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FINAL LABORATORY REPORT

EXPERIMENT 1: DETERMINATION OF TOTAL ACIDITY OF VINEGAR

Don King O. Evangelista1, Geneizzel B. Gotuato1, Jackielyn B. Ocbina1, Jann Andre H. Padua1
1

Group 2, III-Bachelor of Science in Chemistry for Teachers, Philippine Normal


University

Performed June 21, 2012


Professor Allen A. Espinosa, CHEM5 Professor

ABSTRACT
The experiment aims to determine the accurateness of
the data presented by vinegar-manufacturing factories in
the Philippines as their acetic acid content in their labels
using the direct titration method, specifically the analyte
Datu Puti. Three samples of 25.0 mL aliquot volumes were
titrated using the KHP-standardized NaOH sample which is
found to be of 0.05962 M using the indicator
phenolphthalein with observance to its equivalence point.
Data shows that the percent acetic acid of Datu Puti whether
by weight or by volume is less than the alleged 8% acetic
acid content according to its label, but with consideration to
the computed relative error of 35.73%. The experimenters
commend the titration process but recommend to lessen
errors such as systematic and instrument errors.

I. Introduction
Acid-base titrations are used routinely in virtually all fields of chemistry and in
related areas, such as biology, pharmacy, medicine and geology. In addition to
inorganic compounds, thousands of organic compounds exhibit sufficient acidity and
basicity that they can be determined by titration. Excellent understanding of acidbase properties, together with the relative ease, speed and low-cost of performing
titrations, are major factors contributing to the popularity of the acid-base titration. 1
In this experiment, an organic compound, household vinegar which is mainly used
in cooking and bleaching, is subjected to the titration process, specifically direct
titration, for analyses of its concentration and percent acetic acid as compared to its
reported percent acetic acid written on its labels. Direct titration is a kind of titration
where the reactants involved are primarily the titrant and the analyte aA + tT pP.
2

This experiment aims to (1) Test the reliability of the reported vinegar content
of acetic acid in the label by titration process, (2) Experience how analysts go over
1

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

the processes of quantitative analysis through the experiment and (3) Manifest
appreciation of Chemistry by maintaining accuracy and precision in the experiment
without sacrificing time and resources.
Generally, titrations are performed to determine the amount of analyte
present in a sample. To do this, the volume of titrant needed to reach the
equivalence point must be measured. An equivalence point by definition means
occurs when all the moles of H+ ions present in the original volume of acid
solution have reacted with an equivalent number of moles of OH- ions added
from

the

buret.4 These equivalence points were determined most often by

chemical indicators, in this case phenolphthalein, primarily because of the inherent


simplicity of this technique, but also because of availability of many excellent
indicators. These acid-base indicators are weak organic acids or bases whose
conjugate forms different colors. The indicator acts as a second acid or base in the
solution being titrated and must be weaker than the analyte acid or base so that it
reacts last with the titrant. The amount of indicator added must be kept small
compared to that of the analyte present so that it does not consume an appreciable
amount of titrant in the process of indicating or changing from one conjugate form
to the other. For this reason, indicators must be very intensely colored so that only a
few drops of a dilute solution, for this experiment, phenolphthalein with a color of
pink, are needed to produce a color that is observed by the eye.

Before titration, the standardization of the molarity of NaOH must be made


using potassium hydrogen phthalate, often abbreviated KHP with a molecular
formula of KHC8H4O4. This compound has a high equivalent weight and is not
hygroscopic. This compound, being a weak acid, the pH at the equivalence point of
its titration with a strong base is in the alkaline region makes it as a good primary
standard on standardizing bases.
Acetic acid, the acid found in vinegar, is in definition a weak acid. Therefore,
the titration to be made is a weak acid titration to a strong base, which is NaOH. The
reaction of this titration is:
CH3COOH + OH- CH3CO2- + H2O1
In this reaction, we can divide it into four. Before the addition of the titrant,
the main constituent is only the acetic acid, which the experimenters will treat as a
weak acid. Before the equivalence point, acetic acid is also present plus the
2

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

presence of CH3COONa that is now a buffer. At the equivalence point, CH 3COONa is


only present which a weak base is now. After the equivalence point, CH 3COONa is
present plus NaOH, which is now a strong base.

