ABSTRACT / SUMMARY

An experiment is conducted to identify an unknown

monoprotic acid by obtaining the pKa value form titration curves. 10
millilitres of the unknown acid is titrated with approximately 0.1 M of
sodium hydroxide solution. Three trials are conducted and therefore
three titration curves are plotted. The values of pKa and Ka of the
unknown acid from the titration process are 4.537 and 2.90 x 10 -5
respectively. Whereas, the pKa and Ka values obtained from using
the initial pH of the unknown acid are 4.81 and 1.53 x 10 -5
respectively. Theoretically, the pKa and Ka values of the unknown
monoprotic acid, which is believed to be of acetic acid are 4.75 and
1.76 x 10-5. Therefore, an error of 4.48 percents of the pKa value
and 64.77 percents of the Ka value from the titration process are
calculated. Meanwhile, an error of 1.26% and 13.1% of pKa and Ka
values obtained from using the initial pH of the unknown acid is
calculated. Therefore, there is only a slight difference from the
theoretical value compared to the values from th etitration process.
Hence, the unknown monoprotic acid is identified as acetic acid and
the value determined from using the initial pH value of the acid is a
more accurate method. The experiment is completed and
successfully conducted.

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 INTRODUCTION

Acid-base titration is a method of neutralization process which

provides information regarding the properties as well as nature of
either acid or base applied during the process. Likewise, it is useful
to determine the molecular mass and pKa values of the substances.
The end-point of such titration can be monitored by using indicators
or as what is used in this experiment, a pH meter with electrodes.

A titration curve is a graph of measured pH values obtained

from pH meter readings versus volume of titrant being added in
millimetres. Basically, the most important information that is
supposed to be obtained from acid-base titration is the equivalence
point. The equivalence point is theoretically reached when the
number of moles of base being added into the Erlenmeyer flask is
equal to the number of moles of acid. It occurs in the titration curve
in the region where there is a large and noticeable change in pH with
a relatively small change in volume of titrant.

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 AIMS / OBJECTIVES

The experiment is conducted to achieve main objective, which

is to identify the unknown monoprotic acid by comparing the
calculated average Ka values from the data obtained from this
experiment with the Ka values of some common acids found in a
general chemistry book. In order to get the Ka values for the
unknown acid, it can be obtained by performing titration process
based on the pH value. Besides that, the Ka value can also be
determined by using the initial pH of the unknown monoprotic acid.

THEORY

In this experiment, we will be dealing with monoprotic acid.

Based on Brønsted and Lowry, an acid is a proton donor whereas a
base is a proton acceptor. This portrays a very important idea to
understanding monoprotic and polyprotic acids and bases since
monoprotic, as a matter of fact, is basically referred to the transfer
of one proton. On the contrary, polyprotic corresponds to the
transfer of more than one proton. Therefore, monoprotic acid is an
acid that can donate one proton while polyprotic acid is an acid that
can donate more than one proton. To be more precise, monoprotic

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acid can release one proton per molecule and hence, have only one
equivalence point.

When a weak monoprotic acid (HA) is dissolved in water, only

certain of its molecules will dissociate to yield hydronium ions,
H3O+, and A- ions. At this point, the reaction has reached dynamic
equilibrium. Consider the following reaction:

HA (aq) + H2O (liq.) <−> H3O+ (aq) + A- (aq)

Under such equilibrium conditions, the total concentrations of

each species remain constant, even though the species in solution
are constantly dissociating and recombining. The ionization constant
of the weak monoprotic acid is used to characterize the acid, and is
calculated by using the following equation:

Ka = [H3O+] [A-]......................... (1)

[HA]

In this expression, Ka refers to acid ionization constant. Strong

acids typically dissociate completely, and therefore would have a Ka
value of greater than 1. Weak acids have Ka values much smaller
than 1, typically less than 10 -4 to be more precise. For instance, the
Ka value of propanoic acid is 1.3 x 10 -5 and its pKa value is 4.874.
In prioritizing the convenience, scientists often use the pKa values
of weak acid, as it allows them to deal with whole numbers.

