Electrode potential is defined as the potential of a cell consisting of the electrode in question acting as a cathode and the standard hydrogen electrode acting as an anode. Reduction always takes place at the cathode, and oxidation at the anode. According to the IUPAC convention, the term electrode potential is reserved exclusively to describe half-reactions written as reductions. The sign of the half-cell in question determines the sign of an electrode potential when it is coupled to a standard hydrogen electrode.
Electrode potential is defined by measuring the potential relative to a standard hydrogen half cell
The convention is to designate the cell so that the oxidised form is written first. For example
The e.m.f. of this cell is
By convention, at p(H2) = 101325 Pa and a(H+) = 1.00, the potential of the standard hydrogen electrode is 0.000 V at all temperatures. As a consequence of this definition, any potential developed in a galvanic cell consisting of a standard hydrogen electrode and some other electrode is attributed entirely to the other electrode
Indicator is a substance used to show the presence of a chemical substance or ion by its colour. Acid-base indicators are compounds, such as phenolphtaleine and methyl orange, which change colour reversibly, depending on whether the solution is acidic or basic. Oxidation-reduction indicators are substances that show a reversible colour change between oxidised and reduced forms.
Glass electrode is a hydrogen-ion responsive electrode usually consisting of a bulb, or other suitable form, of special glass attached to a stem of high resistance glass complete with internal reference electrode and internal filling solution system. Glass electrode is also available for the measurement of sodium ions.
The glass electrode, which consists of a thin wall glass bulb, has an extremely high electrical resistance. The membrane of a typical glass electrode (with a thickness of 0.03 mm to 0.1 mm) has an electrical resistance of 30 MΩ to 600 MΩ. The surface of a glass membrane must be hydrated before it will function as a pH electrode. When a glass surface is immersed in an aqueous solution then a thin solvated layer (gel layer) is formed on the glass surface in which the glass structure is softer. This applies to both the outside and inside of the glass membrane.
The simplest explanation for the working of the thin glass electrode is that the glass acts as a weak acid (Glass-H).
The hydrogen ion activity of the internal solution is held constant. When a solution of different pH from the inside comes in contact with the outside of the glass membrane, the glass is either deprotonated or protonated relative to the inside of the glass. The difference in pH between solutions inside and outside the thin glass membrane creates electromotive force in proportion to this difference in pH.
Inert electrode is an electrode that serves only as a source or sink for electrons without playing a chemical role in the electrode reaction. Precious metals, mercury, and carbon are typically used as inert electrodes. The inert nature of the electrode can sometimes be questioned. While the electrode may not take part in the reaction as a reactant or product, it still can act as an electrocatalyst.
Ion selective electrode (ISE) is an electrode or electrode assembly with a potential that is dependent on the concentration of an ionic species in the test solution and is used for electroanalysis. Ion-selective electrodes are often membrane type electrodes.
For general reaction of some redox system
dependence of electrode potential of redox system upon activity of oxidised and reduced form in solution is described in Nernst’s equation for electrode potential:
where E = to electrode potential of redox system
E° = standard electrode potential of redox system
R = universal gas constant
T = thermodymical temperature
F = Faraday’s constant
z = number of electrons exchanged in redox reaction
aO = activity of oxidised form
aR = activity of reduced form
n = stechiometrical coefficient of oxidised form
m = stechiometrical coefficient of reduced form
By use of suitable radioactive isotopes biochemical processes can be observed in plants, animals and humans, by measuring radioactive radiation of radioactive indicator. Artificial radioactive isotopes have the same chemical properties as natural ones, which enable us to mark those natural isotopes with addition of artificial ones and in this way follow the path of those elements during a chemical reaction. One of the most important radioactive indicators is the radioactive carbon 14C.
Referent electrode is an electrode whose potential is known and completely independent of analyte concentration. Mostly used referent electrodes are calomel and silver/silver chloride electrode.
Table: Dependence of referent electrodes potentials on KCl concentration
| Potential vs. SHE / V | |||||
| calomel electrode | Ag/AgCl electrode | ||||
| t / °C | 0.1 mol dm-3 | 3.5 mol dm-3 | sat. solution | 3.5 mol dm-3 | sat. solution |
| 15 | 0.3362 | 0.254 | 0.2511 | 0.212 | 0.209 |
| 20 | 0.3359 | 0.252 | 0.2479 | 0.208 | 0.204 |
| 25 | 0.3356 | 0.250 | 0.2444 | 0.205 | 0.199 |
| 30 | 0.3351 | 0.248 | 0.2411 | 0.201 | 0.194 |
| 35 | 0.3344 | 0.246 | 0.2376 | 0.197 | 0.189 |
Silver/silver-chloride electrode is by far the most common reference type used today because it is simple, inexpensive, very stable and non-toxic. It is mainly used with saturated potassium chloride electrolyte, but can be used with lower concentrations such as 3.5 mol dm-3 or 1 mol dm-3 potassium chloride. Silver/silver-chloride electrode is a referent electrode based on the following halfreaction
| Potential vs. SHE / V | ||
|---|---|---|
| t / °C | 3.5 mol dm-3 | sat. solution |
| 15 | 0.212 | 0.209 |
| 20 | 0.208 | 0.204 |
| 25 | 0.205 | 0.199 |
| 30 | 0.201 | 0.194 |
| 35 | 0.197 | 0.189 |
Standard electrode potential (E°) (standard reduction potentials) are defined by measuring the potential relative to a standard hydrogen electrode using 1 mol solution at 25 °C. The convention is to designate the cell so that the oxidised form is written first. For example,
The e.m.f. of this cell is -0.76 V and the standard electrode potential of the Zn2+|Zn half cell is -0.76 V.
Generalic, Eni. "Indicator electrode." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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