EXPT.

2 pH TITRATION OF WEAK ACID -

DETERMINE OF pKa OF ACETIC ACID
Structure
2.1 Introduction
Objectives
2.2 Principle
2.3 Requirements
2.4 Procedure
2.5 Calculations
2.6 Results

2.1 INTRODUCTION
We have already disused pH-metry in detail in the unit 3 of MCH -004 course. In this
experiment you are going to perform a titration of a weak acid against a strong base and
we measure pH changes during titration by pH meter. The pKa value of acetic acid is
determined by plotting pH titration curve.

Objectives
After performing this experiment you will be able to:
• Describe the relationship between the equilibrium constant of weak acids with
hydrogen ion concentration,
• perform a pH titration of a weak acid with a strong base.
• determine the pKa of the given weak acid by plotting pH titration curve,
• state the advantages of pH titrations, and
• practice the precautions while performing a pH titration experiment.

2.2 PRINCIPLE
When a weak acid, HA, is dissociated in water, the following equilibrium is setup.

HA (aq) ⇌ H+ (aq) + A − … (1)

where, HA (aq) is the weak acid, H+ (aq) is the hydrogen ion and A- is the conjugated
base. The equilibrium constant Ka for this reaction is called dissociation constant of the
acid HA.

[ H + ] [ A −1 ]
Ka =
[HA]

To calculate Ka we need to know [H+ ], [A − ] , and [HA]. The concentration of

hydrogen ion, [H+], is determined directly by measuring the pH.
pH = ─ log [H+]

Unfortunately, calculating [HA] and [A − ] is not as straight forwards. A convenient

method for determining Ka is to measure the pH of a solution of the acid after a strong
base has been added to half neutralize it. We can calculate the amount in millimoles
(mmol) of base added by multiplying the volume in cm3 by the concentration in mmol
per cm3, which is the same as the molar concentration (in moles per dm3) since both the
numerator and denominator are divided by 1000.

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SpectroscopicMethods c = c ( mol / 1000) = c
Lab. ( mol / dm 3 ) mmol / cm 3
dm 3 / 1000)

n( mmol) = V ×c
( cm 3 ) ( mmol / cm 3 )

Now consider, if 10 cm3 of 0.10 M NaOH is added to 20 cm3 of 0.10 M acetic acid,
the solution will initially contain 10 cm3 × 0.10 mmol/cm3 = 1 mmol of NaOH and 20
cm3 × 0.10 mmol/cm3 = 2 mmol of acetic acid.

OH − + CH 3 COOH ⇌ H 2O + CH 3COO −

Initial 1 mmol 2 mmol

Change -1 mmol -1 mmol +1 mmol

Final 0 mmol 1 mmol 1 mmol

In this example 1 mmol NaOH is completely consumed converting 1 mmol of acetate

mmoles of Acetate ion 1 mmol
ions. Then [HA] = [A − ] = =
total volume 30 cm.3
The Ka expression is simplified because equal terms cancel out

[H + ] [CH 3COO − ] [ H + ] (0.033)

Ka = = = [H+]
[CH 3COOH] (0.033)
Thus at the point of half neutralization,
Ka = [H+]

or pKa = pH … (1)
The pH at the half neutralization of a weak acid can be determined by measuring the pH
with a pH meter after each addition of a strong base and creating a titration curve which
resembles the one shown in the Fig. 2.1 below. Once the equivalence has been
determined, the pH can be read halfway to the equivalence point, and from it the Ka of
the acid can be calculated.

Fig. 2.1: pH titration curves: 0.10 Acetic acid with 0.10 NaOH.

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2.3 REQUIREMENTS
Apparatus
pH meter with combination pH electrode

Chemicals
Oxalic acid solution, 0.10 M NaOH solution, 0.10 CH3CHOOH solution.

2.4 PROCEDURE
Part A: Standardization of NaOH and Acetic acid.
1. Prepare oxalic acid solution (0.1 M) by dissolving appropriate amount of oxalic
acid to 100 cm3 of distilled water in a volumetric flask of 100 cm3. Using this
solution as primary standard, standardize NaOH solution (0.1N) using
phenolphthalein indicator. Report your observations in the observation Table 1.
2. Similarly, using above NaOH solution as secondary standard, standardize given
acetic acid solution. Report your observations in the observation Table 2.

