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.
Weak electrolytes are those electrolytes which in water solutions dissociate only partially, giving ions and which are in equilibrium with undissociated molecules. Their water solutions conduct electric current weakly. For example, acetic acid partially dissociates into acetate ions and hydrogen ions, so that an acetic acid solution contains both molecules and ions.
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
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 |
Sacrificial protection is the protection of iron or steel against corrosion by using a more reactive metal. Pieces of zinc or magnesium alloy are attached to pump bodies and pipes. The protected metal becomes the cathode and does not corrode. The anode corrodes, thereby providing the desired sacrificial protection. These items are known as sacrificial anodes and "attract" the corrosion to them rather than the iron/steel. The sacrificial anodes must be replaced periodically as they corrode.
The iron pipe will be connected to a more reactive metal such as magnesium through cooper wires, the magnesium will donate its electrons to the iron preventing it from rusting. Iron which is oxidises will immediately be reduced back to iron.
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.
Standard hydrogen electrode is a system in which hydrogen ion and gaseous hydrogen are present in their standard states. The convention is to designate the cell so that the standard hydrogen electrode is written first.
The electrode is used as a reference (of zero) for the values of other standard electrode potentials.
The carbon dioxide ion selective electrode uses a gas-permeable membrane to separate the sample solution from the electrode internal solution. Dissolved carbon dioxide in the sample solution diffuses through the membrane until an equilibrium is reached between the partial pressure of CO2 in the sample solution and the CO2 in the internal filling solution. In any given sample the partial pressure of carbon dioxide will be proportional to the concentration of carbon dioxide. The diffusion across the membrane affects the level of hydrogen ions in the internal filling solution:
The hydrogen level of the internal filling solution is measured by the pH electrode located behind the membrane. The internal filling solution contains a high concentration of sodium bicarbonate (e.g. 0.1 mol/L NaHCO3) so that the bicarbonate level can be considered constant.
Generalic, Eni. "Valentni elektron." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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