Measurement of pH with Cobra4

TEC

Related concepts
Potentiometric determination of pH, glass electrode, pH indicators, acid-base titrations.
Principle
The course, reaction rate and equilibrium position of many chemical reactions are strongly influenced by the concentration
or, more accurately, the activity of hydrogen ions in solution aH+. Rapid and accurate determinations of hydrogen ion activity are
thus of great importance. Since aH+ can vary over many orders of magnitude, it has proved convenient to introduce the pH scale
(pH from the Latin pondus hydrognii meaning amount of hydrogen). The most important and common method used to determine the pH value is to measure the potential of an electrode which is sensitive to hydrogen ion activity. In certain practical situations, however, a simpler and more direct method of determining pH is required, and use is often made of pH indicators.
Tasks
Calibrate the following pH-sensitive electrodes in buffer solutions of known pH:

the glass electrode

the antimony electrode

the quinhydrone electrode.

Using these calibrated electrodes, measure the pH of an unknown solution. Compare and contrast the results obtained
with the three pH-sensitive electrodes.
Use the glass electrode to determine the pH range in which the following indicators change colour:

methyl orange

bromothymol blue

phenolphthalein.
Compare the suitability of the three indicators for the following different types of acid-base titrations.
Equipment
Cobra4 Mobile-Link set, incl. recharge1
able batteries, SD memory card, USB
cable and software "measure"
1
Cobra4 Sensor-Unit Chemistry
1
pH electrode, glass
1
Reference electrode, AgCl
1
Platinum electrode in protective tube
1
Antimony electrode
1
Immersion probe NiCr-Ni, teflon, 300 C
1
Adapter, BNC-plug/socket 4 mm.
1
Connecting cord, l = 500 mm, black
1
Magnetic stirrer, mini
1
Magnetic stirrer bar, l = 30 mm
Set of Precision Balance Sartorius CPA
1
623S and measure software, 230 V
1
Weighing dishes, 80 x 50 x 14 mm
1
Support for two electrodes
2
Spring balance holder
1
Burette clamp, roller mounting
2
Burette, 50 ml, lateral stopcock
1
Retort stand, h = 750 mm
1
Right angle clamp
1
Universal clamp
17 Glass beaker, 150 ml, tall
1
Graduated cylinder, 100 ml
1
Volumetric flask, 1000 ml

12620-55
12630-00
18452.00
18475-00
45206-00
18477-00
13615-05
07542-26
07361-05
47334-93
46299-02
49224-88
45019-05
45284-01
03065-20
37720-00
36517-01
37694-00
37697-00
37715-00
36003-00
36629-00
36552-00

2
4
2
1
1
2
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1
1

Volumetric pipette, 10 ml
Volumetric pipette, 50 ml
Graduated pipette, 25 ml
Pipettor
Pipette dish
Funnel, glass, do = 55 mm
Funnel, glass, do = 80 mm
Spoon
Microspoon
Pasteur pipettes
Rubber bulbs
Wash bottle, 500 ml
Potassium hexacyanoferrate(II), 250 g
Potassium hexacyanoferrate(III), 100 g
Quinhydrone, 100 g
Methyl orange solution, 0.1%, 250 ml
Bromthymol blue, 1 g
Phenolphthalein solution, 1%, 100 ml
Citric acid, 250 g
Hydrochloric acid, 1 M, 1000 ml
Sodium hydroxide solution, 1 M, 1000 ml
Buffer solution, pH 4.62, 1000 ml
Buffer solution, pH 7.01, 1000 ml
Buffer solution, pH 9.00, 1000 ml
Ethyl alcohol, absolute, 500 ml
Water, distilled, 5 l

36578-00
36581-00
36602-00
36592-00
36589-00
34457-00
34459-00
33398-00
33393-00
36590-00
39275-03
33931-00
30101-25
30100-10
31195-10
31573-25
31138-01
31714-10
30063-25
48454-70
48329-70
30280-70
46271-12
30289-70
30008-50
31246-81

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Measurement of pH with Cobra4

Fig. 1: Experimental setup.

