Electric potentials, formation

Schuurmans, J. J. Casey, R. P Kraayenhof, R. Transmembrane electrical potential formation in spinach chloroplasts investigation using a rapidly-responding extrinsic probe. FEBS Lett. 1978, 94, 405-409. 

Shahak Y, Admon A and Avron M (1982) Transmembrane electrical potential formation by chloroplast ATPase complex (CFj -CFq) proteoliposomes, FEBS Lett. 150, 27-31. 

A general prerequisite for the existence of a stable interface between two phases is that the free energy of formation of the interface be positive were it negative or zero, fluctuations would lead to complete dispersion of one phase in another. As implied, thermodynamics constitutes an important discipline within the general subject. It is one in which surface area joins the usual extensive quantities of mass and volume and in which surface tension and surface composition join the usual intensive quantities of pressure, temperature, and bulk composition. The thermodynamic functions of free energy, enthalpy and entropy can be defined for an interface as well as for a bulk portion of matter. Chapters II and ni are based on a rich history of thermodynamic studies of the liquid interface. The phase behavior of liquid films enters in Chapter IV, and the electrical potential and charge are added as thermodynamic variables in Chapter V. 

The deliberate raising of the electrical potential of titanium, either by the attachment of discrete particles of a noble metal, such as platinum or palladium, at the surface, or by the application of positive direct current to force the formation of a protective film, is dealt with at a later point. The electrochemical aspect of the corrosion of titanium is comprehensively treated in a number of papers ... 

As shown in Fig. 24, the mechanism of the instability is elucidated as follows At the portion where dissolution is accidentally accelerated and is accompanied by an increase in the concentration of dissolved metal ions, pit formation proceeds. If the specific adsorption is strong, the electric potential at the OHP of the recessed part decreases. Because of the local equilibrium of reaction, the fluctuation of the electrochemical potential must be kept at zero. As a result, the concentration component of the fluctuation must increase to compensate for the decrease in the potential component. This means that local dissolution is promoted more at the recessed portion. Thus these processes form a kind of positive feedback cycle. After several cycles, pits develop on the surface macroscopically through initial fluctuations. 

In a similar way, electrochemistry may provide an atomic level control over the deposit, using electric potential (rather than temperature) to restrict deposition of elements. A surface electrochemical reaction limited in this manner is merely underpotential deposition (UPD see Sect. 4.3 for a detailed discussion). In ECALE, thin films of chemical compounds are formed, an atomic layer at a time, by using UPD, in a cycle thus, the formation of a binary compound involves the oxidative UPD of one element and the reductive UPD of another. The potential for the former should be negative of that used for the latter in order for the deposit to remain stable while the other component elements are being deposited. Practically, this sequential deposition is implemented by using a dual bath system or a flow cell, so as to alternately expose an electrode surface to different electrolytes. When conditions are well defined, the electrolytic layers are prone to grow two dimensionally rather than three dimensionally. ECALE requires the definition of precise experimental conditions, such as potentials, reactants, concentration, pH, charge-time, which are strictly dependent on the particular compound one wants to form, and the substrate as well. The problems with this technique are that the electrode is required to be rinsed after each UPD deposition, which may result in loss of potential control, deposit reproducibility problems, and waste of time and solution. Automated deposition systems have been developed as an attempt to overcome these problems. 

The presence of an electrical potential drop, i.e., interfacial potential, across the boundary between two dissimilar phases, as well as at their surfaces exposed to a neutral gas phase, is the most characteristic feature of every interface and surface electrified due to the ion separation and dipole orientation. This charge separation is usually described as the formation of the ionic and dipolar double layers. The main interfacial potential is the Galvani potential (termed also by Trasatti the operative potential), which is the difference of inner potentials (p and of both phases. It is a function only of the chemical... 

It follows from the above that the mechanism for electrical potential oscillation across the octanol membrane in the presence of SDS would most likely be as follows dodecyl sulfate ions diffuse into the octanol phase (State I). Ethanol in phase w2 must be available for the transfer energy of DS ions from phase w2 to phase o to decrease and thus, facilitates the transfer of DS ions across this interface. DS ions reach interface o/wl (State II) and are adsorbed on it. When surfactant concentration at the interface reaches a critical value, a surfactant layer is formed at the interface (State III), whereupon, potential at interface o/wl suddenly shifts to more negative values, corresponding to the lower potential of oscillation. With change in interfacial tension of the interface, the transfer and adsorption of surfactant ions is facilitated, with consequent fluctuation in interface o/ wl and convection of phases o and wl (State IV). Surfactant concentration at this interface consequently decreased. Potential at interface o/wl thus takes on more positive values, corresponding to the upper potential of oscillation. Potential oscillation is induced by the repetitive formation and destruction of the DS ion layer adsorbed on interface o/wl (States III and IV). This mechanism should also be applicable to oscillation with CTAB. Potential oscillation across the octanol membrane with CTAB is induced by the repetitive formation and destruction of the cetyltrimethylammonium ion layer adsorbed on interface o/wl. Potential oscillation is induced at interface o/wl and thus drugs were previously added to phase wl so as to cause changes in oscillation mode in the present study. 

In addition to their use as reference electrodes in routine potentiometric measurements, electrodes of the second kind with a saturated KC1 (or, in some cases, with sodium chloride or, preferentially, formate) solution as electrolyte have important applications as potential probes. If an electric current passes through the electrolyte solution or the two electrolyte solutions are separated by an electrochemical membrane (see Section 6.1), then it becomes important to determine the electrical potential difference between two points in the solution (e.g. between the solution on both sides of the membrane). Two silver chloride or saturated calomel electrodes are placed in the test system so that the tips of the liquid bridges lie at the required points in the system. The value of the electrical potential difference between the two points is equal to that between the two probes. Similar potential probes on a microscale are used in electrophysiology (the tips of the salt bridges are usually several micrometres in size). They are termed micropipettes (Fig. 3.8D.)... 