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 By assuming a 1:1 molar ratio of acid : base, the volume as
well as concentration of sodium hydroxide, which is the base can be
used to determine the number of moles of acid present:

Ƞbase = massbase ......................(2)

Mr base

Ƞacid = Ƞbase x 1 mol of acid ..................(3)

1 mol of base

The pH of a solution is related to the hydronium ions, H3O+,

concentration by the equation:

pH = −log [H3O+] ....................(4)

and the pKa of an acid is simply:

pKa = −log Ka ...........................(5)

By considering equation (1), take –log on both sides:

-log Ka = -log [H3O+] – log [A-] ..................................(6)

[HA]

Thus, by substituting equation (6) into equation (5):

pKa = - log [H3O+] – log [A-] ..................................(7)

[HA]

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and therefore, by substituting equation (4) into equation (7):

pKa = pH – log [A-] ..................................(8)

[HA]

However, since pKa is constant and pH varies,hence:

pH = pKa + log [A-] ..................................(9)

[HA]

Therefore, when [A-] = [HA], thus:

pH at half-equivalence point = pKa ........................(10)

This is the midway point to the equivalence point. A titration

curve is needed to analyze the acid ionization constant, Ka values of
the unknown monoprotic acid to be identified in this experiment. The
titration curve represents the pH values at particular volume of
sodium hydroxide being added. Thus, pKa values can be read
directly from titration curve. From the titration data collected from
the experiment conducted, three titration curves of pH versus volume
of base added in millilitres are plotted. On each curve, the volume of
base at equivalence point is clearly marked. Next, the volume of
base at half-equivalence point at each curves are determine and
clearly marked. The pH values at that particular half-equivalence
point are then extrapolated. The pH values can now be used to
calculate the acid ionization constant and the average value is
determined. In addition, the volume of base titrated at the
equivalence point is used to calculate the concentration of the

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unknown monoprotic acid. The average is determined as well. The
average acid ionization constant is then used to identify the unknown
monoprotic acid.

APPARATUS / REAGENTS

~ 50-millilitre burette, 10-millilitre graduated cylinders, 50 and 250-

millilitre beakers, Erlenmeyer flask, retort stand and burette clamp,
pH meter, spatula, analytical balance, filter funnel, magnetic stirrer,
pellets of sodium hydroxide, distilled water, 10 millilitres of unknown
monoprotic acid.

EXPERIMENTAL PROCEDURE

1. An approximately 2.0 grams of pellets of sodium hydroxide, NaOH

is weighted to the nearest four decimal points and dissolved in 500
millilitres of distilled water.

2. A burette is cleaned, rinsed and filled with NaOH solution.

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3. 10 millilitres of unknown monoprotic acid is prepared and then
transferred into the Erlenmeyer flask.

4. The flask is then placed on a stir plate and a magnetic stirrer is

inserted into the flask and let to stir the solution.

5. A pH meter is calibrated using buffer solution before the

electrode is being rinsed well with distilled water and blotted dry.

6. The pH electrode is inserted into the flask and the position of the
electrode is adjusted so that the magnetic stirrer does not hit it.

7. The acid is titrated and the pH reading as recorded with the

following increments:
At pH 1 until 5.5 : 1 millilitre of NaOH at a time
At pH 5.5 until 10.5 : 0.5 millilitre of NaOH at a time
At pH 10.5 until 12.5 : 1 millilitre of NaOH at a time

8. The titration is continued to at least a pH of 12.

9. The data of pH readings and the volume of NaOH solution added

and titrated are recorded and tabulated.

10. A titration curve of pH versus volume of NaOH solution titrated is

plotted. Based on the titration curve, pKa value of the acid is
calculated and the acid is identified.

