Chemistry 26.

1 Laboratory Manual 1
EXPERIMENT 3
VOLUMETRIC DETERMINATION OF ACETIC ACID IN VINEGAR

OBJECTIVES
1. To understand the concepts involved in a volumetric analysis.
2. To be able to differentiate volumetric and gravimetric types of analysis.
3. To get oriented with titrimetric techniques such as the use of a volumetric flask in
the preparation of solutions and the correct handling of pipets and burets.

INTRODUCTION
Volumetric methods of analysis are generally more rapid than gravimetric methods.
For carrying out volumetric processes, there are several requirements: a reliable balance with
which to weigh standard substances and the material for analysis; analytical glassware in
which to measure the volumes of the solutions employed; standard solutions or solutions the
concentrations of which are accurately known; indicators that will furnish accurate evidence
of the point at which the desired reaction is completed.
The process whereby a standard solution is brought into a reaction is called a titration,
and the point at which the reaction is exactly completed is called the equivalence point. An
indicator shows the end point of the titration, usually by a marked change in color, and ideally
the end point and the equivalence point should coincide. The volume of the standard solution
used and its concentration furnish a measure of the substance being determined. The
mathematics involved in the calculations is known as stoichiometry.
The processes of volumetric analysis are classified as:
1. Neutralization methods — an acidic substance is titrated with a standard solution of
an alkali or base (acidimetry) or a basic substance is titrated with a standard solution
of an acid (alkalimetry)
2. Oxidation-reduction or Redox methods — a reducing substance is titrated with a
standard solution of an oxidizing agent or an oxidizing substance is titrated with a
standard solution of a reducing agent.
3. Precipitation or Saturation methods — a substance is titrated by precipitating it with
a standard solution of a precipitating agent. The calculations should involve the
volume and concentration of the standard solution of the precipitating agent. If the
basis is the mass of the precipitate, then the method will be considered under
gravimetric analysis.
4. Complex formation methods — a substance is titrated with a standard reagent
forming a complex ion.
Neutralization methods will be used in this experiment to analyze vinegar samples.
The principal acid in vinegar is acetic acid, HC 2H3O2 and quality standards require at least 4 g
of acetic acid per 100 mL of vinegar. The total quantity of acid can be readily determined by
titration with a standard solution of base using phenolphthalein indicator. Although other
acids are present, the result is calculated as acetic acid.
 Chemistry 26.1 Laboratory Manual 2
MATERIALS
three 250-mL or 125-mL Erlenmeyer flasks NaOH pellets (AR grade)
500-mL Erlenmeyer flask or beaker solid KHP (AR grade)
500-mL volumetric flask phenolphthalein solution with dropper
250-mL beaker dropper
10-mL delivery pipet analytical balance
buret top-loading balance
wash bottle iron stand with buret clamp
hot plate vinegar sample
clean plastic reagent bottle or PET bottle (500- mL) capacity with cap

PROCEDURE
A. Preparation and Standardization of 0.1 N Sodium hydroxide (NaOH) Solution
Boil 600 mL of distilled water in an Erlenmeyer flask or beaker with a watch glass as
cover for at least an hour. Let water reach ambient temperature. Weigh approximately 2
grams AR grade NaOH pellets in a 250-mL beaker. Add a little of the recently cooled water
and stir until all NaOH particles are completely dissolved. Add more water to ensure
complete dissolution. Transfer the mixture to a clean 500-mL volumetric flask. Wash the
beaker with water and add the washings to the mixture. Perform this at least three times. Fill
the volumetric flask to the mark with water. Transfer the base solution into a clean and
properly labeled plastic reagent bottle.
Clean the buret with soap and water. Use the prepared NaOH solution for the final
rinse and hang the buret upside down in an iron stand for at least 10 minutes to completely
dry.
Obtain KHP standard that has been dried for 1 hour at 110˚C from your instructor.
Using weighing by difference, accurately weigh 0.3 to 0.4 grams of the standard into a clean
and dry
250 mL Erlenmeyer flask. Add 50 mL of water and swirl until all of the solid is dissolved.
Add 2-3 drops phenolphthalein indicator and titrate with the prepared NaOH solution until a
permanent faint pink color is obtained. Record the volume of the base used. Perform 3 trials.
Each group member should perform one trial.

