Hoffman electrolysis apparatus used in electrolysis of water
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Epilators, Electrolysis

In chemistry and manufacturing, electrolysis is a method of separating bonded elements and compounds by passing an electric current through them. This can be seen in isolating copper compound from its ore. more...

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Overview

An ionic compound is dissolved with an appropriate solvent, or otherwise melted by heat, so that its ions are available in the liquid. An electrical current is applied between a pair of inert electrodes immersed in the liquid. The negatively charged electrode is called the cathode, and the positively charged one the anode. Each electrode attracts ions which are of the opposite charge. Therefore, positively charged ions (called cations) move towards the cathode, while negatively charged ions (termed anions) move toward the anode. The energy required to separate the ions, and cause them to gather at the respective electrodes, is provided by an electrical power supply. At the probes, electrons are absorbed or released by the ions, forming a collection of the desired element or compound.

In electrolysis, the anode is the positive electrode, meaning it has a deficit of electrons; species in contact with the anode can be stripped of electrons (i.e., they are oxidized). The cathode is the negative electrode, meaning it has a surplus of electrons. Species in contact with the cathode tend to gain electrons (i.e., they are reduced).

The amount of electrical energy that must be added equals the change in Gibbs free energy of the reaction plus the losses in the system. The losses can (theoretically) be arbitrarily close to zero, so the maximum thermodynamic efficiency equals the enthalpy change divided by the free energy change of the reaction. In most cases the electric input is larger than the enthalpy change of the reaction, so some energy is released in the form of heat. In some cases, for instance in the electrolysis of steam into hydrogen and oxygen at high temperature, the opposite is true. Heat is absorbed from the surroundings, and the heating value of the produced hydrogen is higher than the electric input. In this case the efficiency can be said to be greater than 100%. (It is worth noting that the maximum theoretic efficiency of a fuel cell is the inverse of that of electrolysis. It is thus impossible to create a perpetual motion machine by combining the two processes. See water fuel cell for an example of such an attempt.)

A higher current flow (amperage) through the cell means it will be passing more electrons through it at any given time. This means a faster rate of reduction at the cathode and a faster rate of oxidation at the anode. This corresponds to a greater number of moles of product. The amount of current that passes depends on the conductance of the electrodes and electrolyte, though it also depends on how much current the power source itself can generate. Current also makes a difference in that it can shift chemical equilibria by sheer mass action. The processes in an electrolytic cell with just two or three reactants can become very, very complex. Most of the time it is best to search the literature to see what current density works best for a desired process. For instance, metals plated at a certain current density might form a durable and shiny coating on the substrate, while some other current density might form an excessively grainy, dull coating.

Read more at Wikipedia.org


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