Electrochemical cell is a device that converts chemical energy into electrical energy or vice versa when a chemical reaction is occurring in the cell. It consist of two electronically conducting phases (e.g., solid or liquid metals, semiconductors, etc) connected by an ionically conducting phase (e.g. aqueous or non-aqueous solution, molten salt, ionically conducting solid). As an electric current passes, it must change from electronic current to ionic current and back to electronic current. These changes of conduction mode are always accompanied by oxidation/reduction reactions.
An essential feature of the electrochemical cell is that the simultaneously occurring oxidation-reduction reactions are spatially separated. E.g., in a spontaneous chemical reaction during the oxidation of hydrogen by oxygen to water, electrons are passed directly from the hydrogen to the oxygen.
In contrast, in the spontaneous electrochemical reaction in a galvanic cell the hydrogen is oxidised at the anode by transferring electrons to the anode and the oxygen is reduced at the cathode by accepting electrons from the cathode. The ions produced in the electrode reactions, in this case positive hydrogen ions and the negative hydroxyl (OH-) ions, will recombine in the solution to form the final product of the reaction: water. During this process the electrons are conducted from the anode to the cathode through an outside electric circuit where the electric current can drive a motor, light a light bulb, etc. The reaction can also be reversed: water can be decomposed into hydrogen and oxygen by the application of electrical power in an electrolytic cell.
Electrolysis is the decomposition of a substance as a result of passing an electric current between two electrodes immersed in the sample.
Electrolytes are substances which, when melted or dissolved in water, conduct electric current. By melting or dissolving they are dissociated into electrically charged particles (ions) which are able to conduct electric current. By passing of electric current the transfer of matter occurs. Positively charged particles (cations) travel towards the negative pole (the cathode) and negatively charged particles (the anions) travel towards the positive pole (the anode). Liquid metals, in which the conduction is by free electrons, are not usually regarded as electrolytes. Solid conductors of ions, as in the sodium-sulphur cell, are also known as electrolytes. Depending upon how it conducts electric current, matter can be divided into strong electrolytes, weak electrolytes and nonconductors.
Transference number of an ion is the fraction of the total current that is carried by that ion during electrolysis. Different ions carry different fractions of the current because different ions move at different speeds under the same potential gradient. In general, a cation and an anion differ in the amount of current they can carry during electrolysis.
Volt (V) is the SI derived unit of electric potential. One volt is the difference of potential between two points of an electric conductor when a current of 1 ampere flowing between those points dissipates a power of 1 watt. It was named after the Italian physicist Alessandro Volta (1745-1827).
Electrolytic cell is an electrochemical cell that converts electrical energy into chemical energy. The chemical reactions do not occur spontaneously at the electrodes when they are connected through an external circuit. The reaction must be forced by applying an external electric current. It is used to store electrical energy in chemical form (rechargeable battery). It is also used to decompose or produce (synthesise) new chemicals by the application of electrical power. This process is called electrolysis, e.g., water can be decomposed into hydrogen gas and oxygen gas. The free energy change of the overall cell reaction is positive.
Faraday’s laws of electrolysis are two laws found by British chemist and physicist Michael Faraday (1791-1867) in his experiments on electrolysis:
1. The quantity of matter extracted on the electrode is proportional to the quantity of charge (Q = I·t) which has flown in electrolysis time.
where z = number of electrons changed in reaction and F = Faraday’s constant which equals 96 487 C mol-1.
2. The masses of the elements liberated by the same quantity of electricity are directly proportional to their chemical equivalents.
96 487 C will discharge 1 mol Ag and 1/2 mol Cu. The relevant half reactions are:
Voltametry is a common name for a large group of instrumental techniques which are based on measuring the electric current formed by a continuous potential shifting on the electrodes.
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.
Galvanic cell (voltaic cell) is a simple device with which chemical energy is converted into electrical energy. Galvanic cells consist of two separate compartments called half cells containing electrolyte solutions and electrodes that can be connected in a circuit. Two dissimilar metals (e.g., copper and zinc) are immersed in an electrolyte. If the metals are connected by an external circuit, one metal is reduced (i.e., gains electrons) while the other metal is oxidized (i.e., loses electrons).
In the example above, copper is reduced and zinc is oxidized. The difference in the oxidation potentials of the two metals provides the electric power of the cell.
A voltaic cell can be diagrammed using some simple symbols. In the diagram the electrodes are on the outer side of the diagram and a vertical line (|) is used to separate the electrode from the electrolyte solution found in the compartment. A double vertical line (||) is used to separate the cell compartments and is symbolic of the salt bridge. Usually in a diagram the species oxidized is written to the left of the double slash. Here is an example of the Daniell cell:
The names refer to the 18th-century Italian scientists Alessandro Volta (1745-1827) and Luigi Galvani (1737-1798).
Generalic, Eni. "Difuzijska struja." Croatian-English Chemistry Dictionary & Glossary. 29 June 2022. KTF-Split. {Date of access}. <https://glossary.periodni.com>.
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