Instrumental Analytical Methods

Lab Report 2013

Anastazija Ristovska
Experiment 9
pH-Metric Titration of Acetic Acid

The purpose of this experiment was to perform a pH-metric titration of acetic acid using
a standard sodium hydroxide solution in order to find the equivalence point and use this point to
find the starting concentration i.e. mass of sulfuric acid in the solution. There are several types of
pH-metric titrations: strong acid v. strong base, weak acid v. weak base, weak acid v. strong base,
and strong acid v. strong base. Our titration is a weak acid v. strong base one. In a titration
involving a strong acid the acid is completely dissociated, however acetic acid dissociates only
partially with a pKa of 4.75 i.e. Ka=1.76*10-5. For comparison, strong acids (nitric, sulfuric,
hydrochloric, chloric, perchloric, hydrobromic, and hydroiodic) all have pKa smaller than 1 and Ka
values larger than 1.
The pH of the solution throughout the titration was measured accurately using a pH
meter instrument. Two electrodes were used, a glass electrode as the indicator electrode and a
calomel electrode as the reference electrode. The potential difference between the two electrodes
was used to determine the pH i.e. the concentration of protons H+ in the solution. At the
equivalence point the pH value changed most rapidly as the protons in solution were completely
neutralized by the base added and at one moment the OH- ions concentration began rapidly
increasing causing the pH to jump to basic values.
At the equivalence point pH=7 since this is the point of neutralization. At half
equivalence point pH=pKa and in our titration since the pKa of acetic acid was 4.75, at the halfequivalence point pH=4.75. In the titration the half-equivalence point was reached when 2.5ml
0.1M NaOH titrant had been added. The definition of equivalence point pH is the HendersonHasselbach equation pH = pKa + log ([base]/[acid]), or pH = pKa + log ([A-]/[HA]), and at halfequivalence point exactly half of the acetic acid has been neutralized by the base added so
[A-]/[HA] = 1. At the equivalence point the initial number of moles of acetic acid present equals
the number of moles NaOH added, and the [CH3COO-]/[CH3COOH] ratio becomes larger and
in this case equals 102,25 or 178, i.e. the concentration of CH3COO- is 178 times larger than the
concentration of undissociated acetic acid. As more base titrant is added this ration becomes
even larger, and at pH=14 it is 178*107 or 1780 million.
The neutralization reaction taking place is

The Lewis structural formula of acetic acid and its conjugate base is given in figure 1.

Figure 1

Since acetic acid is a monoprotic acid there is only one equivalence point. Otherwise in
diprotic and polyprotic acids there are as many equivalence points as the number of acidic
protons of the acid molecule. The volume of sodium base added is measured carefully and based
on the volumes added at the half-equivalence and equivalence points the initial sulfuric acid
concentration can be determined. At half-equivalence point 2.5ml 0.1M NaOH titrant has been
added to the solution, whereas at the equivalence point 3.85ml 0.1M sodium base has been
added. We will only use the equivalence point volume in our calculations.
20
18

3,90ml

16

pH/V

14

12
10
pH/V

8
6
4
2
0
0,00

1,00

2,00

3,00

4,00

5,00

6,00

7,00

8,00

Volume of 0.1M NaOH added

m(Acetic Acid)/20ml=0.0039L*0.1mol/L*60.05g/mol
m(Acetic Acid)/20ml =0.02342g
Mass of Acetic Acid total in the Volumetric Flask: 0.1171g
Mass of Acetic Acid total in the Volumetric Flask: 117.1mg

14,00

12,00

10,00

3,90ml;
pH=8,36

pH value

8,00

3,80ml;
pH=6,56

6,00

pH

4,77
4,00

2,00

0,00
0

Volume of 0.1M NaOH added

m(Acetic Acid)/20ml=V(NaOH)*[NaOH]*MW(Acetic Acid)

m(Acetic Acid)/20ml=0.00385L*0.1mol/L*60.05g/mol
m(Acetic Acid)/20ml=0.02312g
Mass of Acetic Acid total in the Volumetric Flask: 0.1156g
Mass of Acetic Acid total in the Volumetric Flask: 115.6mg