B. Analysis of Vinegar
Record the brand name or if locally produced, the place of production of your vinegar
sample. Pipet out 10 mL of your vinegar sample into a 50-mL volumetric flask and dilute to
mark with distilled water. Transfer 10 mL aliquots into a clean 250-mL or 125-mL Erlenmeyer
flask and add about 10 mL of distilled water. Add 2-3 drops of phenolphthalein indicator and
swirl to mix.
Titrate with the standard base solution until a faint pink color is obtained. Perform
three trials. Each group member should perform one trial. Report the acetic acid content in
g/100 mL of vinegar.
 Chemistry 26.1 Laboratory Manual 3
*Store the unused NaOH in a plastic reagent bottle with cap and save for Experiment 4.

POSTLAB QUESTIONS
1. A certain brand of vinegar is analyzed using a standard NaOH solution. The following data
were obtained:
N of standard NaOH: 0.4789 ± 0.0009
Total V of vinegar: 110.00 ± 0.30 mL
V aliquot of vinegar: 10.00 ± 0.05 mL
V of NaOH used (± 0.10 mL)
Trial# 1 24.95
2 25.10
3 24.90
Calculate the acetic acid content in g/100 mL. Include the relative uncertainties per trial.
Report average values of all calculations and relative uncertainties.

2. Use standard deviation and relative standard deviation (RSD) in % to express the precision
and accuracy of your analysis. Compare with the standard requirement of 4 grams acetic
acid per 100 mL vinegar.

RECOMMENDED REFERENCES
1. Fritz, J.S. and G.H. Schenck, Jr. Quantitative Analytical Chemistry, 6 th ed. Allyn and Bacon,
Boston, 2003.
2. Hamilton, L.F. and Simpson, G. Quantitative Chemical Analysis, 15th ed. J Marnillan Co.,
New York, 1980.

Waste Disposal: 1. All neutralized solutions to sink, flush with water

2. Unused NaOH should be collected separately (additional bottle)
 Chemistry 26.1 Laboratory Manual 4
EXPERIMENT 3
VOLUMETRIC DETERMINATION OF ACETIC ACID IN VINEGAR

NAME: _________________________________ SECTION: ___________________

GROUP NO.:_______ DATE STARTED: ____________
DATE FINISHED: ____________

DATA
A. Standardization of NaOH solution
Trial 1 Trial 2 Trial 3
Mass of KHP standard (±_______g)
Initial mass ______________ _____________ ______________
_
Final mass ______________ _____________ ______________
_
Mass KHP used ______________ _____________ ______________
_
Volume of NaOH (±________mL)
Initial volume ______________ _____________ ______________
_
Final volume ______________ _____________ ______________
_
Volume of NaOH used ______________ _____________ ______________
_

B. Analysis of Vinegar
Brand name of vinegar or place of production, if locally produced __________________

Trial 1 Trial 2 Trial 3

Volume of vinegar aliquot _____________ _____________ ______________
_ _
Volume of NaOH (±_______mL)
Initial volume _____________ _____________ ______________
_ _
Final volume _____________ _____________ ______________
_ _
Volume of NaOH used _____________ _____________ ______________
_ _

CALCULATED RESULTS
Trial 1 Trial 2 Trial 3
 Chemistry 26.1 Laboratory Manual 5
Normality of NaOH (eq/L) _______±_______ _______±_______ _______±_______
Mean N of NaOH _______±_______
Acetic acid content (g/100 _______±_______ _______±_______ _______±_______
mL)
Mean acetic acid content _______±_______

