The Substrates

We shall now examine how these factors can influence an electroorganic reaction, keeping in mind that they usually are interconnected in a not necessarily simple or predictable way. 

With the wide range of SSE s presently available, it should be possible to get an experimental value of Ein or E for almost any substrate, except possibly for those which are extremely difficult to reduce or oxidize or tend to form films. In the rare cases where an experimental value cannot be obtained, a reasonable value can often be inter- or extrapolated using known correlations between Hiickel MO parameters and oxidation or reduction potentials, or between gas phase ionization potentials and oxidation potentials 66 A very thorough discussion of structural effects on electrode reactions is available 24 as well as a comprehensive list of oxidation potentials of organic compounds 10  

Having obtained an approximate measure of E1/2 or E for the substrate, one can then compare it with the electrochemical properties of the SSE to be used. If the limit of the SSE is outside the range in which the substrate reacts one can be fairly sure that cpe will give products resulting from the substrate electrode process. If this is not the case, one should not be discouraged from running a preparative experiment at a series of different potentials, as has already been pointed out (Sect. 4.4). 

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Enzymes are classified in terms of the reactions which they catalyse and were formerly named by adding the suffix ase to the substrate or to the process of the reaction. In order to clarify the confusing nomenclature a system has been developed by the International Union of Biochemistry and the International Union of Pure and Applied Chemistry (see Enzyme Nomenclature , Elsevier, 1973). The enzymes are classified into divisions based on the type of reaction catalysed and the particular substrate. The suffix ase is retained and recommended trivial names and systematic names for classification are usually given when quoting a particular enzyme. Any one particular enzyme has a specific code number based upon the new classification. 

Oxidoreduciases. Enzymes catalysing redox reactions. The substrate which is oxidized is regarded as the hydrogen donor. This group includes the trivially named enzymes, dehydrogenases, oxidases, reductases, peroxidases, hydrogenases and hydroxylases. 

Hydrolases. Enzymes catalysing the hydrolytic cleavage ofC —O, C —N and C —C bonds. The systematic name always includes hydrolase but the recommended name is often formed by the addition of ase to the substrate. Examples are esterases, glucosidases, peptidases, proteinases, phospholipases. Other bonds may be cleaved besides those cited, e.g. during the action of sulphatases and phosphatases. 

Besides the material based characteristics, the difference of density of the used particle/substrate combination is a very important criterion. The difference of density influences the contrast of the radiographic tests. Tungsten carbides were used as mechanically resistant particles and titanium based alloys as substrate. The substrate material is marked by an advantageous relation of strength to density. This material is often used in aeronautics, astronautics, and for modification of boundary layers. The density of tungsten carbide (15.7 g/cm ) is about 3.5 times higher than the density of titanium (4.45-4.6 g/cm ). 

Due to the absorbed photon energy in the moment of the beam admission the particles and the substrate surface warm up very fast. As a consquence of the thermal induced stresses between the relative brittle hard particles, some particles brake apart and, because of the released impulse energy, they are ejected out of the effective beam zone, transmission... 

One ordinarily attributes the difference in surface potentials between that of the substrate and that for the film-coated surface to the film. Two conducting... 

Customarily, it is assumed that e is unity and that ]l = p,cos 9, where 0 is the angle of inclination of the dipoles to the normal. Harkins and Fischer [86] point out the empirical nature of this interpretation and prefer to consider only that AV is proportional to the surface concentration F and that the proportionality constant is some quantity characteristic of the film. This was properly cautious as there are many indications that the surface of water is structured and that the structure is altered by the film (see Ref. 37). Accompanying any such structural rearrangement of the substrate at the surface should be a change in its contribution to the surface potential so that AV should not be assigned too literally to the film molecules. 

While the canal viscometer provides absolute viscosities and the effect of the substrate drag can be analyzed theoretically, the shear rate is not constant and the measurement cannot be made at a single film pressure as a gradient is required. Another basic method, more advantageous in these respects, is one that goes back to Plateau... 

Theoretical models of the film viscosity lead to values about 10 times smaller than those often observed [113, 114]. It may be that the experimental phenomenology is not that supposed in derivations such as those of Eqs. rV-20 and IV-22. Alternatively, it may be that virtually all of the measured surface viscosity is developed in the substrate through its interactions with the film (note Fig. IV-3). Recent hydrodynamic calculations of shape transitions in lipid domains by Stone and McConnell indicate that the transition rate depends only on the subphase viscosity [115]. Brownian motion of lipid monolayer domains also follow a fluid mechanical model wherein the mobility is independent of film viscosity but depends on the viscosity of the subphase [116]. This contrasts with the supposition that there is little coupling between the monolayer and the subphase [117] complete explanation of the film viscosity remains unresolved. 

In actual practice the soluble component usually is injected into the substrate solution after the insoluble monolayer has been spread. The reason is that if one starts with the solution, the surface tension may be low enough that the monolayer will not spread easily. McGregor and Barnes have described a useful injection technique [265]. 

An interesting consequence of covering a surface with a film is that the rate of evaporation of the substrate is reduced. Most of these studies have been carried out with films spread on aqueous substrates in such cases the activity of the water is practically unaffected because of the low solubility of the film material, and it is only the rate of evaporation and not the equilibrium vapor pressure that is affected. Barnes [273] has reviewed the general subject. 

The most common situation studied is that of a film reacting with some species in solution in the substrate, such as in the case of the hydrolysis of ester monolayers and of the oxidation of an unsaturated long-chain acid by aqueous permanganate. As a result of the reaction, the film species may be altered to the extent that its area per molecule is different or may be fragmented so that the products are soluble. One may thus follow the change in area at constant film pressure or the change in film pressure at constant area (much as with homogeneous gas reactions) in either case concomitant measurements may be made of the surface potential. 