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 RESULTS

Mass of sodium hydroxide pellets dissolved : 2.0823 grams

Vol. NaOH pH pH pH Average
(mL) (Trial 1) (Trial 2) (Trial 3) pH
0.0 2.89 2.87 2.98 2.91
1.0 4.08 3.70 3.67 3.82
2.0 4.23 4.09 4.05 4.12
3.0 4.42 4.32 4.26 4.33
4.0 4.68 4.55 4.53 4.59
5.0 4.85 4.79 4.72 4.79
6.0 5.17 5.04 5.02 5.08
7.0 5.89 5.46 5.43 5.59
7.5 6.33 6.11 5.90 6.11
8.0 11.17 10.63 10.56 10.79
9.0 11.55 11.34 11.26 11.38
10.0 11.73 11.52 11.52 11.63
11.0 11.83 11.64 11.67 11.71
12.0 11.90 11.72 11.77 11.80
13.0 11.93 11.77 11.82 11.84
14.0 12.00 11.80 11.87 11.89
15.0 12.04 11.84 11.90 11.93

Volume of NaOH at equivalence point (mL) 7.5951

pH at half-equivalence point ≈ pKa 4.537
Acid ionization constant, Ka 2.90 x 10-5

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 13
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11
10
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7
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5
4
3
2
1
0
0 2 4 6 8 10 12 14 16

SAMPLE CALCULATION

By using equation (2):

Ƞbase = massbase
Mr base

= 2.0823 g
39.997 g/mol
= 0.0521 mol

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From the reaction equation, number of moles of base is equivalent to
the number of moles of acid. Thus,

Ƞacid = Ƞbase
= 0.0521 mol

By using equation (10), pH at half-equivalence point = pKa = 4.535

To calculate the acid ionization constant, by using equation (5):

pKa = −log Ka
4.537 = -log Ka
Ka = arc log -4.535
= 2.90 x 10-5

Likewise,from the reaction equation,

HA (aq) + H2O (liq.) <−> H3O+ (aq) + A- (aq)

by considering the following “ICE” table:

components HA H3O+ A-
Initial 0.1 0 0
concentration
Change in 0.1 – x + x + x
concentration
Concentration at 0.1 - x x x
Equilibrium

the concentration of H3O+ is calculated using the average value of

pH reading from the titration conducted in th earlier experiment.
pH = -log [H3O+]

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 2.91 = -log [H3O+]
[H3O+] = arc log (-2.91)
= 1.23 x 10-3

Thus, the acid ionization constant, Ka of the unknown monoprotic

acid is dtermine by using equation (1) :

Ka = x.x__
1.1 – x
= x2___
1.1 – x
= (1.23 x 10-3)2
1.1 – 1.23x10-3
= 1.53 x 10-5
Thus, the pKa is equal to:
pKa = -log Ka
= -log (1.53 x 10-5)
= 4.81

SAMPLE ERROR CALCULATION

The unknown monoprotic acid is identified to be acetic acid.

However, theoretically, the pKa value for acetic acid is 4.75,
whereas the Ka value corresponds to the unknwon monoprotic acid
from the titration is 1.76 x 10 -5. Thus, the percentage errors for each
theoretical value to the calculated value are:

Percentage error (pKa) = │4.75 – 4.537 │ x 100%

4.75
= 4.48 %

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 Percentage error (Ka) = │ 1.76 x 10-5 - 2.90 x 10-5│x100%
1.76 x 10-5
= 64.77 %

For the identifying the unknown acid using the pH value in order to
determine the Ka value,the value is slightly different from the one
obtained from the titration process. The percentage error is
calculated to be:

Percentage error (pKa) = │4.75 – 4.81│ x 100%

4.75
= 1.26%

Percentage error (Ka) = │1.76x10-5 – 1.53x10-5│x100%

1.76x10-5
= 13.1%

DISCUSSION

A lot of information is required in order to assure that the

identity of the unknown acid is conclusive. Notice that one
equivalence point is obtained, therefore one pKa value. After
analyzing it as well the Ka value, it is concluded to be remarkably
similar to acetic acid. The unknown’s Ka value is 2.90 x 10 -5 whereas

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acetic acid’s Ka is merely different which value is 1.76 x 10 -5.
As for the pKa value of the unknown acid is calculated to be 4.537
whereas acetic acid’s pKa value is 4.75.

The main objective of the experiment is to determine the Ka

value of the unknown monoprotic acid so as to identify the acid.
However, an error of 64.77 percents after comparing the theoretical
value with the experimental value is obtained. Therefore, a few
mistakes or lack of awareness of the precautions that must be
considered when conducting the experiments may be the reasons
that lead to the erroneous calculations.