STATISTICAL ANALYSIS OF AVERAGE ACETIC ACID CONTENT

Standard deviation ________________
Relative standard deviation ________________
 Chemistry 26.1 Laboratory Manual 6
PRELABORATORY REPORT FOR EXPERIMENT 3
Volumetric Determination of Acetic Acid in Vinegar

NAME: _________________________________
SECTION: _______________________________
DATE: __________________________________

1. Briefly define or describe the following:

a. Standardization in analytical work

b. Primary standards

c. Secondary standards

d. Aliquot

e. Technique of weighing by difference

f. Volumetric analysis

g. Titrimetric analysis

2. Give the balanced chemical equation pertinent to the reaction between acetic acid and
NaOH.
 Chemistry 26.1 Laboratory Manual 7
EXPERIMENT 4
DETERMINATION OF ASPIRIN BY INDIRECT TITRATION

OBJECTIVES
1. To evaluate the purity of an aspirin sample.
2. To develop the techniques for the proper dilution of a solution to a definite volume
and the use of a volumetric pipet.
3. To learn how to carry out calculations involving back-titration.

INTRODUCTION
Direct titration methods are those in which the substance to be measured (or a
constituent chemically equivalent to it) is directly titrated to an end point by a standard
solution. Indirect methods do not involve measuring the substance itself but a quantity of a
reagent is added which is known to be in excess with respect to a specific reaction, and the
unused excess is determined by titration.
Aspirin is a compound derived from two acids, acetic acid and salicylic acid. It can be
hydrolyzed by alkali and the two components neutralized simultaneously.
The weak acid salts of acetic acid and salicylic acid would give a pH at the equivalence
point that lies within the range of phenol red indicator (pH 6.8-8.4), although phenolphthalein
may be used. The procedure given is an indirect one since it degrades the aspirin. More
sophisticated methods such as HPLC or quantitative TLC can readily analyze intact aspirin. It
is quite important to distinguish between intact aspirin and its degraded form in assessing
the potency of the drug.

MATERIALS
250 mL Erlenmeyer flask standard 0.1 N NaOH solution (from Expt. 3)
250 mL Volumetric Flask concentrated HCl solution
100 mL Volumetric Flask phenol red and phenolphthalein indicator
20.00 mL pipette clean reagent bottle
50.00 mL pipette ordinary pan/digital balance
50.00 mL acid burette analytical balance
50.00 mL base burette hot plate
25.00 or 50.00 mL graduated cylinder
aspirin sample (tablet or sample from Chem 31.1)

PROCEDURE
A. Preparation and Standardization of 0.1 N HCl Solution
Prepare 250 mL 0.1 N HCl solution using a volumetric flask. Let instructor check your
calculations before proceeding with the preparation. Store prepared solution in a clean and
properly labeled reagent bottle.
Pipet out 20.00 mL of the prepared acid solution into a 250 mL Erlenmeyer flask. Add
 Chemistry 26.1 Laboratory Manual 8
2-3 drops phenolphthalein. Titrate with the standard NaOH solution until a permanent faint
pink color is achieved. Perform 3 trials.

B. Analysis of Aspirin
Weigh out to the nearest tenth of a milligram 0.1 g of previously ground aspirin
sample into a 250 mL Erlenmeyer flask. Add 50.00 mL of standard 0.1 N NaOH solution.
Simmer gently for 10-15 minutes to hydrolyze the aspirin sample.
Cool the reaction mixture and transfer into a 250 mL volumetric flask. Wash the flask
several times with distilled water and pour into the volumetric flask. Dilute the reaction
mixture and washings to the mark with distilled water, then mix well by several inversions of
the stoppered flask.
Titrate 50.00 mL aliquot portions of the stock solution of hydrolyzed aspirin with the
standardized HCl solution using 2-3 drops indicator to a yellow end point. Make 3 trials.