Another concept is that vinegar has a high acid concentration, thus it is good
to dilute the sample by incorporating aliquots to it. By diluting it, the quantity of the
acetic acid in the bottle of vinegar can be determined by introducing a dilution
factor. This factor will relate the amount of acetic acid in the diluted vinegar
solution per volume of portions of the aliquot.

With these concepts in hand, the percent by weight and percent by volume of
acetic acid in the sample can now be easily determined and calculated.
II. Methodology
Ample amounts of vinegar from the bottle of Datu Puti randomly picked in the
supermarket were undergone in an analysis. This was undergone into a quantitative
analysis using direct titration and phenolphthalein as an indicator against sodium
hydroxide to determine the acetic acid content. The following are the procedures in
the direct titration process:
First, standardize the prepared assumed .1M NaOH against KHP in three trials
with ranges of weights from 0.2 to 0.3 g. These samples were distilled in 50 mL of
distilled water and was titrated with phenolphthalein indicator as endpoint.
According to the data, the NaOH called for 16.07 mL, 18.22 mL and 17.32 mL for
the 0.195 g, 0.2171 g and 0.2074 g samples of KHP respectively.
Next, the density of the vinegar, denoted by d = m/v, is measured by the
different groups by the process of weighing and concept of the Archimedes principle
which deducts the mass of the container itself. From these data, the experimenters
got the average mass of the 10 mL vinegar versus the volumes and found out that
the average density of vinegar is 0.98706 g/mL.
Lastly, the standardized NaOH from the first part, which is now measured
with concentration of 0.05962 mol/L (M) was now utilized to direct titrate the three
samples of vinegar aliquot with phenolphthalein indicator. The vinegar aliquot is
produced by diluting a 25-mL sample of pure vinegar with 250-mL of volumetric
flask. Then, the titration proceeded. Phenolphthalein endpoint is indicated by a faint
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Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

pink color, exceeding this pink color means that the titration is above its endpoint.
According to the data tables, each 25.0 mL aliquot of acetic acid needed volumes of
37.4 mL, 35.9 mL and 46.9 mL of NaOH for the three trials respectively.
The photo that follows shows the reactions and the succession of the titration
process:

Figure 1: The Titration Process (from: Chemistry, The Molecular Nature of Matter and
Change 4th Edition by Silberberg)

After gathering all the data from the three parts, these data is plotted in data
tables and are subject for statistical treatments, specifically the usage of the mean,
which indicated the central measurement and the deviation, standard deviation,
variance and coefficient of variance which are measures of variability.
The schematic diagram on the following page explains and summarizes all
procedures done in the experiment.

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

III. Data and Results with Sample Calculations


The following data tables were computed first using a scientific calculator
then rechecked using MS Excel.
Table 1: Data for the Standardization of prepared 0.1 M NaOH
Details
Mass of KHP (g)
mmol of KHP (204.23 g/mol)
mmol of NaOH
Final volume of NaOH (mL)
Initial volume of NaOH (mL)
Delivered volume of NaOH (mL)
Molarity of NaOH (mmol/mL or M)
Average Molarity (mmol/mL or M)
Deviation
Relative Deviation
Standard Deviation
Coefficient of Variance

1
0.195
0.9548
0.9548
16.07
0.00
16.02
0.0596
0.00002
3.35 x 10-4

Trial
2
0.2171
1.0680
1.0680
18.22
0.20
18.02
0.0589
0.05962
0.00072
0.01207
0.00105
1.7611 %

3
0.2074
1.0155
1.0155
17.32
0.50
16.82
0.06037
0.00075
0.01257

Supporting Calculations for Table 1 (using Data in Trial 1 with reference to Table 1)

mmol

of

( 0.195 g KHP )

KHP

1 mole KHP 1000 mmol KHP


=0.9548 mmol KHP
( 204.23
g KHP )( 1 mole KHP )

Balanced equation of NaOH and KHP


NaOH + KHC8H4O4 KNaC8H4O4 + H2O
Mole ratio: 1 mmol of NaOH = 1 mmol of KHP, thus, mmol of NaOH corresponds also
to each mmol of KHP, therefore, mmol of NaOH = mmol of KHP.
Molarity of NaOH =

mmol NaOH
=0.0596 M NaOH
( 0.9548
16.02mL NaOH )

