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Fachhochschule Mannheim Institute for Physical Chemistry

Hochschule für Technik Experiment 3b


und Gestaltung
Electrochemistry

Determination of the Selectivity Coefficient KM-S and the


Detection Limit of an Ion-Selective Electrode
1. Selectivity

Ion selective electrodes are not absolutely specific, often there exists a more or less marked
sensitivity towards other interfering ions. The knowledge of this interference is essential when
determining ion concentrations with ion-selective electrodes. The influence of interfering ions on
the potential of an ion-selective electrode can be approximated by an expanded Nernst equation:

E = E 0 + S * log(a M + ∑ K M − S * a SZ M / Z S )
s (1)

KM-S = selectivity coefficient of the measured ion M towards the interfering ion S
aM = measured ion activity
aS = interfering ion activity
zM = charge of the measured ion
zS = charge of the interfering ion
S = effective electrode slope

A small value of KM-S corresponds to a high selectivity for the measured ion M in the presence of the
interfering ion S. For example, if the value of KM-S is 10-3, the measured ion M is detected 1000
times more sensitively than the interfering ion S. Thus, the selectivity coefficient can be used to
determine the concentration limit of interfering ions at which ion-selective electrodes can no longer
be used. The following simplifications, which can be applied under certain conditions, will be made
in the following when determining the selectivity coefficient experimentally:

- only the presence of one type of interfering ion is assumed,


- measured and interfering ion possess the same charge,
- concentrations will be used instead of ion activities

Thus, equation (1) simplifies to:

E = E 0 + S *log(c M + K M − S * cS ) (2)

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2. Method of Determination

The selectivity coefficient will be determined by using the "Method of constant interfering ion
concentration with variable measured ion concentrations".
In this method a dilution range of the measured ion M is established and an identical amount of
interfering ion S is added to the individual dilution steps. By plotting the potential difference ∆E of
the measuring system as a function of cM, a curve similar to the one given in Figure 1 is obtained.

In the linear portion of the curve to the right, the potential is determined only by the measured ion
M, while in the left horizontal portion, the potential is only determined by the interfering ion S. Both
lines would intersect with point P only if the other ion was not present in solution. Using equation
(2) the intersection point P is given as:

cS = 0 (only measured ions) EP = Eo + S * log cM,P

cM = 0 (only interfering ions) EP = Eo + S * log (KM-S * cS)

From this KM-S can be calculated:

cM ,P
K M −S =
cS (3)

3. Detection Limit

Even without the presence of interfering ions, each calibration curve at lower measured ion
concentration ends at a horizontal line, as a certain equilibrium concentration of measured ions is
established by the electrode itself. This is important for the determination of the detection limit. In
order to calculate this limit the same method can be used as described above, but without extra
interfering ions and determine the intercept of the extrapolated linear portion of the calibration
curve (Figure 1).
Drawing a perpendicular line from the intercept of the two lines give the limiting concentration cN.

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4. A Chloride-Selective Measuring Wand

chloride electrode reference electrode


type 15 213 3000 type 373-90-WTE-ISE-S7

1 plug-in head 1 plug-in head


2 plastic body 11 refill opening for bridging electrolyte
(POM copolymer)
3 Ag/AgCl internal outlet 12 internal reference electrolyte
4 electrical insulation (maintenance-free)
5 air tube 13 Ag/AgCl reference element
6.8.9 silicon washers 14 internal (ceramic) diaphragm
7 plastic module body 15 tapered diaphragm
(POM copolymer)
10 ion-selective pressed membrane

5. Procedure
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a. Determination of the selectivity coefficient KNa-K and the limiting concentration of a Na-
selective electrode.
Electrode: Na+-selective glass electrode type pNa 271 (Fa.Ingold)
Reference electrode: Ag/AgCl electrode with electrolyte (salt) bridge
Bridge electrolyte: 1mol/l NH4NO3 solution.
Measuring temperature: 25•C
Starting solutions: TRIS buffer pH 9.8
(400 mg/l Tris(hydroxymethyl)aminomethane)
10-1 mol/l NaCl solution (solvent = TRIS buffer)
5*10-1 mol/l KCl solution (solvent = TRIS buffer)
By diluting the 10-1 molar NaCl solution with the TRIS buffer, a dilution range to 10-8 mol/l NaCl is
produced. Dilution step 1:10 each time.
Take 40 ml from each solution and determine the potential difference ∆E. Wait for 3-5 minutes
before recording the measurement and note the constant end value. Next, add 10.0 ml of the 5*10-1
mol/l KCl solution and after exactly 5 minutes note the potential difference ∆E.
All measurements should be taken using the same stirring speed. Before dipping the electrode in
the next solution, wash the electrodes in distilled water and wipe with a clean paper towel: only dab
the ion-selective membrane carefully when cleaning it as it is very delicate (easily breakable).

b. Determination of the selectivity coefficient KCl-Br and the detection limit for a Cl-selective
electrode
Electrode: Cl selective crystal membrane electrode type 15213300 (Fa.Ingold)
Reference electrode: same as a.
Measuring temperature: 25•C
Starting solutions: 10-1 mol/l NaCl solution
5*10-5 mol/l NaBr solution

After dilution of the 10-1 molar NaCl solution with distilled water, a dilution range to 10-7 mol/l
NaCl is produced. Take 40 ml from each solution and determine the potential difference, ∆E. Next,
add 10.0 ml of the 5*10-5 mol/l NaBr solution to each solution and note the potential difference, ∆E.
At the conclusion of the measurements wash the electrodes with distilled water. The Na+ electrode
is kept in a 0.1 molar NaCl solution and the Cl- electrode is kept dry and protected from light.

6. Evaluation

a. Plot ∆E as a function of log cNa+ and ∆E as a function of log cCl- and determine the
concentrations cNa+,P and cCl-,P , respectively, from the intercept point P, as done in Figure
1. From equation 3 calculate the selectivity coefficients KNa-K and KCl-Br .
b. Determine the detection limit of the Na-selective and the Cl-selective electrodes (give
answer in moles of Na+ and Cl-, respectively).
c. Plot the maximum allowable ratio of cK+/cNa+ and cBr-/cCl- in the measurement of Na+ ions
and Cl- ions, respectively, if the error should not exceed 1%.

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