange indicator
Unknown Sample (base mixture)

Apparatus and Glassware

2pcs 1-Lvolumetric flask

10-mL pipette
50-mL beaker
250-mL Erlenmeyer flasks
2pcs Acid and base burettes
Graduated cylinder
Suction bulb

Procedure

A. Preparation of 1L of Approximately 0.01 M HCl Solution

1. With a measuring pipet, measure about 8 to 9 mL of concentrated HCl.
Caution! Be very careful in measuring this concentrated acid placed in the
fume hood.
2. Place the measured concentrated HCl to about 200 mL of distilled water
(previously boiled and cooled) in a 1-L volumetric flask. Mix thoroughly
and store in a glass-stoppered bottle. Label.

NOTE
a. Standard solutions of base are reasonably stable as long as they
are protected from contact with the atmosphere.
b. A tightly capped low-density polyethylene bottle can usually provide
sufficient short-term protection against the uptake of atmospheric
carbon dioxide.
c. Before capping, the flexible bottle is squeezed to minimize the
interior air space. Care should also be taken to keep the bottle

Page 3 of 7 Experiment 2 CM124-1L

 closed except during the brief periods when the contents are being
transferred to a burette.
d. Sodium hydroxide solutions will ultimately cause a polyethylene
bottle to become brittle.
e. The concentration of solutions of sodium hydroxide decreases slowly
(0.1 to 0.3% per week) when the base is stored in glass
bottles.
f. The loss in strength is caused by the reaction of the base with the
glass to form sodium silicates. For this reason, standard solutions of
base should not be stored for extended periods (longer than 1 or 2
weeks) in glass containers.
g. In addition, bases should never be kept in glass-stoppered
containers because the reaction between the base and the stopper
may cause the stopper to “freeze” after a brief period.
h. To avoid the same type of freezing, burette with glass stopcocks
should be promptly drained and thoroughly rinsed with water after
use with standard base solutions. This problem is avoided when a
burette equipped with Teflon stopcocks is used.

A. Preparation of 1L of Approximately 0.01 M NaOH Solution which is

Carbonate- Free
1. With a measuring pipette, measure about 4 to 5 mL of 50% NaOH.
Caution! Use extreme care in handling 50% NaOH, which is highly corrosive.
If the reagent comes into contact with skin, immediately flush the area with
copious amounts of water.

2. Place the measured NaOH solution to about 200 mL of distilled water

(previously boiled and cooled) in a 1-L volumetric flask. Mix thoroughly,
and store in a tightly capped polyethylene bottle. Label. After each removal
of base, squeeze the bottle while tightening the cap to minimize the air
space above the reagent. The bottle will become embrittled after extensive
use as a container for bases. Protect the solution from unnecessary contact
with the atmosphere.

B. Standardization of Sodium Hydroxide against Potassium Hydrogen

Phthalate
1. Dry a quantity of primary-standard potassium hydrogen phthalate (KHP).
2. Weigh (to the nearest 0.1 mg) individual 0.7-g to 0.8-g triplicate samples of
the dried primary-standard KHP (oven dried for about 2 hours at 110oC and
cooled in a desiccator) into 250-mL Erlenmeyer flasks.
3. Dissolve each in 50 to 75 mL of distilled water.
4. Add 2 drops of phenolphthalein; titrate with base until the pink color of
the indicator persists for 30 s.
5. Calculate the molarity of NaOH for the three titrations, the mean and the

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 uncertainty based on 95% confidence level.

If both acid and base solutions have been prepared, it is useful to determine
their volumetric combining ratio. Knowledge of this ratio and the concentration of
one solution permit the calculation of the other.

C. Standardization of HCl using Secondary Standard NaOH

1. Place a test tube or a small beaker over the top of the burette that holds
the NaOH solution to minimize contact between the solution and the
atmosphere.
2. Record the initial volumes of acid and base in the burettes to the nearest
0.01 mL. Do not attempt to adjust the initial reading to zero. Deliver 25
mL of the acid into a 250-mL Erlenmeyer flask. Rinse the tip of the burette
with a little distilled water from a wash bottle.
3. Add two drops of phenolphthalein and then a sufficient base to render the
solution a definite pink. Introduce acid dropwise to discharge the color,
and again rinse down the walls of the flask. Carefully add base until the
solution again requires a faint pink hue that persists for at least 30 s.
4. Record the final burette volumes (again, to the nearest 0.01 mL). Repeat
the titration twice. Calculate the molarity of HCl.
5. Calculate the molarity of HCl for the three titrations, the mean and the
uncertainty based on 95% confidence level.

D. Determination of the Components of a Base Mixture by the Double

Indicator Method

1. Secure from the instructor a liquid sample containing a mixture of bases.

2. Pipette triplicate 25-mL aliquot portions of liquid into separate Erlenmeyer
flasks. Add 2 drops of phenolphthalein indicator and titrate the solution
with the standard HCl to the appearance of a very light pink color. Record
the volume of HCl used. (This is Vphe)
3. To the same solution, add 2 drops of methyl orange indicator and
continue the titration until the color becomes salmon pink (peach). Record
the volume of HCl used to complete the methyl orange end point. (This is
Vmo)
4. From the two volumes of HCl, determine the components of the unknown
sample as to (NaOH and Na2CO3) or (NaHCO3 and Na2CO3).
5. Compute the concentration of the two basic components in the unknown
mixture (mg NaOH/mL solution and mg Na2CO3/mL solution) or (mg
NaHCO3/mL solution and mg Na2CO3/ mL solution).
6. Calculate the mean and the uncertainty based on 95% confidence level.

DATA SHEET

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 A. Standardization of NaOH Solution using Potassium hydrogen
phthalate (KHP) Primary Standard

Trial 1 Trial 2 Trial 3

Weight of KHP primary standard, g

Volume of NaOH solution used, mL

Molarity of NaOH solution, mmoles/mL

Average molarity of NaOH solution, mmoles/mL

B. Standardization of HCl solution using NaOH Secondary Standard

Trial 1 Trial 2 Trial 3

Volume of HCl solution titrated, mL

Volume of NaOH solution used, mL

Average molarity of NaOH solution,
mmoles/mL (from Table A)
Molarity of HCl solution, mmoles/mL

Average molarity of HCl solution, mmoles/mL

C. Determination of the Components of a Base Mixture by the

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 Double Indicator Method

Sample No.:

Trial 1 Trial 2 Trial 3

Average Molarity of HCl solution,
mmoles/mL (from Table B)
Volume of sample (aliquot), mL

Volume of HCl (phen. end point) used, mL

Volume of HCl (mo end point) used, mL

Comparison of the two volumes of HCl

Components of the base mixture

Component 1,
Concentration of the mmol/mL
unknown sample Component 2,
mmol/mL
Component 1,
Average
mmol/mL
concentration of the
Component 2,
unknown sample
mmol/mL

Page 7 of 7 Experiment 2 CM124-1L