Average

Molarity

of

NaOH

( 0.0596 M + 0.05893 M +0.06037 M )=0.05962 M NaOH


Deviation (|d|) = M Mave
6

d1 = 0.0596 0.05962 = 0.00002


Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

d2 = 0.0589 0.05962 = 0.00072


d3 = 0.06073 0.05962 = 0.00075
Relative deviation (dr) = di/M
dr1 = 0.00002 / 0.05962 = 3.35 x 10-4
dr2 = 0.00072 / 0.05962 = 0.01207
dr3 = 0.00075 / 0.05962 = 0.01257
Standard

Deviation

(s)

d i2
(0.00002+0.00072+0.00075)2
=
=1.05 1030.00105
n1
31

Coefficient of Variance (CV) =

S
0.00105
100 =
100 =1.7611
M
0.05962

Table 2: Determination of Average Density and Mass of Vinegar


Entry
Volume of Vinegar (mL)
Mass of 50-mL beaker (g)
Mass of beaker + 10 mL vinegar
(g)
Mass of 10 mL vinegar (g)
Average mass of 10 mL vinegar (g)
Average density (g/mL)

1
38.0696
48.0853
10.0157

Volume of Vinegar taken from bottle (mL)

Mass of vinegar (g)

Volume Added
2
10.00
40.0615
49.7062
9.6447
9.8706
0.98706 g/mL
25.00
24.6765 g

3
29.0932
39.0447
9.9515

Supporting Calculations for Table 2


Mass of 10 mL vinegar (g) = (Mass of beaker + 10 mL vinegar) Mass of beaker
= 48.0853 38.0696
= 10.0157 g
Average Mass of 10 mL vinegar = (Sum of Three masses) / 3
= (10.0157 + 9.6447 + 9.9515)/3
=9.8706 g/mL
Average Density = Average Mass / Volume
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Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

= 9.8706 g / 10.00 mL
= 0.098706 g/mL
Mass of vinegar from Vinegar Taken from Bottle:
Density of vinegar = mass of vinegar / volume of vinegar
Therefore: Mass of vinegar = (density of vinegar)(volume of vinegar)
Since: Density of vinegar does not change (Intensive property)
Mass of Vinegar = (0.098706 g/mL)(25 mL)
= 24.6765 g
Table 3: Data on Determination of Datu Putis Acetic Acid Content
Details
1
Average Molarity of NaOH (Table 1) (mmol/mL)
Final volume of NaOH (mL)
Initial volume of NaOH (mL)
Delivered volume of NaOH, Vf Vi (mL)
Volume of aliquot (mL)
mmol NaOH
mmol CH3COOH in aliquot
Volume of Aliquot (mL)

37.4
0.00
37.4
2.2297
2.2297

Volume of Diluted Vinegar in Volumetric flask (mL)

Dilution Factor
mmol CH3COOH in volumetric flask (mL)
Mass of CH3COOH (60.06 g/mol) (g)
Mass of 25.0 mL vinegar (from table 2)
% CH3COOH (w/w)
Average % of CH3COOH
Molarity of Vinegar (Acetic acid soln,
mmol/mL)
% CH3COOH (w/v)
Average % CH3COOH (w/v)
Deviation
Relative Deviation
Standard Deviation
Coefficient of Variance
Accepted % acid value (from vinegar label)
Absolute error (E)
Relative error (Er ,%)

22.297
1.3393
24.6765
5.4276
0.053572
5.3572%
0.3814
0.9335

| -2.6428|
33.035%

Trial
2
0.05962
35.9
0.00
35.9
25.0
2.1403
2.1403
25.0
250.0
10
21.403
1.2854
24.6765
5.2090
5.8138%
0.051416
5.1416%
5.7386%
|-0.2156|
0.8907
1.3838
24.1138%
8%
|-2.8584|
35.73%

3
46.9
0.00
`46.9
2.7961
2.7961

27.961
1.6793
24.6765
6.8052
0.067172
6.7172%
1.36
1.1705

|-1.2828|
16.035%

Supporting Calculations for Table 3 using Trial 1

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

( 37.4 mL NaOH )

mmol of NaOH =

NaOH
( 0.05962mLmmol
)=2.2297 mmol NaOH
NaOH

Balanced equation of NaOH and KHP


CH3COOH + NaOH H2O + NaC2N3O3
Mole ratio: 1 mmol of NaOH = 1 mmol of acetic acid, thus, mmol of NaOH
corresponds also to each mmol of acetic acid, therefore, mmol of NaOH = mmol of
acetic acid.
mmol of acetic acid = 2.2297 mmol NaOH
mmol

of

CH3COOH

( 2.2297 mmol acetic acid )


mass

of

aliquot

vinegar
=22.297 mmol AceAcid
( 250mL
25 mL aliquot )

