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.
Calomel electrode is a type of half cell in which the electrode is mercury coated with calomel (Hg2Cl2) and the electrolyte is a solution of potassium chloride and saturated calomel. In the calomel half cell the overall reaction is
Table: Dependence of potential of calomel electrode upon temperature and concentration of KCl according to standard hydrogen electrode
Potential vs. SHE / V | |||
---|---|---|---|
t / °C | 0.1 mol dm-3 | 3.5 mol dm-3 | sat. solution |
15 | 0.3362 | 0.254 | 0.2511 |
20 | 0.3359 | 0.252 | 0.2479 |
25 | 0.3356 | 0.250 | 0.2444 |
30 | 0.3351 | 0.248 | 0.2411 |
35 | 0.3344 | 0.246 | 0.2376 |
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
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 |
Conditional or formal electrode potential (E°’) is equal to electrode potential (E) when overall concentrations of oxidised and reduced form in all its forms in a solution are equal to one. Conditional electrode potential includes all effects made by reactions that do not take part in the electron exchange, but lead to change of ion power, changes of pH, hydrolysis, complexing, precipitating, etc.
At 298 K (25 °C) and by converting natural (Napierian) logarithms into decimal (common, or Briggian) logarithms, Nernst’s equation for electrode potential can be written as follows:
Standard mean ocean water (SMOW) is a standard sample of pure water of accurately known isotopic composition which is maintained by the International Atomic Energy Agency. It is used for precise calibration of density and isotopic composition measurements.
Dropping mercury electrode (DME) is a working electrode arrangement for polarography in which mercury continuously drops from a reservoir through a capillary tube (internal diameter 0.03 - 0.05 mm) into the solution. The optimum interval between drops for most analyses is between 2 and 5 s. The unique advantage to the use of the DME is that the constant renewal of the electrode surface, exposed to the test solution, eliminates the effects of electrode poisoning.
Generalic, Eni. "Standard hidrogen electrode." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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