CHEMISTRY

Escuela Politécnica de
Ingeniería de Gijón
Universidad de Oviedo EXPERIMENT 6

pH POTENTIOMETRIC DETERMINATION

OBJECTIVE: (i) Use an electrochemical pH sensor to assess the buffering capacity of a buffer
solution formed by a weak acid-base conjugate pair; and, (ii) Be able, not only to measure the pH
correctly, but also to understand and explain how a buffer solution works.

MATERIAL REAGENTS

1 volumetric flask (50 mL) HCH3COO (aq) 10 % (m/m);

1 volumetric flask (100 mL) d= 1.02 g/mL; MW = 60.05 g/mol
1 graduated pipette (10 mL) NaCH3COO (s)
2 beakers (100 mL) NaOH(aq) 0.1 M
1 graduated cylinder (100 mL) HCl(aq) 0.1 M
1 Pasteur pipette and a glass stirring rod NaOH(aq) 2M
1 pH-meter HCl(aq) 2M
1 volumetric flask (50 mL)

7.1. pH MEASUREMENT
In aqueous solutions, H3O+ and OH- concentrations are related through ion product constant for
water, Kw:

Kw = [H3O+][OH-] = 1.0x10-14

Since the H3O+ concentrations range from 1 M (in strong acid solutions) to 10-14 M (in strong base
solutions), it is much more useful to express them on a logarithmic scale known as the pH scale.

The pH is a logarithmic index that measures the molar concentration of hydrogen ions (H +), also
called hydronium ions (H3O+), in aqueous solution.

pH = -log[H3O+]

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The following table summarizes the pH range for acidic, neutral and basic solutions:

Type of Solution [H3O+] [OH-] pH value

Acidic > 1.0 x 10-7 < 1.0 x 10-7 < 7.00
Neutral = 1.0 x 10-7 = 1.0 x 10-7 = 7.00
basic < 1.0 x 10-7 > 1.0 x 10-7 > 7.00

Although, we can find strongly acidic solutions with negative pH or very basic solutions with a pH
higher than 14, the most common pH range is between 0 and 14. In addition to the acid-base
nature, pH controls many other aqueous solution properties (solubility of salts, formation of
complexes between metal cations and ligands, drinking quality of water, etc.). Therefore, it is very
important to easily measure the pH by means of a digital pH-meter.

Q1. Write pH value of three known substances

7.2. pH-meter
The electromotive force of an electrochemical cell depends, not only on the identity of the metals of
the electrodes, but also on the concentration of the chemical species present in the aqueous
solution that acts as an ion conductor. This dependence provides the basis of the electrochemical
sensors, which are electrochemical cells designed so that their electromotive force varies
selectively with the concentration of a certain chemical species. A very important example is the pH
sensitive glass electrode.

Glass is a mixture of calcium and sodium

silicates (CaSiO3, Na2SiO3) with additives that Fill hole
give color and consistency. (KCl(aq) 3M)
Glass properties are related to the presence of
a molecular skeleton of silicate anions (SiO42-) Ag|AgCl reference
that make up an irregular three-dimensional electrode (external)
network of tetrahedron with shared vertices
where Na+ or Ca2+ cations are intercalated. Porous wick (allows the ionic
contact with the external solution)
Thus, some glass membranes, whose surface
is hydrated, are able to exchange some Ag|AgCl reference
sodium ions, Na+, for hydronium ions, H3O+, of electrode (internal)
the solution. pH-sensitive glass-membrane
A glass membrane of these characteristics is
considered sensitive to pH.

If a pH-sensitive glass separates two solutions, one with a known concentration of H3O+ and the
other one with unknown concentration of H3O+ (the sample), then an electric potential difference
across the membrane is generated due to the asymmetry in ion exchange processes:
Na+ (glass) + H3O+ (aq)  H3O+ (glass) + Na+ (aq)

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In order to detect the potential difference associated to this equilibrium, an electrochemical cell is
built including an indicator electrode with a pH-sensitive glass membrane and a reference
electrode that provides a constant potential. In fact, the two electrodes that make up the pH
sensor are usually mounted in a single body (a combination glass electrode for measuring pH).

The pH-meter includes a digital voltmeter to measure the potential of cell, E. The potential and pH
are theoretically related through the Nernst equation (see below). At 25°C, the value of the slope
is 59.16 mV. The constant k' collects the contributions of the rest of the system (the reference
electrode, etc.) and its absolute value must be determined by a previous calibration with standard
solutions.

THE DESCRIPTION OF THE COMPONENTS, CALIBRATION AND HANDLING

OF THE pH-meter WILL BE EXPLANED BY THE INSTRUCTOR.

