Electrolysis is the decomposition of a substance as a result of passing an electric current between two electrodes immersed in the sample.
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.
Electrophoresis is a technique for the analysis and separation of colloids, based on the movement of charged colloidal particles in an electric field. The migration is toward electrodes of charge opposite to that of the particles. The rate of migration of the particles depends on the field, the charge on the particles, and on other factors, such as the size and shape of the particles.
Electrophoresis is important in the study of proteins. The acidity of the solution can be used to control the direction in which a protein moves upon electrophoresis.
Electroplating (also called electrodeposition) is the deposition of a metallic coating onto an object by putting a negative charge onto the object and immersing it into a solution which contains a salt of the metal to be deposited. The metallic ions of the salt carry a positive charge and are attracted to the part. When they reach it, the negatively charged part provides the electrons to reduce the positively charged ions to metallic form.
Typically, a brass or nickel object is coated with a layer of silver by making use of electrolysis of a silver solution, using the object to be coated as the cathode. The anode consist of pure silver, and the cathode is the object to be plated. The electrolyte is a mixure of silver nitrate with potassium cyanide. The reactions are:
The cyanide ensures a low concentration of silver ions, a condition for providing the best plating results.
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:
Fuel cell is a device that converts chemical energy into electrical energy. It is different from a battery in that the energy conversion continues as long as fuel and oxidising agent are fed to the fuel cell; that is, in principle indefinitely. (A battery is manufactured with a limited amount of chemicals, and it is exhausted when all the chemicals have reacted.) It is a galvanic cell where spontaneous chemical reactions occur at the electrodes. The fuel is oxidised at the anode, and the oxidising agent (almost always oxygen or air) is reduced at the cathode. Presently, the most commonly used fuel is hydrogen. More conventional fuels (e.g., petrol or natural gas) must be converted (reformed) into hydrogen before they can be utilised in a fuel cell.
Some fuel cells employ an aqueous solution as electrolyte, that can be either acidic or basic (alkaline), or an ion-exchange membrane soaked in aqueous solution can act as the electrolyte. These fuel cells operate at relatively low temperatures (from room temperature to not much above the boiling point of water). Some fuel cells employ molten salts (especially carbonates) as electrolytes and have to operate at temperatures of several hundred degrees centigrade (Celsius). Others employ ionically conductive solids as electrolyte and must operate close to 1 000 °C.
Geiger counter (Geiger-Muller counter) is a device used to detect and measure ionising radiation. It consists of a tube containing a low-pressure gas (usually argon or neon with methane) and a cylindrical hollow cathode through the centre of which runs a fine-wire anode. A potential difference of about 1 000 V is maintained between the electrodes. An ionising particle or photon passing through a window into the tube will cause an ion to be produced and the high potential will accelerate it towards its appropriate electrode, causing an avalanche of further ionisations by collision. The consequent current pulses can be counted in electronic circuits or simply amplified to work a small loudspeaker in the instrument. It was first devised in 1908 by the German physicist Hans Geiger (1882-1945). Geiger and W. Muller produced an improved design in 1928.
Ilkovic equation is a relation used in polarography relating the diffusion current (id) and the concentration of the depolarizer (c), which is the substance reduced or oxidized at the dropping mercury electrode. The Ilkovic equation has the form
Where k is a constant which includes Faraday constant, π and the density of mercury, and has been evaluated at 708 for max current and 607 for average current, D is the diffusion coefficient of the depolarizer in the medium (cm2/s), n is the number of electrons exchanged in the electrode reaction, m is the mass flow rate of Hg through the capillary (mg/sec), and t is the drop lifetime in seconds, and c is depolarizer concentration in mol/cm3.
The equation is named after the scientist who derived it, the Slovak chemist, Dionýz Ilkovič 1907-1980).
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).
Grätzel solar cell is photoelectrochemical cell, developed by Michael Grätzel and collaborators, simulates some characteristics of the natural solar cell, which enables photosynthesis take place. In natural solar cell the chlorophyll molecules absorb light (most strongly in the red and blue parts of the spectrum, leaving the green light to be reflected). The absorbed energy is sufficient to knock an electron from the excited chlorophyll. In the further transport of electron, other molecules are involved, which take the electron away from chlorophyll. In Grätzel cell, the tasks of charge-carrier generation and transport are also assigned to different species.
His device consists of an array of nanometre-sized crystallites of the semiconductor titanium dioxide, welded together and coated with light-sensitive molecules that can transfer electrons to the semiconductor particles when they absorb photons. So, light-sensitive molecules play a role equivalent to chlorophyll in photosynthesis. In Grätzel cell, the light-sensitive molecule is a ruthenium ion bound to organic bipyridine molecules, which absorb light strongly in the visible range; titanium dioxide nanocrystals carry the received photoexcited electrons away from electron donors. On the other hand, a donor molecule must get back an electron, so that it can absorb another photon. So, this assembly is immersed in a liquid electrolyte containing molecular species (dissolved iodine molecules) that can pick up an electron from an electrode immersed in the solution and ferry it to the donor molecule. These cells can convert sunlight with efficiency of 10 % in direct sunlight and they are even more efficient in diffuse daylight.
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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