CH3COOH

( 22.297 mmol acetic acid )

in

in

volumetric

flask

mmolacet . acid
1g
=1.3393 g AceAcid
( 60.06
)(
1mmol acet . acid
1000 mg )

Molarity = 1.3393 g / 25 mL = 0.053572 M


% acetic acid (w/v) = (1.3393 g/ 25 mL) x 100 % = 5.35%
% acetic acid (w/w) = (1.3393 g/(25 mL x 0.98706 g/mL)) x 100% = 5.4272%
Absolute error for (w/v) = 5.3572 % - 8% = |-2.6428|
Relative error for (w/v) = (2.6428/8) x 100% = 35.73%
IV. Discussions and Guide Questions
According to the data tables shown in the third part of the report, these three
points are noted.
(1) The expected molarity of the standard base NaOH falls short than expected.
According to Table 1 which shows the standardization of prepared 0.1 M
NaOH against KHP, the average molarity of the solution is roughly 0.05962 M,
almost half than expected. Some factors that can be accounted for is the reaction of
solid sodium hydroxide with atmospheric carbon dioxide. This is the most
troublesome aspect of NaOH, as it reacts with atmospheric carbon dioxide in a
reaction CO2 + 2OH- CO32- + H2O. Both the solid reagent and its solutions can
9

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

react this way; consequently, an already standardized sodium hydroxide solution


must be protected from atmospheric CO 2, thus before preparation, distilled water is
boiled because often distilled water is saturated with carbon dioxide and after
preparation it is immediately capped. Although the concentration of NaOH is
reduced when it comes to contact with carbon dioxide, its reactive capacity towards
acids may not change. Unfortunately, the most common application of sodium
hydroxide titrants are for the titration of weak acids, which require an indicator with
a basic transition range, for this experiment, is phenolphthalein. In this case, each
carbonate ion will be titrated to bicarbonate, reacting with only one hydronium ion
for the analyte in the reaction: CO32- + H3O+ HCO3- + H2O. As a result, the
effective concentration of the base solution is decreased and a determinate error
will be incurred as we can see in the results.
(2) The concentration of acetic acid in the vinegar is considerably low as compared
to its reported concentration.
Seen on Table 3, we can infer that more or less, the amount of acetic acid in
the vinegar itself is 71% lower than expected. The experimenters got an average of
5.7386 than of the accepted value of 8%. A factor that can be considered is that
they may have other acids that can interfere with the results of the experiment, for
example, the carbonic acid formed with carbon dioxide.
(3) The data is not accurate but precise.
According to the statistical treatment done to the data tables, the data is
precise because the deviations between the data is small and is supported by the
coefficient of variance, however, it is not accurate because there is a large error in
the data as manifested by the results of the absolute and relative errors computed.
The following are other points and the answers to the guide questions for
discussion in reference to the guide questions drawn from the laboratory manual.
[1] There is a need to boil distilled water since that distilled water is saturated with
carbon dioxide. The reaction is discussed above on the first point.
[2] The reaction of phenolphthalein with NaOH is as follows:
HC2H3OH
HIndic

10

(aq)

+ NaOH
+ H 2O

(aq)

H 2O

(l)

+ NaC2H3

(aq) (TITRATION RXN)

H3O + Indic-

(INDICATOR RXN)

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

Figure 2: Shift of electrons in phenolphthalein that indicates its color. (Retrieved from:
Fundamentals of Analytical Chemistry 5th Edition)

[3] The faint pink color of phenolphthalein indicates that it reached its endpoint,
therefore, the number of moles of H+ is equal to the number of OH ions in the
solution. This color must be taken because excess of this will lead to an error
(darker pink color), as the equilibrium is disturbed. The factors that affect the
endpoint sharpness in this titration is the pH range of the selected indicator and the
distinction of the person of the color itself.
[4] The standard reagent is a strong base rather than a weak base because a weak
base will result in partial dissociation of the ions rather than if the base is strong,
even if the acid is weak, the dissociation becomes complete and a 1:1
stoichiometric ratio is achieved.
[5] As said in the preceding page, the data is not accurate but precise.
[6] The errors that are committed in this experiment are the following:
6.1 Determinate Errors
6.1.a Method Error. As said in the first point of the discussion part,
the molarity of the standardized NaOH is lower than to the expected. Therefore, the
titration period became longer, and can trigger contamination within the NaOH with
its longer contact time with atmospheric conditions. The experimenters accept the
11
Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