7.3. Experimental Procedure: pH measurement

1. The pH measuring glass electrode is initially immersed into a beaker containing a storage
solution (or distilled water). Remove it.

2. Place an empty baker under the pH electrode, and rinse the pH electrode with distilled
water.

3. Gently blot the electrode on a laboratory cleaning tissue to remove the excess rinse water.

4. Dip the electrode in a 100 mL beaker containing about 50 mL of the solution whose pH has
to be measured. Be sure that the electrode does not touch the bottom and/or the walls of
the beaker. Shake the beaker slightly.

5. Star the pH measurement by pressing the button pH in the pH-meter. Once the instrument
reading is established, record the pH measured value.

6. Remove the electrode from the solution, rinse the electrode and dry it before immersing it
again in another solution or leaving it in a beaker if you are finished.

7.4. BUFFERING CAPACITY

When reagents are mixed in aqueous medium, the acidity of the medium will depend on the
formation of certain products and on the extent to which they are formed. In order to maintain
medium acidity under control, buffer solutions are normally used. These solutions offer a pH
resistance when small amounts of a strong acid or a strong base is added to them.

In fact, a buffer solution is a solution which consists of equimolar amounts of an acid (HA) and its
conjugate base (A-) with the equilibrium constant Ka. Under these conditions, the theoretical
analysis of the corresponding acid-base equilibrium:

HA(aq) + H2O  A-(aq) + H3O+(aq)

leads us to the Henderson equation for the calculation of the pH of a buffer solution:

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 Buffer solutions:

If concentrations [A-] and [HA] are approximately equal, then pH = pKa.

Although, when varying the proportions, another pH buffer is specified. If sufficient concentration of
HA and A- is available, changes caused by the addition of OH- or H+ can be absorbed by the
neutralization of HA or A-, respectively. The pH changes are only a few hundredths as long as the
[A-] / [HA] ratio remains close to the initial value.

Q2. Most common buffer solutions are formed by:

If in the laboratory 0.1 M CH3COOH, NH3, HCl, NaOH, NH4Cl and NaCH3COO solutions
are available, choose those appropriate for the examples below and, in each case, identify
the acid and base.

a weak acid and its conjugates base EXAMPLE:

a weak base and its conjugates acid EXAMPLE

Experimental Procedure:

Prepare an acid-base buffer solution and assess its buffer capacity against additions of strong
acids or strong bases.

1. Preparation of a 0.1 M sodium acetate solution by weighing.

How much sodium acetate is needed to prepare 100 mL of a 0.1 M solution?

Weigh the amount of sodium acetate previously calculated in a beaker. Dissolve the solid
using a portion of distilled water. Transfer the mixture quantitatively into a 100 mL
volumetric flask (previously rinsed with distilled water) and make up to the final volume.

2. Preparation of a 0.1 M acetic acid solution by dilution.

How much acetic acid (10 %) is needed to prepare 50 mL of a 0.1 M solution?

Wash a graduated pipette with distilled water and use it to transfer the calculated volume
of acetic acid into a 50 mL volumetric flask. Make up to the final volume with distilled
water.

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3. Preparation of a sodium acetate-acetic acid buffer solution.
In a baker, mix the necessary volumes to prepare 100 mL of a solution, with maximum
buffer capacity, starting from the previously prepared sodium acetate and acetic acid
solutions of acetic acid.
Do you need to use the graduate cylinder necessary?

4. Checking the buffering properties:

Prepare 50 mL of the solutions indicated in each test, in a 100 mL beaker. Add the
indicated amount of each reagent and stir the mixture with a glass stirring rod. Measure
the pH in each case record the value in the table, along with the corresponding
explanation.

Test Content pH Explanation

1 50 mL distilled H2O

2 50 mL H2O + 20 drops of HCl 0.1 M

3 50 mL H2O +20 drops of NaOH 0.1 M

4 50 mL (CH3COOH + CH3COONa)

5 50 mL (CH3COOH + CH3COONa)
+ 5 drops of HCl 0.1 M

6 50 mL (CH3COOH + CH3COONa)
+ 20 drops of HCl 0.1 M

7 50 mL (CH3COOH + CH3COONa)
+ 10 drops of HCl 2 M

8 50 mL (CH3COOH + CH3COONa)

9 50 mL (CH3COOH + CH3COONa)
+ 5 drops of NaOH 0.1 M

10 50 mL (CH3COOH + CH3COONa)
+ 20 drops of NaOH 0.1 M

11 50 mL (CH3COOH + CH3COONa)
+ 10 drops of NaOH 2 M