A characteristic property of electrochemical membranes is the formation of an electric potential difference between the two sides of the membrane,... 

As the membrane has a surface charge leading to formation of a diffuse electrical layer, the adsorption of ions on the BLM is affected by the potential difference in the diffuse layer on both outer sides of the membrane 02 (the term surface potential is often used for this value in biophysics). Figure 6.12 depicts the distribution of the electric potential in the membrane and its vicinity. It will be assumed that the concentration c of the transferred univalent cation is identical on both sides of the membrane and that adsorption obeys a linear isotherm. Its velocity on the p side of the membrane (see scheme 6.1.1) is then... 

Based on the above results and discussion, the mechanism for the rhythmic oscillations at the oil/water interface with surfactant and alcohol molecules may be explained in the following way [3,47,48] with reference to Table 1. As the first step, surfactant and alcohol molecules diffuse from the bulk aqueous phase to the interface. The surfactant and alcohol molecules near the interface tend to form a monolayer. When the concentration of the surfactant together with the alcohol reaches an upper critical value, the surfactant molecules are abruptly transferred to the organic phase with the formation of inverted micelles or inverted microemulsions. This step should be associated with the transfer of alcohol from the interface to the organic phase. Thus, when the concentration of the surfactant at the interface decreases below the lower critical value, accumulation of the surfactant begins and the cycle is repeated. Rhythmic changes in the electrical potential and the interface tension are thus generated. 

In classical kinetic theory the activity of a catalyst is explained by the reduction in the energy barrier of the intermediate, formed on the surface of the catalyst. The rate constant of the formation of that complex is written as k = k0 cxp(-AG/RT). Photocatalysts can also be used in order to selectively promote one of many possible parallel reactions. One example of photocatalysis is the photochemical synthesis in which a semiconductor surface mediates the photoinduced electron transfer. The surface of the semiconductor is restored to the initial state, provided it resists decomposition. Nanoparticles have been successfully used as photocatalysts, and the selectivity of these reactions can be further influenced by the applied electrical potential. Absorption chemistry and the current flow play an important role as well. The kinetics of photocatalysis are dominated by the Langmuir-Hinshelwood adsorption curve [4], where the surface coverage PHY = KC/( 1 + PC) (K is the adsorption coefficient and C the initial reactant concentration). Diffusion and mass transfer to and from the photocatalyst are important and are influenced by the substrate surface preparation. 

Bronsted acid sites) or metal atoms with unsatisfied coordination (Lewis acid sites) react with water to form surface charge (13). Isomorphic substitution in the interlayer region of layered silicates results in a negative surface charge. In each case chemical "exchange" of ions between phases results in the formation of surface charge and the development of an electrical potential. 

CalcitrioPs action primary function is in regulating plasma calcium concentration. In health, the plasma total calcium concentration is tightly controlled at 2.35-2.55 mmol/1. Only the ionized or free fraction, amounting to about 50% of the total, is physiologically active in for example, maintenance of membrane electrical potential and bone formation. The hormone causes increased bone resorption via activation of osteoclasts (see Section 9.4) and increased intestinal absorption of calcium following the synthesis of a specific binding protein in mucosal cells. As described in Section 4.7, some... 

In 1848 du Bois-Reymond [21] suggested that the surfaces of biological formations have a property similar to the electrode of a galvanic cell and that this is the source of bioelectric phenomena observed in damaged tissues. The properties of biological membranes could not, however, be explained before at least the basic electrochemistry of simple models was formulated. The thermodynamic relationships for membrane equilibria were derived by Gibbs in 1875 [29], but because the theory of electrolyte solutions was formulated first by Arrhenius as late as 1887, Gibbs does not mention either ions or electric potentials. 

The electrochemical systems described so far are equilibrium systems. However, many membrane systems are not in equilibrium. Irreversible processes connected with charge transfer take part in the formation of electrical potential differences. If this charge transfer occurs in a homogeneous phase (for example. 

The only process occurring in a Hquid junction is the diffusion of various components of the two solutions in contact with it. The various mobilities of the ions present in the Hquid junction lead to the formation of an electric potential gradient, termed the diffusion potential gradient. A potential difference, termed the liquid-junction potential, A0x,. is formed between two solutions whose composition is assumed to be constant outside the Hquid junction. 

Thus, thioarylation may be facilitated electrochemically. The conventional nucleophilic substitution of the phenylthio gronp for bromine in 4-bromobenzophenone requires extremely rigid conditions. When a difference in electric potentials is set up, the reaction proceeds readily and gives products in a high yield (80%). It is sufficient to set up only the potential difference necessary to ensure the formation of the substrate anion-radical (with the potential and current strictly controlled). The chemical reaction takes place in the bulk of solution and yields 4-(phenylthio)benzophenone (Pinson and Saveant 1974) (Scheme 5.1). 

All PV cells depend upon the absorption of light, the subsequent formation and spatial separation of electrons and holes, and the collection of the electrons and holes at different energies (called electrical potential). The efficiency of electron and hole formation, separation, and collection determines the photocurrent, whereas the energy difference between the electrons and the holes in their final state before leaving the cell determines the photovoltage. 

The previous section discussed the structure at the junction of two phases, the one a solid electron conductor, the other an ionic solution. Why is this important Knowledge of the structure of the interface, the distribution of particles in this region, and the variation of the electric potential in the double layer, permits one to control reactions occurring in this region. Control of these reactions is important because they are the foundation stones of important mechanisms linked to the understanding of industrial processes and problems, such as deposition and dissolution of metals, corrosion, electrocatalysis, film formation, and electro-organic synthesis. 

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