POST-LAB QUESTIONS
1. What would be the effect of a more dilute solution of NaOH on the back titration?
2. What volume of 1.00 N NaOH is used in the hydrolysis of four 250 mg tablets of aspirin
(90% pure acetylsalicylic acid) if 10.00 mL of 0.0500 N HCl is consumed in the back
titration?
RECOMMENDED REFERENCES
1. Blaedel, W.J. And V.W. Melonche, Elementary Quantitative Analysis: Theory and Practice. 2nd
ed. Harper and Row, New York, 1993.
2. Christian, G., Analytical Chemistry, 3rd ed. John Wiley and Sons, New York, 1980.
3. Laboratory Manual for Elementary Analytical Chemistry, UP Diliman, 2nd ed., 1994.

Waste Disposal: 1. All neutralized solutions to sink, flush with water

2. Mix equal volume of HCL and NaOH until neutral then discard to
sink
 Chemistry 26.1 Laboratory Manual 9
EXPERIMENT 4
DETERMINATION OF ASPIRIN BY INDIRECT TITRATION

NAME: _________________________________ SECTION: ___________________

GROUP NO.:_______ DATE STARTED: ____________
DATE FINISHED: ____________

DATA
A. Preparation and Standardization of NaOH solution
Normality of concentrated HCl ______________
Volume of HCl used to prepare 0.1 N ______±_______

Normality of standard NaOH ________±_______

Trial 1 Trial 2 Trial 3
Volume of HCl titrated (±_______) _____________ ______________ ______________
_
Volume of NaOH used (±_______) _____________ ______________ ______________
_
Normality of HCl ______±______ ______±_______ ______±_______
_

Mean normality of HCl ______±_______

RSD ______________

B. Analysis of Sample

Mass of ASA sample (±_________) ______________

Trial 1 Trial 2 Trial 3
Volume aliquot (±_________) _____________ ______________ ______________
_
Volume of HCl used (±_________) _____________ ______________ ______________
_
Mass ASA in sample (grams) ______±______ ______±_______ ______±_______
_
% ASA _____________ ______________ ______________
_
Mean mass ASA ______±_______
RSD ______________
Mean % ASA ______________
Chemistry 26.1 Laboratory Manual 10
 Chemistry 26.1 Laboratory Manual 11
PRELABORATORY REPORT FOR EXPERIMENT 4
Determination of Aspirin by Indirect Titration

NAME: _________________________________
SECTION: _______________________________
DATE: __________________________________

A. Provide the following information for acetylsalicylic acid (ASA):

1. Chemical Formula

2. Formula Mass

3. Number of acidic protons or H+ per particle

4. Chemical Structure

2. Give the balanced chemical equation pertinent to the reaction between ASA and NaOH
during hydrolysis.

3. Define back titration.

4. Give an example of an analysis where back titration is employed.

 Chemistry 26.1 Laboratory Manual 12
EXPERIMENT 5
DETERMINATION OF IRON IN IRON SUPPLEMENTS BY REDOX TITRATION

OBJECTIVES
1. To learn the technique and calculations involving blank titration.
2. To determine the iron content of a sample using oxidation-reduction reaction.
3. To illustrate the use of self-indicating agent.

INTRODUCTION
The amount of an oxidant present in a sample is determined by titrating with a
standard solution of reducing agent. Similarly, the reducing capacity of a substance may be
obtained by titrating against a standard solution of an oxidizing agent.
Potassium permanganate is a strong oxidizing agent which quantitatively oxidizes
most of the common reducing agents when added in equivalent amount. The intense purple
color of the permanganate ion serves as a self-indicator; one drop in excess will impart a
distinct color to a large volume of solution.
There are, however, some undesirable qualities of permanganate. Care must be taken
in preparing a standard solution of this reagent that is free of reducing agents, for any
reduction occurring after the solution is prepared causes MnO 2 to precipitate, and the solid
MnO2 particles in the solution catalyze further decomposition. Light also causes
decomposition of the solution; the solution should be kept in a dark bottle if the solution is
intended to be a permanent standard. Even with precautions, KMnO4 solutions may show
decomposition with time, and it is advisable to restandardize the solution at frequent
intervals.
Commercially available iron supplements typically contain iron(II) sulfate or ferrous
sulfate, ferrous gluconate, ferrous fumarate, etc. This medication is used to treat or prevent
low levels of iron in blood as in the case of anemia. Iron is essential in the production of red
blood cells and in growth and development. The different forms of iron in supplements
contain varying amounts of elemental iron, which are usually indicated on the packaging.

