Experiment 2-A ACID-BASE TITRATIONS

CHM 1041 The Equivalent Mass of an Unknown Acid EqWt.wpd

DISCUSSION
Brknsted-Lowry theory defines an acid as a hydrogen ion (H+) donor and a base as a hydrogen
ion (H+) acceptor. Some compounds are amphiprotic, i.e., they have the ability to act as an acid
or a base. Water has this potential:

H2O + H+  H3O+ H2O  OH- + H+

base acid

In aqueous solutions, very strong acids force water to act as a base and one hundred percent of
the acidic molecules ionize. For example, when molecular hydrogen chloride gas is bubbled
through water it ionizes completely to yield hydronium ions and chloride ions in solution:

HCl (g) + H2O (l)  H3O+(aq) + Cl-(aq) 100% ionization

Therefore in water solutions, acids much stronger than H3O+ are completely converted to H3O+, and
it follows that the strongest acid possible in water1 in appreciable concentration is the hydronium
ion, H3O+.

Very strong bases cause water to act as an acid, thereby generating the hydroxide ion, OH-. For
example, oxide ion reacts completely with water giving only hydroxide ion.

O2- + H2O  OH- + OH-

Bases much stronger than OH- are completely converted to OH- when placed in water solvent, and
therefore the strongest base that can exist in water2 in appreciable concentration is OH-. Many
ionic oxides react with water to give hydroxide solutions, for example

Na2O (s) + H2O (o)  2 Na+(aq) + 2 OH-(aq)

When a very strong aqueous acid reacts with a very strong aqueous base, the net reaction occurs
between the hydronium and hydroxide ions.

H3O+(aq) + OH-(aq)  2 H2O (o)

This is the actual reaction that occurs when a very strong aqueous acid is neutralized with a very
strong aqueous base. Note that one mole of hydronium ions reacts exactly with one mole of
hydroxide ions to accomplish neutralization, and one mole of hydrogen ions (H+) has been
transferred from acid to base.

Acids weaker than hydronium ion only partially ionize in water solution. An equilibrium is

1
H3O+ is the conjugate acid of water. In nonaqueous solvents, the strongest acid possible would be the conjugate acid of the solvent,
e.g., in liquid methanol,
CH3OH + H+  CH3OH2+

2
OH- is the conjugate base of water. In nonaqueous solvents, the strongest base possible would be the conjugate base of the
solvent, e.g., in liquid methanol,
CH3OH - H+  CH3O-
 2

established in which the weaker molecular acid (reactant) is the acid present in solution in greater
abundance. Consider 0.1 M HCO2H (formic acid):

HCO2H (aq) + H2O (aq) õ H3O+(aq) + HCO2-(aq) J4% ionization

Neutralization of an aqueous solution of a moderate acid and a very strong base therefore would
be best described as a reaction between the molecular acid and the hydroxide ion. For example,
consider the reaction between formic acid and hydroxide ion:

HCO2H (aq) + OH-(aq)  H2O (o) + HCO2-(aq)

Here again, one mole of hydrogen ions has been transferred from the acid to the base. Formic
acid has only one acidic hydrogen per molecule and is therefore described as monoprotic. Many
acids, however, have more than one acidic hydrogen per molecule and are capable of donating
more than one mole of hydrogen ions per mole of acid. For example, oxalic acid is diprotic since
it contains two acidic hydrogens per molecule, and requires two moles of hydroxide base per mole
of acid to accomplish neutralization.

H2C2O4 (aq) + 2 OH-(aq)  C2O42-(aq) + 2 H2O (o)

The point at which an acid-base reaction is stoichiometrically complete may be referred to as the
neutralization or equivalence point. At this condition, the hydrogen ion donating capacity of the acid
has just been matched by the hydrogen ion accepting capacity of the base.

Equivalent Mass and Normality

The equivalent mass (or equivalent weight) of an acid or base is the mass of the acid or base that
donates or accepts one mole of hydrogen ions in the reaction being considered. One equivalent
mass is also called one equivalent (1 eq). As an example, consider the following acid-base
reaction:

H3PO4 (aq) + 3 OH-(aq)  PO43-(aq) + 3 H2O (o)

One mole of phosphoric acid donates three moles of hydrogen ions in this reaction and is behaving
as a triprotic acid;3 therefore 1 mole = 3 eq. The equivalent mass of H3PO4 may now be calculated:

98.0 g x 1 mol = 32.7 g

mol 3 eq eq

This means that 32.7 grams of H3PO4 donate one mole of hydrogen ions when it reacts with
enough hydroxide. The equivalent mass is always related to the molar mass by a small whole
number (1,2, or 3), this number being the number of hydrogen ions donated/accepted by one mole
of the acid/base that is reacting. Some other examples of acids/bases and their common
equivalent relationships follow.

