Cathode Cations

Isotachophoresis. In isotachophoresis (ITP), or displacement electrophoresis or multizonal electrophoresis, the sample is inserted between two different buffers (electrolytes) without electroosmotic flow. The electrolytes are chosen so that one (the leading electrolyte) has a higher mobility and the other (the trailing electrolyte) has a lower mobility than the sample ions. An electric field is applied and the ions start to migrate towards the anode (anions) or cathode (cations). The ions separate into zones (bands) determined by their mobilities, after which each band migrates at a steady-state velocity and steady-state stacking of bands is achieved. Note that in ITP, unlike ZE, there is no electroosmotic flow and cations and anions cannot be separated simultaneously. Reference 26 provides a recent example of capillary isotachophoresis/zone electrophoresis coupled with nanoflow ESI-MS. 

Figure 12.18 shows the layout of an electrolytic cell used for the commercial production of magnesium metal from molten magnesium chloride (the Dow process). As in a galvanic cell, oxidation occurs at the anode and reduction occurs at the cathode, electrons travel through the external wire from anode to cathode, cations move through the electrolyte toward the cathode, and anions move toward the anode. But unlike the spontaneous current in a galvanic cell, a current must be supplied by an external electrical power source. This current drives electrons through the wire in a predetermined direction (Fig. 12.19). The result is...

Typically, the potential is adjusted to deposit the metal desired, and then the current is adjusted to deposit it as fast as possible and still get a good quality deposit. Regardless of the application, all are based on the law developed by Michael Faraday in 1833. He was the first to use the word electrode and used it for either electrode. Now the negative electrode is called the cathode (cation attracting), and the positive electrode is called the anode (anion attracting). 

These results, which revealed the competition between cathodic anion release and cathodic cation, e.g. Cs", binding into PP" FCN, led us to a further examination of this phenomenon using PP" CIO4 and PP OTs. The results demonstrated that the nature of the anion caused major differences in the competition between anion loss and cation gain. Perchlorate, for example, was more easily lost than tosylate into aqueous NaCl solution. It is hypothesized that the more hydrophobic tosylate is more strongly bound and preferentially retained. 

On the other hand, if the electrode above the center of the gel is cathode, cationic surfactant molecules adsorb on the surface of the anionic gel facing the ground which cause the center of the gel to move toward the cathode electrode. This is because the cathode electrode above the center of the gel attracts the surfactant molecules. 

As long as /t p > fif in (6.3. lOd), anionic species will also move toward the cathode. Cationic species wiU, however, move much faster toward the cathode, at a speed higher than the bulk velocity arising from the electroosmotic flow. These behaviors are schematically illustrated in Figure 6.3.5(c). Obviously, individual cationic species will move at different net velocities, (i/jz). The detector near the cathode will be detecting the appearance of each such ionic species, cationic or anionic, at different times. If the sample to be analyzed and injected near the anode into the capillary contains different species, one would like to know how well these species will be separated, what would be the value of the resolution, what is the maximum number of species that can be separated, etc. 

The left-hand electrode in Figure 2.1 is called the cathode (cations go to the electrode), which is a negatively charged electrode in the EC. The right-hand electrode is the positively charged anode, and anions go to the electrode. The polarity of the electrodes in an EC is defined by the polarity of the power supply, for example, the battery shown in Eigure 2.1. 

Note that chemists tend to refer to positive ions as cations (attracted to the cathode m electrolysis) and negative ions as anions (attracted to an anode). In this section of the encyclopedia, the temis positive ion and negative ion will be used for the sake of clarity. 

Solutions of nitric acid in 100% sulphuric acid have a high electrical conductivity. If nitric acid is converted into a cation in these solutions, then the migration of nitric acid to the cathode should be observed in electrolysis. This has been demonstrated to occur in oleum and, less conclusively, in concentrated acid, observations consistent with the formation of the nitronium ion, or the mono- or di-protonated forms of nitric acid. Conductimetric measurements confirm the quantitative conversion of nitric acid into nitronium ion in sulphuric acid. ... 

Capillary zone electrophoresis also can be accomplished without an electroosmotic flow by coating the capillary s walls with a nonionic reagent. In the absence of electroosmotic flow only cations migrate from the anode to the cathode. Anions elute into the source reservoir while neutral species remain stationary. 

The anode and cathode chambers are separated by a cation-permeable fluoropolymer-based membrane (see Membrane technology). Platinum-electroplated high surface area electrodes sold under the trade name of TySAR (Olin) (85,86) were used as the anode the cathode was formed from a two-layer HasteUoy (Cabot Corp.) C-22-mesh stmcture having a fine outer 60-mesh stmcture supported on a coarse inner mesh layer welded to a backplate. The cell voltage was 3.3 V at 8 kA/m, resulting ia a 40% current efficiency. The steady-state perchloric acid concentration was about 21% by weight. 

