Chemistry Laboratory (CY1094D)

Dr. Mausumi Chattopadhyaya

Assistant Professor
Department of Chemistry
mausumi@nitc.ac.in
+919433710271

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 Experiment – 1
pH Metry: Determination of strength of an acid using a pH meter

Objective:
To determine the strength of the given acid by titrating it against an alkali using a pH meter.

Expected learning outcomes:

After doing the experiment, the students should be able to
❖ Operate a pH meter
❖ Perform a pH metric titration
❖ Plot pH vs volume of titrant to get a sigmoid graph and plot ∆pH/∆V vs volume of titrant
to get a first derivative graph
❖ Read the end point from the graphs
❖ Calibrate the pH meter
❖ Get familiar with the glass electrode and reference electrode
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Theory:
When an acidic solution is added to an alkali solution the pH of the solution decreases
slowly, but at the vicinity of the equivalence point, the rate of change of pH of the solution is
very rapid. From the sharp break in the curve, we can find the equivalence point, from
which the strength can be calculated. Combination probes are
most common
Electrodes:
❖ Ag/AgCl is the reference electrode
❖ Glass electrode is the working electrode

Glass composition: 22% Na2O, 6% CaO and 72% SiO2.  3

Cell representation and cell reactions:

Replace with Ag/AgCl

Consider the cell: Ag│AgCl │KCl (sat) ║ H+ │glass membrane │HCl(1N)│ Ag

Ecell = E(right/indi.) – E (left/ref.) (In terms of Reduction Potential)

or
Ecell = EG – EAg/AgCl
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EG = Eb + EAg/AgCl + Easy
EG = 0.05916 log(a1/a2) + EAg/AgCl + Easy
EG = 0.05916 loga1 – 0.05916 loga2 + EAg/AgCl + Easy

Ecell = 0.05916 loga1 – 0.05916 loga2 + EAg/AgCl + Easy – EAg/AgCl

Ecell = 0.05916 loga1 – 0.05916 loga2 + Easy

Constant

Ecell = Constant – 0.05916 pH

pH = (Constant – Ecell)/0.05916

Calibration:
The instrument, which measures the potential of the above cell and display the
corresponding pH is called a pH-meter
Setting the value of the “constant” in the above equation by setting the expected pH of the
solution of the known pH is called Calibration.
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Calibration solutions:
Potassium hydrogen phthalate (weak acid and a salt
of weak acid and strong base): pH 4
Disodium hydrogen phosphate (Strong acid and a
disalt of strong base): pH 7 Potassium hydrogen phthalate Disodium hydrogen phosphate

pH-metric titration:
Determination of the concentration of an acid (or base) by titrating it against a standard base (or
acid, as the case may be) while monitoring the pH of the titrated solution, is called pH-metric titration.
As the solution from the burette is added, the concentration of the titrant in the cell varies linear to
the volume of the titrant added.
Since the cell potential has a logarithmic relationship to the concentration of the H+, the plot of Ecell vs
volume of the titrant added is a sigmoid curve.
As pH in the cell is linear to Ecell, one gets a similar sigmoid curve for the plot of pH vs volume of
titrant added.
The abscissa (volume point) corresponding to the inflection point on the sigmoid graph is the end
point of the titration.
The maximum point corresponding to the volume of titrant from the first derivative curve (∆pH/∆V vs
volume of titrant) is the end point of the titration. 6
Titration curves:

First derivative of titration

curve

Apparatus:
pH-Meter with glass electrode and Chemicals/Solutions:
SCE (or combined electrode: glass Standard NaOH
electrode and Ag/AgCl electode) Diluted HCl
Pipette, 20/25 mL Potassium hydrogen phthalate
Burette, 50 mL Disodium hydrogen phosphate
Beaker, 100 mL

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 Procedure:
Step A: Calibration of the pH-Meter:
1. Pour about 40 mL of acid buffer (potassium hydrogen phthalate) in a 100 mL beaker.
2. Immures the glass electrode and saturated calomel electrode (or a combined glass electrode is a
combination of glass electrode and an Ag/AgCl reference electrode.
3. Gently swirl the contents and read the pH of the solution by the pH-meter. It should be pH 4.
4. Empty the beaker, clean it and pour about 40 mL of neutral buffer (disodium hydrogen phosphate)
and immures the electrodes. Gently swirl the contents and read the pH of the solution by the
pH-meter. It should be pH 7.