3
H3PO4 may behave as a diprotic acid with bases weaker than OH-, e.g., ammonia.

H3PO4 (aq) + 2 NH3 (aq)  2 NH4+(aq) + HPO42-(aq)

In this reaction, 1 mole of H3PO4 equals 2 equivalents.

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Ca(OH)2 dibasic, therefore.... 1 mole = 2 eq

74.1 g x 1 mol = 37.0 g

mol 2 eq eq

H2SO4 diprotic, therefore.... 1 mole = 2 eq

98.1 g x 1 mol = 49.0 g

mol 2 eq eq

HC2H3O2 monoprotic, therefore.... 1 mole = 1 eq

60.1 g x 1 mol = 60.1 g

mol 1 eq eq

A solution's concentration is often conveniently expressed as the molarity of that solution, M. The
molarity is the number of moles of the solute dissolved in one liter of the solution (moles/L). An
alternative for expressing a solution's concentration that is based on the number of equivalents of
solute rather than the number of moles is called normality, N. The normality is the number of
equivalents of the solute dissolved in a liter of solution (eq/L). Molarity and normality are easily
related by small whole numbers:

0.25 M H3PO4 triprotic, therefore.... 1 mole = 3 eq

0.25 mol x 3 eq = 0.75 eq or 0.75 N H3PO4

L mol L

4.82 x 10-3 N Ba(OH)2 dibasic, therefore.... 1 mole = 2 eq

4.82 x 10-3 eq x 1 mol = 2.41 x 10-3 mol or 2.41 x 10-3 M

L 2 eq L

Volumetric Analysis
Analysis of an unknown sample of an acid may be accomplished by reaction with a known sample
of a base to the point of equivalence (or an unknown base may be analyzed with a known acid).
The fundamental premise here is that the number of equivalents of base will be equal to the
number of equivalents of acid at neutralization. Titration is the procedure used to accurately
measure the volume of a reactant solution which is stoichiometrically equivalent to an accurately
measured quantity of a second reactant. The reactant solution is called the titrant and is delivered
by a buret. An indicator, a substance which changes color, is added to detect the equivalence or
end-point. If the normality of the titrant is accurately known, the number of equivalents of titrant
may be calculated:

N x V = Number of equivalents

If the titrant was a basic solution of known normality, the number of equivalents of base delivered
may be calculated, and this is equal to the number of equivalents of unknown acid that reacted with
the base. For example, how many equivalents of unknown acid are present if the acid was titrated
to the equivalence point with 42.17 mL of 0.1024 N KOH solution?
 4

N x V = 0.1024 eq x 0.04217 L = 0.004318 eq or 4.318 x 10-3 eq KOH

L
Therefore, 4.318 x 10-3 equivalent of unknown acid was neutralized by the KOH titrant.

EXPERIMENTAL

In part A, you will determine the normal concentration (standardize) of a stock solution of sodium
hydroxide. In part B, you will use the standard sodium hydroxide solution to titrate weighed
samples of an unknown acid, and then calculate the equivalent mass of the unknown acid.

A. The Standardization of a Sodium Hydroxide Solution

A stock solution of unknown concentration has been prepared for use as the titrant in part B of this
experiment. First the normality of the of the NaOH titrant must be accurately determined. This can
be done by titrating the NaOH solution with a solution of a solid acid that can be accurately
weighed.4 The solid acid, known as a primary standard, must be of high purity and remain free of
moisture. The primary standard used in this experiment is potassium hydrogen phthalate,
KHC8H4O4, which is monoprotic and abbreviated "KHP". The KHP is dissolved in water and titrated
with the NaOH to the equivalence point using phenolphthalein indicator.5

Three standardization titrations of KHP with the stock NaOH solution have been done for you.
Obtain these data and carefully record it on the following data table. You will use these data to
calculate the normal concentration of the stock NaOH solution. In the space provided, show the
method/set-up for each set of calculations for each titration. INCLUDE UNITS. Finally, calculate
the average normality for the stock NaOH solution. This is the normality value that will be used in
part B of this experimental section.