Setup
Set up the experiment as shown in Fig. 1. Prepare the buffer solution of pH 2.60 as follows:
Weigh 21.014 g of citric acid monohydrate in a 1000 ml volumetric flask, dissolve it in 200 ml of 1 M sodium hydroxide solution,
and make up to the mark with distilled water.
1. pH-sensitive electrodes
a) Glass electrode
Calibrate the unit against two buffer solutions of pH 4.62 and pH 9.00 in accordance with the Operating Instructions manual
supplied with the pH meter. Measure the pH of the unknown solution.
b) Antimony electrode
Switch the meter to voltmeter mode. Connect the reference electrode to the ground socket and the antimony electrode to the input socket of the meter. Place the electrodes into each of the four buffer solutions (about 50 ml buffer in a 150 ml beaker) and
record the e.m.f of the cell. Repeat this procedure twice. Plot a calibration curve of the mean cell e.m.f. as a function of the pH.
Measure the cell voltage in an unknown solution, and read the corresponding pH from the calibration curve.
c) Quinhydrone electrode
Replace the antimony electrode by a platinum electrode, and saturate buffer solutions of pH 2.60, 4.62 and 7.00 with
quinhydrone. Place each of the solutions on the magnetic stirrer, put in a magnetic stirrer bar, and measure the e.m.f of the cell
under
continuous stirring. Repeat this procedure twice, and plot a calibration curve. Measure the unknown solution (saturated with
quinhydrone), and determine the pH value of it from the curve.
2. pH indicators
Weigh 0.1 g of bromothymol blue into a 150 ml beaker and dissolve it in 80 ml of distilled water and 20 ml of pure ethanol by
stirring on a magnetic stirrer. Use the solutions of phenolphthalein and methyl orange as supplied. Investigate the response of
the indicators to changes in pH by adding an acid or a base to a buffer solution containing the
respective indicator. The buffer solutions (solution A) and the acid or base solutions (solution B) to be added are listed in Table
1.
The procedure is identical for each indicator: Add 50 ml of solution A to a 150 ml beaker, put in a magnetic stirrer bar and place
it on the magnetic stirrer. Immerse the temperature probe and the pH sensor in the solution. Clamp a 50 ml burette into position
above the beaker and fill it with 50 ml of solution B. Add solution B slowly to the buffer solution. Observe the colour of the solution and record it together with the pH. Use reference solutions of the pure acid form and of the pure conjugate base form of
the indicator as an aid to assessing the progress of the colour change. Prepare them as described in Table 1 and place them on
a sheet of white paper next to the magnetic stirrer.

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Measurement of pH with Cobra4

TEC

Theory and evaluation

The most common method to determine pH is potentiometry, the measurement of the potential caused by hydronium ions. The
tools used for this are a pH meter to measure and transform the voltage, a reference electrode to give a constant potential and a
pH electrode to sense the hydronium ions and to produce a potential.
Glass electrode
The pH sensitive part of the glass electrode consists of a glass tube which has a glass membrane melted to the end of it. The
glass tube contains a 3 molar solution of potassium chloride, which is buffered to pH 7 and has a silver / silver chloride lead
dipped into it. The glass membrane swells when in contact with a solution. In contrast to the larger counter ions, the very small
hydronium ions can penetrate into the swollen layer and move in it. This separation of charges generates a voltage. The measured potential is made up of three parts: The voltage of the silver / silver chloride system, which is constant when the concentrations of the three components remain the same; the voltage at the inner side of the glass membrane, which is also kept constant
by the pH 7 buffer solution; the medium-pH voltage at the outer side of the glass membrane which is variable. A second lead
that is independent of the medium and the pH is required to be able to measure the voltage. This reference electrode, also a silver / silver chloride one, has a diaphragm as porous connection to the medium. Both leads supply a voltage, but as these are
equal and opposite, they cancel each other out. In the glass electrode system

there are two solution membrane surface interfaces (G,I) and (G,II). Equilibrium exists at each of these:

Equilibrium implies that the electrochemical potential of the hydrogen ions must be equal:

The electrochemical potential of a species is defined as the sum of the chemical and electrical energies. Equation 2 may
therefore be expressed as

where
H+ (I), H+ (II)

Chemical potential of hydrogen ions in

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H+ (G, I), H+ (G, II)

I, II
G,I, G,II

Measurement of pH with Cobra4

solution I or II respectively
Chemical potential of hydrogen ions in
the membrane surface layers
Electric potential of the solutions
Electric potential of the membrane surface layer

The buffer action of the silicic acid / silicate gel causes the activities, and therefore the chemical potentials of the hydrogen ions
in the gel layers, H+ (G, I), H+ (G, II), to be equal. Furthermore, the cations within the extremely thin SiO2 matrix of the glass
membrane ensure that the two surface layers are in electrical contact and G,I = G,II. The right hand sides of Eqs. 3a and 3b
are thus seen to be equal. Equating the left hand sides, we obtain