Step B: pH-Metric Titration (Pilot Titration):

5. Pipette out 40 mL of the given NaOH (known concentration) solution in a 100 mL of beaker (cell).
6. Fill the burette with the HCl (unknown concentration) solution.
7. Immures the electrodes and read the pH of the solution.
8. Run 1 mL from the burette into the cell, swirl the content and read the stable pH.
9. Continue to add 1 mL each time, read the corresponding pH and enter the data in the table.
10. Stop further addition of HCl, if you observe the abrupt change in pH.
11. Note down the burette readings between which the pH has abruptly changed. 8
 Step 3: pH-Metric Titration (Final Titration):
12. Repeat the steps 5-9 (pilot titration), till the upper burette reading cited in step 11. Enter the data in a
fresh table.
13. Run only 0.1 mL portion from the burette, read the corresponding pH and enter the data in the table.
14. Repeat step 13 till the lower burette reading cited in the step 11 is reached.
15. Switch to run 1 mL portions from the burette till the final burette reading is the sum of the two
readings cited is step 11.

Observations: Three tables have given for three different concentrations.

Table 1. Unknown HCl (A)
Volume of HCl added pH ∆V ∆pH ∆pH/∆V
0 11.18
1 10.59
2 10.40
3 9.73
3.1 9.57
3.2 9.32
3.3 8.80 9
Table 1. Continuation
Volume of HCl added pH ∆V ∆pH ∆pH/∆V
3.4 6.61
3.5 5.70
3.6 3.78
3.7 3.36
3.8 3.09
3.9 2.99
4.0 2.93
5 2.52
6 2.46
7 2.37
8 2.30
9 2.24
10 2.20

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Table 2. Unknown HCl (B)
Volume of HCl added pH ∆V ∆pH ∆pH/∆V
0 11.59
1 11.55
2 11.45
3 11.32
3.1 11.29
3.2 11.25
3.3 11.23
3.4 11.21
3.5 11.18
3.6 11.16
3.7 11.14
3.8 11.12
3.9 11.09
4.0 11.05
4.1 11.01
4.2 10.99 11
Table 2. Continuation

Volume of HCl added pH ∆V ∆pH ∆pH/∆V

4.3 10.97
4.4 10.85
4.5 10.69
4.6 10.25
4.7 9.81
4.8 9.68
4.9 9.41
5.0 9.30
5.1 8.90
5.2 6.69
5.3 5.90
5.4 5.49
5.5 4.62
5.6 4.11
5.7 3.72
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Table 2. Continuation

Volume of HCl added pH ∆V ∆pH ∆pH/∆V

5.8 3.24
5.9 3.08
6.0 2.99
7 2.80
8 2.52
9 2.31
10 1.98

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Table 3. Unknown HCl (C)
Volume of HCl added pH ∆V ∆pH ∆pH/∆V
0 11.37
1 11.01
2 10.43
3 10.25
3.1 10.21
3.2 10.18
3.3 10.14
3.4 10.12
3.5 10.06
3.6 10.01
3.7 9.95
3.8 9.89
3.9 9.83
4.0 9.73
4.1 9.58
4.2 9.50 14
Table 2. Continuation

Volume of HCl added pH ∆V ∆pH ∆pH/∆V

4.3 9.34
4.4 9.07
4.5 8.88
4.6 8.34
4.7 6.76
4.8 6.01
4.9 5.66
5.0 4.94
6 4.15
7 3.20
8 2.53
9 2.43
10 2.35

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Calculations and graphs:
Graph 1: Plot pH on y-axis and volume of HCl on x-axis. A sigmoid graph will appear as shown in slide
7 (figure 2). Show the end point
Graph 2: Plot ∆pH/∆V on y-axis and volume of HCl on x-axis. A graph with a maximum point will appear
as shown in slide 7 (figure 3). Identify the end point. Include this end point volume in the calculations.

Normality of NaOH (N1) = 0.01 N

Volume of alkali pipetted (V1) = 50 mL
Volume of acid corresponding to the equivalence point from the graph (V2) = X mL
Normality of HCl (N2) = ?
N1V1 = N2V2
0.01 × 50 = N2 × X
N2 = Y N
Strength of the acid solution = Mol. Wt of acid × N2
= 36.5 x Y = Z g/Lit
Result:
The strength of the given acid solution = Z g/Lit
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Precautions:
▪ Do not disturb any knobs of the pH meter once it is calibrated.
▪ Stir the contents in the beaker gently lest the fragile glass electrode should break.

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Thank you

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