Part B: Determination of the Ka of Acetic Acid.

1. Perform a titration by taking 10 cm3 acetic acid against NaOH using
phenolphthalein indicator to know the position of end point.
2. Again take 25 cm3 acetic acid in a 100 cm3 beaker add 20-25 cm3 of distilled
water and dip the pH electrode, find the initial pH using pH meter (you pH meter
should be pre-calibrated with standard buffers). Add standardized NaOH from
the burette in small instalments of 1-2 cm3 and stir well. Record the pH after each
addition. Near the end point, NaOH should be added in very small instalments of
0.1-0.5 cm3. At the end point, you will observe sudden change in the pH and
continue the titration until pH readings remain relatively constant at a pH of 10-
12. Record your observation in the observation Table 3. Your pH reading should
provide a smooth titration curve. If not, try again.
3. Plot a graph of pH (y-axis) vs. volume NaOH added (x-axis). Determine the
equivalence point from the graph. Find out the NaOH volume used in complete
neutralization of acetic acid. From plotted curve find out the cm3 of NaOH and
pH at ½ at the neutralization of acetic acid. Calculate the value of Ka using Eq.
pKa = pH.

Observations

Observation Table 1: Standardization of NaOH and Acetic Acid.

S.No. Volume of oxalic acid (cm3) Volume of NaOH(cm3)

1. 10

2. 10

3. 10

cm3 of NaOH added at end point……………………

Molarity of NaOH…………………………………..

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SpectroscopicMethods Observation Table 2: Standardization of Acetic acid
Lab.

S.No. Volume of Acetic acid (cm3) Volume of NaOH(cm3)

1. 10

2. 10

3. 10

cm3 of NaOH added at the end point………..

Molarity of Standardized NaOH………….

Calculated the molarity of Acetic acid ………

Observation Table 3: Determination of the Ka of CH3COOH

S.No. Volume of NaOH added (cm3) pH

1. 0.0

2. 2.0

3. 4.0

4. 6.0

5. 8.0

6. 10.0

7. 12.0

8. 14.0

9. 16.0

10. 18.0

11. 20.0

12. 22.0

13. 24.0

14. 24.5

15. 25.0

16. 26.5

17. 27.0

18. 27.5

19. 28.0

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2.5 CALCULATION
Volume of NaOH added to get equivalence point………………. cm3 (from the plotted
graph)
Volume of NaOH added to get half neutralization…………….. cm3

pH at half neutralization ……….

pKa = pH

Ka = antilog (–p Ka ) = antilog (–pH)

Ka =………………………..

Ka can also be calculated using following equation, i.e.

[A − ]
pH = p Ka + log … (2)
[HA ]

In this titration, most A − , generated during the reaction of acetic acid with NaOH.

HA + OH − → A − + H2O … (3)

volume of NaOH in cm 3 × mmol of NaOH

Thus cA − = cNaOH =
total volume
Similarly, HA concentration during titration is the concentration of HA remaining after
the reaction with NaOH.

volume of actic acid × mmol of aceticacid − volume of NaOH × mmol of NaOH

c HA = c CH3COOH =
total volume

Substitute the value of cA − and cHA in above equation and calculate the value of Ka for
the addition of 5 cm3 NaOH, 10 cm3 NaOH and 15 cm3 NaOH

2.6 RESULT
Ka value from half neutralization method =

Average Ka from Eq.3 =

Ka from Literature =

Percentage error

Precautions
• Never touch the membrane of the glass electrode with anything else except soft
tissue paper since it is fragile and is easily ruined if scratched or bumped.
• The electrode(s) must not be removed from the solution unless the selector switch
is at zero.
• Before measuring pH, establish equilibrium between electrodes and titration
solution by stirring solution to ensure homogeneity.

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SpectroscopicMethods • The glass electrode may be covered with a sleeve to save it from jerks.
Lab.
• The standard buffer of pH value as close as possible to the sample pH value must
be taken for the calibration of the system. Commercially available standard
buffers of pH values 4, 7 and 9.2 are commonly used.

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