MATERIALS
600 mL beaker vacuum pump
250 mL beaker thermometer
50 mL graduated cylinder stirring bar
125 mL or 250 mL Erlenmeyer flasks top-loading balance
100 mL volumetric flask analytical balance
50 mL burette hot plate with magnetic stirrer
10 mL pipets mortar and pestle
watch glass AR grade KMnO4
sintered glass or Gooch filtering crucible AR grade Na2C2O4
suction or filtering flask 18 M H2SO4
 Chemistry 26.1 Laboratory Manual 13
glass-stoppered amber bottle
iron supplement tablets/pills/capsules
PROCEDURE
A. Preparation and Standardization of 0.02 N KMnO4 Solution
Weigh on a watch glass or small beaker approximately 0.35 g reagent-grade potassium
permanganate (KMnO4) crystals. Dissolve in 500 mL of distilled water, and either heat in a
covered beaker for 2 hours on a steam bath or boil the solution for 10-15 minutes (Note 1).
Allow the covered beaker to stand overnight in the locker. Then, filter (Note 2) through a
filtering crucible connected to a vacuum pump (Note 3). Store in a clean, glass-stoppered
amber bottle and keep in the dark except when in use. Subsequent decomposition of the
solution can be recognized by the appearance of a brown coating on the walls and bottom of
the bottle.
Accurately weigh three 50-75 mg samples of dry sodium oxalate (Na 2C2O4), in wide-
mouth 250 mL Erlenmeyer flasks. Prepare approximately 1 M sulfuric acid (H2SO4) solution by
pouring about 28 mL concentrated H2SO4 into 500 mL of distilled water. Dissolve the Na 2C2O4
sample in 75 mL of the prepared acid.
Heat the solution (Note 4) to 80-90°C and titrate slowly with the KMnO 4 solution with
automatic stirring using a stirring bar. The end point is a faint pink color that persists for
about 30 seconds. Obtain a blank by heating 75 mL of the prepared 1 M H 2SO4 to 80°C and
titrating with the KMnO4 solution. From the corrected volume of KMnO 4 and the weight
purity of the standard, compute the normality of the KMnO 4. The RSD for three trials should
not exceed 4%.

Notes:
1. Distilled water may contain organic matter which will reduce permanganate. The solution is
heated in order to hasten the oxidation of this material and coagulate the precipitate of
manganese dioxide (MnO2), which forms as a reduction product.
2. All particles of MnO2 should be removed since these particles catalyze further decomposition of
the solution.
3. Filter paper should not be used since particles of the paper suspended in the solution would
lead to further reduction.
4. Place a thermometer in the flask for accurate measurement of the temperature. Remove and
rinse off the thermometer with a small stream of water before titration. Recheck the
temperature just before the end point is reached; if necessary, reheat the solution.

B. Analysis of Iron Tablets

Obtain 2-3 tablets and record the indicated elemental iron content. Grind tablets and
transfer all the ground materials in an Erlenmeyer flask or small beaker. Add about 50 mL of 1
M H2SO4 and swirl to dissolve. Let the residue settle and filter into a 100 mL volumetric flask.
Wash the Erlenmeyer flask and filter paper with the acid several times, adding the washing to
the volumetric flask. Make up to mark with 1 M H2SO4. Invert the flask several times to mix.
Pipet 20 mL aliquot into an Erlenmeyer flask and add 30 mL of 1 M H 2SO4. Titrate with
the standard KMnO4 to a faint pink or purple endpoint. Make at least 3 trials. Perform a blank
measurement by titrating 50 mL of 1 M H 2SO4. Calculate the mass iron per tablet in your
sample and compare to the indicated amount in the packaging.