The chemical potentials H+ (I) and H+ (II) can be expressed as

where
H+ Standard chemical potential at unit hydrogen ion
activity (aH+ = 1)
Substituting equation 5 in (4) leads to the following expression for the electric potential difference between the external sample
solution II and the internal reference solution I:

The zero point of the measuring cell is the pH at which the measurement set-up supplies 0 mV. This is ideally at pH 7, the pH of
the buffer in the glass electrode. In reality, however, there is always a small difference between the inner and outer membrane
surfaces which results in an asymmetry potential of some mV. The slope is the increase in the characteristic pH line, i.e. the mV
value that is given from the sensor when the pH changes by a complete step. According to the Nernst equation, the theoretical
value is 59.16 mV at 25C.
Determining the deviation of the zero point and the slope from their theoretical values and saving these values into the meter is
called calibration.
Antimony electrode
The basis of the measurement procedure is that the position of the redox equilibrium is dependent on the antimony pH.
Acidic environment:

Alkaline environment:

It can be seen from the equilibriums or from the E0 values, that metals are more noble in acidic environments than in alkaline
environments. Below pH 7, many more cations are formed that envelope the metal. The tendency towards further electron
emission is low. The redox equilibrium lies to the left, the metal apprears to be noble. Above pH 7, the antimony hydroxide
Sb(OH)3 precipitate that is first formed dissolves under complex formation. The emission of further electrons is facilitated. The
redox equilibrium lies to the right, the metal appears not to be noble. On changing from an acidic to an alkaline medium, a considerable potential jump to negative occurs.
Solutions of known pH allow a quantitative relationship between the voltage of the antimony electrode and the pH to be derived:
Characteristic line of the antimony electrode (Fig. 2).
The empirically determined straight line equation can also be derived theoretically. The Nernst equation for antimony is:

On converting the natural logarithms to decadic logarithms, and inserting the constants and the temperature, we obtain for
298 K:

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Measurement of pH with Cobra4

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The solubility product of antimony hydroxide is:

The term aSb3+ can so be replaced by aOH-:

With log aOH- = pOH we obtain

The pH is introduced with the relationship pOH + pH = 14:

Bringing the constants together, we have:

When pH = 0 then ESb = E0, analogously ESb = E Sb. We therefore obtain:

This corresponds approximately to the straight line equation from Fig. 2.

Quinhydrone electrode

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Measurement of pH with Cobra4

Quinhydrone is an addition compound, made up of a 1:1 ratio of quinone and hydroquinone, which dissociates into its components in aqueous solution. The reaction which takes place at the surface of the inert platinum electrode is

The Nernst equation for the redox pair at 25C is:

The dissociation of the complex leads to equimolar activities of Q and QH2 at low concentrations aQ = aQH.

The advantage of the quinhydrone electrode is the rapid potential adjustment. It cannot be used in alkaline solutions of pH
above 8.5, however, as hydroquinone is a weak two proton acid that is predominately present as anion in such alkaline solution,
so that the potential no longer shows a simple dependence on the pH.
pH indicators
pH indicators are weak organic acids or bases whose acid form (HIn) and conjugate base form (In-) are differently coloured. The
acid-base equilibrium in solution is

The equilibrium constant for this reaction is the dissociation consant Ka

Taking logarithms produces the expression

For solutions in which pH > pKa the conjugate base form In- is dominant, whereas in solutions with pH < pKa, the equilibrium
lies in favour of the acid form HIn. In a solution containing two coloured components A and B, the human eye judges the colour
of the solution to be that of A if ist concentration is ten times that of component B. Thus in a solution judged to have the colour of
the conjugate base form of the pH indicator In-, the following is valid:

and

Correspondingly, in a solution judged to have the colour of the acid form of the pH indicator HIn,

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Measurement of pH with Cobra4

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and

A solution containing a pH indicator is therefore seen to change colour if the pH of the solution changes by two pH units about
the pKa value of the indicator:

A two-colour indicator is thus able to distinguish three pH

regions:
pH < pKa - 1
pKa - 1 < pH < pKa + 1
pH < pKa + 1

(colour of acid form dominant)

(colour change observed)
(colour of conjugate base form dominant)

A pH indicator must be chosen such that its pH range, within which it is observed to change colour, lies within the pH jump observed at the equivalence point of the titration. In single colour indicators only one form is coloured, the other colourless. In this
case, the eye will not register a change of colour but rather a change in colour intensity, which is less striking.
Data and results
The calibration curves for the antimony and quinhydrone electrodes are shown in Fig. 2. The following colour changes of the
indicators are observed:

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