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
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.
Electrodeposition is a process of depositing solid materials on an electrode surface using electrolysis. It is a somewhat loosely used term that is applied to many technologies. There are a number of metal deposition technologies. However, not only metals but also different compounds can be electrodeposited. This is used most often for the formation of oxides (such as manganese dioxide and lead dioxide) by anodic oxidation of dissolved salts.
Electrodialysis is a procedure of dialysis accelerated with an electric field. Dialyser is divided into three sections. Solution flows through the middle section, between two semipermeable membranes alternately to positive ions and negative ions. An electrodes are placed in the neighbouring sections. Under the influence of electric field, positive ions will travel towards the cathode (the negative electrode), and negative ions towards the anode (the positive electrode), whereby travelling of ions through the membrane is accelerated. In this way, the feed water is separated into two streams: one of pure water and the other of more concentrated solution.
Generalic, Eni. "Calomel electrode." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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