POST-LAB QUESTIONS
1. What chemical species is the reducing agent in the standardization step? The oxidizing
agent?
2. Other oxidizing agents are also employed for the determination of iron in an unknown
sample. What is one obvious advantage of KMnO 4 over K2Cr2O7 and Ce(SO4)2 as
oxidant in the determination of iron?
3. What are the reasons for using 1M H 2SO4 in the standardization of KMnO 4 and in the
preparation and analysis of iron tablets?
4. Why should the Na2C2O4 solution be heated when being titrated with KMnO 4 during
standardization?

RECOMMENDED REFERENCES
1. Fritz, J.S. And G.H. Schenck, Jr. Quantitative Analytical Chemistry. 6 th ed. Allyn and
Bacon, Boston, 2003.
2. Hamilton, L.F. And Simpson, G. Quantitative Chemical Analysis. 15 th ed J. Mcmillan
Co., New York, 1980.
3. Laboratory Manual for Elementary Analytical Chemistry. UP Diliman, 2nd ed., 1994.
4. Pierce, W. C., E.L. Haenisch and D.T. Sawyer. Quantitative Analysis. 7 th ed. John Wiley
and Sons, Inc. 1999.

Waste Disposal: 1. Reaction mixture with KMnO4 to heavy metal waste

2. Excess KMnO4 to heavy metal waste
3. Excess H2SO4 to acid waste
 EXPERIMENT 5
DETERMINATION OF IRON IN IRON SUPPLEMENTS BY REDOX TITRATION

NAME: _________________________________ SECTION: ___________________

GROUP NO.:_______ DATE STARTED: _____________
DATE FINISHED: _____________

DATA AND CALCULATED RESULTS

A. STANDARDIZATION OF 0.02N KMnO4

1 2 3
Final mass of Na2C2O4 & vial (±______g) ____________ ____________ ____________
Initial mass of Na2C2O4 & vial (±______g) ____________ ____________ ____________
Weight purity of Na2C2O4 (_________%)
Mass of Na2C2O4, g (±______ g) ____________ ____________ ____________
Initial burette reading (±____ mL) ____________ ____________ ____________
Final burette reading (±____ mL) ____________ ____________ ____________
Volume KMnO4 used in blank (±___ mL) ____________
Corrected Volume of KMnO4 (±____ mL) ____________ ____________ ____________
Normality of KMnO4 ______±_____N ______±_____N ______±_____N
Mean Normality of KMnO4 __________±________N
Standard Deviation ____________
Relative Standard Deviation (%) ____________

B. ANALYSIS OF IRON TABLETS

Generic and Brand name of sample ________________________
Number of tablets used: _________ 1 2 3
Initial burette reading (±____ mL) ____________ ____________ ____________
Final burette reading (±____ mL) ____________ ____________ ____________
Volume KMnO4 used in blank (±___ mL) ____________
Corrected Volume of KMnO4 (±____ mL) ____________ ____________ ____________
Mass of Iron in sample ______±_____mg ______±_____mg ______±_____mg
Mass of Iron per tablet ______±_____mg ______±_____mg ______±_____mg
Mean mass of Iron per tablet _________±_______mg
Manufacturer's indicated amount (as Fe) _____________mg
Relative Error (ppt) _______________
PRELABORATORY REPORT FOR EXPERIMENT 5
Determination of Iron in Iron Supplements by Redox Titration

NAME: _________________________________
SECTION: _______________________________
DATE: __________________________________

1. What is an oxidation-reduction reaction?

2. Why is blank titration needed in this analysis? How is this integrated in the calculations?

3. What is a self-indicating agent?

4. Give the balanced net ionic equations pertinent to each of the following:
a. Reaction between potassium permanganate and sodium oxalate in standardization step.

b. Reaction between ferrous and permanganate ions in an acidic medium.