Standardization of Stock NaOH Solution

Include correct units and significant figures

Note: KHP L KHC8H4O4 , Molar Mass KHC8H4O4

4
The stock NaOH solution has been prepared by dissolving about 4 grams of NaOH in a liter of boiled, cooled water. The water
was boiled to expel dissolved carbon dioxide, which reacts with water to form carbonic acid, H2CO3. The carbonic acid would react with
and consume hydroxide ion to yield carbonate ion.

CO2 (g) + H2O (l)  H2CO3 (aq)

H2CO3 (aq) + 2 OH-(aq)  CO32-(aq) + 2 H2O (l)

Also, NaOH cannot be used as a primary standard because of its tendency to rapidly absorb moisture. An accurate weighing of pure
NaOH is impractical.

5
In this experiment the indicator used to determine the end-point of the titration is called phenolphthalein, which is abbreviated HPth.
The HPth shows a different color in acid solution than in base solution, where it becomes the ion Pth-.
HPth(aq) + OH-(aq)  H2O (l) + Pth-(aq)
colorless pink

HPth is a weaker acid than any of the acids titrated in this experiment. When all of the titrated acid has been consumed (equivalence
point), the OH- starts to react with the HPth, forming Pth-, and the color of the solution suddenly changes from colorless to pink, marking
the end-point of the titration.
 5

Run 1 Run 2 Run 3

Mass of KHP
Moles of KHP
Since KHP is monoprotic, 1 mole KHP = 1 equivalent KHP
Equivalents KHP

Titrations with NaOH Solution

Final buret reading
Initial buret reading
Total Volume NaOH
Titrated, mL
Volume NaOH, L

Normality NaOH
Average Normality NaOH Solution

Calculations (Include set-up and units):

B. The Equivalent Mass of an Unknown Acid

The equivalent mass of an unknown solid acid will be determined as follows. An accurately
measured mass of solid acid will be titrated to the equivalence point with the standardized NaOH
solution. From the volume of the titrated NaOH solution and its known normality is found the
number of equivalents of NaOH delivered. The number of equivalents of NaOH should be equal
to the number of equivalents of unknown acid. Having found the number of equivalents of acid in
 6

the sample and its accurate mass in grams, the equivalent mass of the acid (g/eq) may be
calculated.

Experimental Procedure
1) Obtain a 50-mL buret, four clean and dry 125-mL Erlenmeyer flasks for sample titrations,
and a wash bottle filled with deionized water.
2) Next, obtain about 100 mL of stock NaOH solution and save it in a clean, dry, labeled
Erlenmeyer flask. Keep the NaOH solution stoppered to minimize reaction with CO2 from
the air.
3) Rinse the inside of the buret with hot water and allow it to drain through the stopcock and
tip. Rinse it again, this time with deionized water, and allow the buret to drain upside down
affixed to the buret clamp.
4) Obtain your sample of unknown solid acid and immediately record its ID number on the
data table.
5) Assemble the four, clean, dry, and labeled 125 mL Erlenmeyer flasks. Tare each flask on
the analytical balance and then carefully add the approximate mass of acid as indicated on
the unknown label. Record on your data table the accurate mass of each sample to the
limit of the balance sensitivity, and then cork each flask.
6) Now return to the buret and rinse the inside of the buret twice with about 3 mL of the stock
NaOH solution, draining through the stopcock and tip. Affix the buret to the buret clamp
right side up, making sure the buret is in a stable, vertical position, and then fill it to just
above the 0.00 mL scale division with the NaOH standard solution. Open the stopcock
briefly to fill the tip with liquid, taking care to expel air bubbles. The liquid level should now
fall below the 0.00 mL mark. Allow the liquid a few moments to settle.
7) Add 25 mL of deionized water and 3 drops of phenolphthalein to each of the Erlenmeyer
flasks containing your unknown solid acids. Swirl the flasks to dissolve the solids.
8) Locate the first sample flask under the buret with the tip well inside the mouth of the flask.
Place a piece of white paper under the flask. Record the initial buret reading on the data
table. Remember to estimate buret readings to the nearest 0.01 mL. Do not attempt to
adjust the initial reading to the 0.00 mL mark.
9) Add the NaOH solution from the buret to the sample in the flask while swirling the flask.
At some time during the titration you will see a flash of pink color where the stream of
NaOH mixes with the solution in the flask. When this pink color begins to fade more slowly,
slow the addition of the NaOH solution from the buret. Ideally, the NaOH solution should
be added one drop at a time as the end-point is approached so that the titration can be
stopped when one drop of NaOH solution turns the solution in the flask from colorless to
a permanent but very faint pink. Just before the end-point is reached, rinse the inside of
the flask with the deionized water from your wash bottle. Record the final buret reading at
the end-point on the data table.