Sodium nitrite has been synthesized by a number of chemical reactions involving the reduction of sodium nitrate [7631-99-4] NaNO. These include exposure to heat, light, and ionizing radiation (2), addition of lead metal to fused sodium nitrate at 400—450°C (2), reaction of the nitrate in the presence of sodium ferrate and nitric oxide at - 400° C (2), contacting molten sodium nitrate with hydrogen (7), and electrolytic reduction of sodium nitrate in a cell having a cation-exchange membrane, rhodium-plated titanium anode, and lead cathode (8). 

For quantitative analysis, the resolution of the spectral analyzer must be significantly narrower than the absorption lines, which are - 0.002 nm at 400 nm for Af = 50 amu at 2500°C (eq. 4). This is unachievable with most spectrophotometers. Instead, narrow-line sources specific for each element are employed. These are usually hoUow-cathode lamps, in which a cylindrical cathode composed of (or lined with) the element of interest is bombarded with inert gas cations produced in a discharge. Atoms sputtered from the cathode are excited by coUisions in the lamp atmosphere and then decay, emitting very narrow characteristic lines. More recendy semiconductor diode arrays have been used for AAS (168) (see Semiconductors). 

Solvent for Electrolytic Reactions. Dimethyl sulfoxide has been widely used as a solvent for polarographic studies and a more negative cathode potential can be used in it than in water. In DMSO, cations can be successfully reduced to metals that react with water. Thus, the following metals have been electrodeposited from their salts in DMSO cerium, actinides, iron, nickel, cobalt, and manganese as amorphous deposits zinc, cadmium, tin, and bismuth as crystalline deposits and chromium, silver, lead, copper, and titanium (96—103). Generally, no metal less noble than zinc can be deposited from DMSO. 

The electrolyte thus formed can conduct electric current by the movement of ions under the influence of an electric field. A cell using an electrolyte as a conductor and a positive and a negative electrode is called an electrolysis cell. If a direct-current voltage is appHed to a cell having inert electrode material such as platinum, the hydrogen ions (cations) migrate to the cathode where they first accept an electron and then form molecular hydrogen. The ions... 

If the cations in solution are condensable as a soHd, such as copper, they can plate out on the cathode of the cell. As the same time, perhaps some hydrogen is also produced at the cathode. The SO can react with a copper anode material by taking it into solution to replace the lost copper ions. Thus the anode is a consumable electrode in the process. 

Electrodialysis. In electro dialysis (ED), the saline solution is placed between two membranes, one permeable to cations only and the other to anions only. A direct electrical current is passed across this system by means of two electrodes, causiag the cations ia the saline solution to move toward the cathode, and the anions to the anode. As shown ia Figure 15, the anions can only leave one compartment ia their travel to the anode, because a membrane separating them from the anode is permeable to them. Cations are both excluded from one compartment and concentrated ia the compartment toward the cathode. This reduces the salt concentration ia some compartments, and iacreases it ia others. Tens to hundreds of such compartments are stacked together ia practical ED plants, lea ding to the creation of alternating compartments of fresh and salt-concentrated water. ED is a continuous-flow process, where saline feed is continuously fed iato all compartments and the product water and concentrated brine flow out of alternate compartments. 

Electrodialysis. Electro dialysis processes transfer ions of dissolved salts across membranes, leaving purified water behind. Ion movement is induced by direct current electrical fields. A negative electrode (cathode) attracts cations, and a positive electrode (anode) attracts anions. Systems are compartmentalized in stacks by alternating cation and anion transfer membranes. Alternating compartments carry concentrated brine and purified permeate. Typically, 40—60% of dissolved ions are removed or rejected. Further improvement in water quaUty is obtained by staging (operation of stacks in series). ED processes do not remove particulate contaminants or weakly ionized contaminants, such as siUca. 

Electrically assisted transdermal dmg deflvery, ie, electrotransport or iontophoresis, involves the three key transport processes of passive diffusion, electromigration, and electro osmosis. In passive diffusion, which plays a relatively small role in the transport of ionic compounds, the permeation rate of a compound is deterrnined by its diffusion coefficient and the concentration gradient. Electromigration is the transport of electrically charged ions in an electrical field, that is, the movement of anions and cations toward the anode and cathode, respectively. Electro osmosis is the volume flow of solvent through an electrically charged membrane or tissue in the presence of an appHed electrical field. As the solvent moves, it carries dissolved solutes. 

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