fact that the distilled water is not totally boiled and that NaOH was not secured
immediately, that most probably be the cause of the error. Another point is that
three days is the gap between the preparation of the NaOH stock and the
standardization with KHP.
6.1.b Instrument Error. Instrument errors are inevitable since they
are only machines that do their functions. The analytical balance, due to its age, is
hard to tare and has the tendencies to have errors. It is greatly manifested by the
fact that vinegar is expected to have a density greater than 1.00 g/mL which is the
density of water since vinegar has more components than of water. Deriving the
relationship of mass (components) with density, it is expected as there is higher
mass, the density also increases.
6.1.c Personal Judgment Error. Measuring using pipet and burette is
hard, since there is called a parallax error or viewing error. This can be eliminated as
well.
6.2 Indeterminate Error
6.2a Constant Error. As said in the discussion part, there is a
speculation of other acids present in the vinegar, for example, carbonic acid, lactic
acid and such acids that can be formed during the fermentation process of the
vinegar. Lactic acid is produced during fermentation in line with carbon dioxide.
Therefore, this error is constant error and unavoidable.
V. Conclusions and Recommendations
In conclusion, the experiment Determination of Total Acidity of Vinegar
assessed the concentration of acetic acid in a famous brand of vinegar Datu Puti
by comparing the reported value of acetic acid versus experimental value. Direct
titration process is employed with NaOH as standard base and phenolphthalein as
indicator. Results showed that the concentration of acetic acid in Datu Puti falls
considerably short rather to the reported value, however, this result has an error
with a range of 35% that is accumulated through many errors, most of them
manipulative and can be avoided.
The experimenters recommend the following points to be considered if the
same experiment would be repeated. First, take note that distilled water must be
boiled to remove the saturated carbon dioxide from the water that interferes with
12

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

the data. Second, NaOH must be on its considerable concentration, therefore, must
be prepared in advance and standardize in advance to reduce time consumption.
Lastly, it would be best if titration must be done in different varieties of vinegar to
find out if which of the vinegar brands had the closest value to their reported
concentration in their labels and which of them is the most acidic.
VI. References
A. Directly Cited Books
(The superscripts here also refer to the superscripts that were used in the
introduction, thus the parts where superscripts are found are cited and the
references were found here.)
1

Harris, Larry G. (1988). Analytical Chemistry (1st Edition). New Jersey. Prentice-Hill

Inc. pp. 94-109.


2

DLSU Chemistry Faculty. (unpublished). Analytical Chemistry 1 Instructional

Materials.
3

Silberberg, Martin S. (2006). Chemistry: The Molecular Nature of Matter and

Change. New York: Mc-Graw Hill. pp.118-119.


4

Roque, Adolfo P. (unpublished). Analytical Chemistry Laboratory Manual.

B. Photo Credits
Harvey, David. (2000). Modern Analytical Chemistry. New York: McGraw Hill.
pp. 284-287 (Electronic Format)
Skoog, Douglas A., et al (2004). Fundamentals of Analytical Chemistry (8th
Edition). Canada: Brooks/Cole. pp. 368-375 (Electronic Format)
Silberberg, Martin S. (2006). Chemistry: The Molecular Nature of Matter and
Change.(4th Edition) New York: Mc-Graw Hill. pp.118-119. (Electronic Format)

If you are wise and understand Gods ways, prove it by living an honorable life, doing good works
with the humility that comes from wisdom. But if you are bitterly jealous and there is selfish
ambition in your heart, dont cover up the truth with boasting and lying. For jealousy and selfishness
are not Gods kinds of wisdom. Such things are earthly, unspiritual and demonic. For wherever there is
jealousy and selfish ambition, there you will find disorder and evil of every kind.
But the wisdom from above is first of all pure. It is also peace loving, gentle at all times and
willing to yield to others. It is full of mercy and good deeds. It shows no favoritism and is
always sincere. And those who are peacemakers will plant seeds of peace and reap a harvest of
righteousness.
James 3:13-18 (NLT)
/dke

13

To God be the glory!

Determination of Total Acidity of Vinegar | GROUP 2 IIIBSCT

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