Repeat this procedure with the remaining samples and check your precision when four runs are
completed. A "Q Test" may be applied to eliminate the least precise run.

The Equivalent Mass of an Unknown Acid

Unknown Acid ID Number

Normality Std NaOH Soln
 7

Run 1 Run 2 Run 3 Run 4

Mass of unknown acid

Final buret reading

Initial buret reading
Volume NaOH Titrated, mL
Precision mL of NaOH
Check g unknown
Volume NaOH, L

Number Equiv. of NaOH

Number Equiv. of Acid

Equivalent Mass of Acid

Average Equivalent Mass of Acid

Calculations (Include set-up and units):

Questions

1. Given the following reagent equation for the standardization of the stock NaOH solution with
potassium hydrogen phthalate, KHC8H4O4, write the net equation.

KHC8H4O4 (aq) + NaOH (aq)  NaKC8H4O4 (aq) + H2O (l)

2. Given the Lewis structure for KHP, KHC8H4O4,
explain the fact that KHP is quite soluble in water.

3. The inventory of aqueous 1 M H2SO4 is: [H3O+] = 1 M and [HSO4-] = 1 M. Given this
information, write the correct equation(s) for any Brknsted-Lowry acid/base reaction(s) which
occur...

a) when 1 mL of 1M H2SO4 is mixed with 1 drop of 1 M NaOH.

b) when 1 drop of 1 M H2SO4 is mixed with 1 mL of 1 M NaOH

DATA/REPORT
Experiment 2A, Acid-Base Titrations Name
Section Date

Standardization of Stock NaOH Solution

Include correct units and significant figures

Note: KHP L KHC8H4O4 , Molar Mass KHC8H4O4

Run 1 Run 2 Run 3

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Mass of KHP
Moles of KHP
Since KHP is monoprotic, 1 mole KHP = 1 equivalent KHP
Equivalents KHP

Titrations with NaOH Solution

Final buret reading
Initial buret reading
Total Volume NaOH
Titrated, mL
Volume NaOH, L

Normality NaOH
Average Normality NaOH Solution

Calculations (Include set-up and units):

Equivalent Mass of an Unknown Acid

Unknown Acid ID Number

Normality Std NaOH Soln

Run 1 Run 2 Run 3 Run 4

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Mass of unknown acid

Final buret reading

Initial buret reading
Volume NaOH Titrated, mL
Precision mL of NaOH
Check g unknown
Volume NaOH, L

Number Equiv. of NaOH

Number Equiv. of Acid

Equivalent Mass of Acid

Average Equivalent Mass of Acid

Calculations (Include set-up and units):

Questions

1. Given the following reagent equation for the standardization of the stock NaOH solution with
potassium hydrogen phthalate, KHC8H4O4, write the net equation.

KHC8H4O4 (aq) + NaOH (aq)  NaKC8H4O4 (aq) + H2O (o)

 11

3. Given the Lewis structure for KHP, KHC8H4O4,

explain the fact that KHP is quite soluble in water.

3. The inventory of aqueous 1 M H2SO4 is: [H3O+] = 1 M and [HSO4-] = 1 M. Given this
information, write the correct equation(s) for any Brknsted-Lowry acid/base reaction(s) which
occur...

a) when 1 mL of 1M H2SO4 is mixed with 1 drop of 1 M NaOH.

b) when 1 drop of 1 M H2SO4 is mixed with 1 mL of 1 M NaOH

4. SAVE your unknown number and the equivalent mass of your unknown acid as
information to be applied in an upcoming experiment (Experiment 3, Freezing Point
Depression, Molar Mass Determination in t-Butyl Alcohol).