First error that might affect the calculated values is done

during weighing the pellets of sodium hydroxide. The weight of an
empty beaker should have been considered as well. Then, it must be
subtracted from the weight of the beaker containing the pellets.
Hence, the titration curves might not have the accurate values as the
concentration of sodium hydroxide is not perfectly 0.1 M.

Second, the pH meter that has been used has never given the
definite readings, as the values that are shown are always changing
rapidly. Thus, one can never tell the accurate readings of pH values.
Therefore, these will also affect the titration curves as well as pKa
values which correspond to the pH values at half equivalence point.

Besides that, the equivalence point is not necessarily being at

pH of 7 as it occurs just when the concentration of acid is equal to

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the concentration of base reacted in solution. Therefore, the final pH
depends on the major species of ions left in the solution after the
reaction.

In addition, the pH electrode might have come into contact with

the magnetic stirrer. Therefore, a problem might be encountered
during the readings of pH values on the pH meter.

CONCLUSION

The experimental values of pKa and Ka of the unknown acid are

4.537 and 2.90 x 10 -5 respectively. Whereas, the pKa and Ka values
obtained from using the initial pH of the unknown acid are 4.81 and
1.53 x 10-5 respectively. Theoretically, the pKa and Ka values of the
unknown monoprotic acid, which is believed to be of acetic acid are
4.75 and 1.76 x 10-5. Therefore, an error of 4.48 percents of the pKa
value and 64.77 percents of the Ka value from the titration process
are calculated. Meanwhile, an error of 1.26% and 13.1% of pKa and
Ka values obtained from using the initial pH of the unknown acid is
calculated. Therefore, there is only a slight difference from the
theoretical value compared to the values from th etitration process.
Hence, the unknown monoprotic acid is identified as acetic acid and
the value determined from using the initial pH value of the acid is a
more accurate method.

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 RECOMMENDATIONS

There are a few recommendations, and precautions that have to

be considered during the experiments in order to get an accurate
value and readings of data.

Firstly, the standard solution that is used should be a hundred

percent pure and stable at room temperatures. Thus, it is more
preferable to use a dried standard material before weighing and
diluted.

Secondly, in order to be more conclusive in identifying the

unknown monoprotic acid, the molecular weight of the acid should be
considered as well. This then can be used to compare it with the
theoretical value of molecular weight of acetic acid. Therefore, it is
more preferable to obtain the mass of solid acid and then only it is
diluted and titrated.

REFERENCES

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~ Steven L. Murov, 2004, Experiments in General Chemistry, 4 th
Edition, United States: Thomson/Brooks/Cole.

~ http://en.wikipedia.org/wiki/Acid-base_titration

~ http:// chemlab.com/Chemistry_3_5_-
_Monoprotic_and_Polyprotic_Acids_-_Chemistry

~ http://www.titrationexperiment.com/html/

APPENDICES

Table 1: Weak Acids, Ka, and pKa values

Acid HA A- Ka pKa

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Acetic CH3COOH CH3COO- 1.76 x 10-5 4.75

Ammonium NH4+ NH3 5.6 x 10-10 9.25

Benzoic C6H5COOH C6H5COO- 6.46 x 10-5 4.19

Carbonic H2CO3 HCO3- 4.3 x 10-7 6.37

HCO3- CO32- 4.8 x 10-11 10.32

Chloroacetic CH2ClCOOH CH2ClCOO- 1.4 x 10-3 2.85

Citric C6O7H8 C6O7H7- 7.41 x 10-4 3.13

C6O7H7- C6O7H62- 1.74 x 10-5 4.76

C6O7H62- C6O7H53- 3.98 x 10-7 6.40

Formic HCOOH HCOO- 1.77 x 10-4 3.75

Phosphoric H3PO4 H2PO4- 7.52 x 10-3 2.12

H2PO4- HPO4-2 6.23 x 10-8 7.21

HPO42- PO43- 2.2 x 10-13 12.67

 Refer to the attachment provided on the next page.

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