CHEMISTRY GLOSSARY

electrical double layer    →   električni dvosloj

Electrical double layer is the structure of charge accumulation and charge separation that always occurs at the interface when an electrode is immersed into an electrolyte solution. The excess charge on the electrode surface is compensated by an accumulation of excess ions of the opposite charge in the solution. The amount of charge is a function of the electrode potential. This structure behaves essentially as a capacitor. There are several theoretical models that describe the structure of the double layer. The three most commonly used ones are the Helmholtz model, the Gouy-Chapman model, and the Gouy-Chapman-Stern model.

electrochemical cell    →   elektrokemijski članak

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.

weak base    →   slaba baza

Weak base is a base that only partially dissociates into ions in solution. Weak bases are weak electrolytes. Ammonia is an example of a weak base

fuel cell    →   gorivi članak

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.

galvanic celll    →   galvanski članak

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).

Kohlrausch’s law    →   Kohlrauschov zakon

Kohlrausch’s law states that the equivalent conductivity of an electrolyte at infinite dilution is equal to the sum of the conductances of the anions and cations. If a salt is dissolved in water, the conductivity of the solution is the sum of the conductances of the anions and cations. The law, which depends on the independent migration of ions, was deduced experimentally by the German chemist Friedrich Kohlrausch (1840-1910).

Gratzel solar cell    →   Gratzelova sunčeva ćelija

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.

Ostwald’s dilution law    →   Ostwaldov zakon razrjeđenja

Ostwald’s dilution law is a relation for the concentration dependence of the molar conductivity Λ of an electrolyte solution, viz.

where c is the solute concentration, K_c is the equilibrium constant for dissociation of the solute, and L₀ is the conductivity at cΛ = 0. The law was first put forward by the German chemist Wilhelm Ostwald (1853-1932).

redox potential    →   redoks potencijal

Redox potential is the potential of a reversible oxidation-reduction electrode measured with respect to a reference electrode, corrected to the hydrogen electrode, in a given electrolyte.

Heyrovsky-Ilkovic equation    →   Heyrovsky-Ilkovičeva jednadžba

The Heyrovsky-Ilkovic equation describes the entire current-potential curve (polarographic wave) of a reversible redox system in polarography

where R is the gas constant, T is the absolute temperature, F is the Faraday constant, n denotes the number of electrons taking part in the electrode reaction. E_1/2 is a unique potential (for a given reaction and supporting electrolyte) termed the half-wave potential.

In order to obtain E_1/2 from the above equation, we plot a graph of ln[(i_d-i)/i] against E. The intercept on the x-axis gives then an accurate value of E_1/2. The slope of the obtained straight line is equal to nF/RT from which n is determined.