I.P.P.D and its relatives have become standard procedures for the characterization of the structure of both clean surfaces and those having an adsorbed layer. Somoijai and co-workers have tabulated thousands of LEED structures [75], for example. If an adsorbate is present, the substrate surface structure may be altered, or reconstructed, as illustrated in Fig. VIII-9 for the case of H atoms on a Ni(llO) surface. Beginning with the (experimentally) hypothetical case of (100) Ar surfaces. Burton and Jura [76] estimated theoretically the free energy for a surface transition from a (1 x 1) to a C(2x 1) structure as given by... 

SIAM Scanning interferometric apertureless microscopy [103b] Laser light is reflected off the substrate, and scattering between an AFM tip and sample is processed interferometrically Diffraction Surface structure... 

The microscopic complexity of the contact angle is illustrated in Fig. X-14, which shows the edge of a solidified drop of glass—note the foot that spreads out from the drop. Ruckenstein [176] discusses some aspects of this, and de Gennes [87] has explained the independence of the spreading rate on the nature of the substrate as due to a precursor film present also surrounding a nonspread-... 

Returning to more surface chemical considerations, most literature discussions that relate adhesion to work of adhesion or to contact angle deal with surface free energy quantities. It has been pointed out that structural distortions are generally present in adsorbed layers and must be present if bulk liquid adsorbate forms a finite contact angle with the substrate (see Ref. 115). Thus both the entropy and the energy of adsorption are important (relative to bulk liquid). The... 

Because of the charged nature of many Langmuir films, fairly marked effects of changing the pH of the substrate phase are often observed. An obvious case is that of the fatty-acid monolayers these will be ionized on alkaline substrates, and as a result of the repulsion between the charged polar groups, the film reverts to a gaseous or liquid expanded state at a much lower temperature than does the acid form [121]. Also, the surface potential drops since, as illustrated in Fig. XV-13, the presence of nearby counterions introduces a dipole opposite in orientation to that previously present. A similar situation is found with long-chain amines on acid substrates [122]. 

Most LB-forming amphiphiles have hydrophobic tails, leaving a very hydrophobic surface. In order to introduce polarity to the final surface, one needs to incorporate bipolar components that would not normally form LB films on their own. Berg and co-workers have partly surmounted this problem with two- and three-component mixtures of fatty acids, amines, and bipolar alcohols [175, 176]. Interestingly, the type of deposition depends on the contact angle of the substrate, and, thus, when relatively polar monolayers are formed, they are deposited as Z-type multilayers. Phase-separated LB films of hydrocarbon-fluorocarbon mixtures provide selective adsorption sites for macromolecules, due to the formation of a step site at the domain boundary [177]. 

Notice in Table XVIII-1 a value for the self-diffusion of Ni on Ni(lll) measured using radioactive Ni. More gross processes can occur. Supported Ni crystallites (on alumina) may show spreading and wetting phenomena due to complex interactions with the substrate [146]. 

Surface states can be divided into those that are intrinsic to a well ordered crystal surface with two-dimensional periodicity, and those that are extrinsic [25]. Intrinsic states include those that are associated with relaxation and reconstruction. Note, however, that even in a bulk-tenuinated surface, the outemiost atoms are in a different electronic enviromuent than the substrate atoms, which can also lead to intrinsic surface states. Extrinsic surface states are associated with imperfections in the perfect order of the surface region. Extrinsic states can also be fomied by an adsorbate, as discussed below. 

Molecular adsorbates usually cover a substrate with a single layer, after which the surface becomes passive with respect to fiirther adsorption. The actual saturation coverage varies from system to system, and is often detenumed by the strength of the repulsive interactions between neighbouring adsorbates. Some molecules will remain intact upon adsorption, while others will adsorb dissociatively. This is often a frinction of the surface temperature and composition. There are also often multiple adsorption states, in which the stronger, more tightly bound states fill first, and the more weakly bound states fill last. The factors that control adsorbate behaviour depend on the complex interactions between adsorbates and the substrate, and between the adsorbates themselves. 

Chemisorption occurs when the attractive potential well is large so that upon adsorption a strong chemical bond to a surface is fonued. Chemisorption involves changes to both the molecule and surface electronic states. For example, when oxygen adsorbs onto a metal surface, a partially ionic bond is created as charge transfers from the substrate to the oxygen atom. Other chemisorbed species interact in a more covalent maimer by sharing electrons, but this still involves perturbations to the electronic system. 

An example of the fomiation of a new reconstmction is given by certain fee (110) metal surfaces. The clean surfaces have (1x1) synunetry, but become (2x1) upon adsorption of oxygen [16, 38]. The (2x1) synuiietry is not just due to oxygen being adsorbed into a (2 x 1) surface unit cell, but also because the substrate atoms rearrange themselves... 

A more dramatic type of restmctiiring occurs with the adsorption of alkali metals onto certain fee metal surfaces [39]. In this case, multilayer composite surfaces are fomied in which the alkali and metal atoms are intemiixed in an ordered stmcture. These stmctiires involve the substitution of alkali atoms into substrate sites, and the details of the stmctiires are found to be coverage-dependent. The stmctiires are influenced by the repulsion between the dipoles fomied by neighbouring alkali adsorbates and by the interactions of the alkalis with the substrate itself [40]. 

In corrosion, adsorbates react directly with the substrate atoms to fomi new chemical species. The products may desorb from the surface (volatilization reaction) or may remain adsorbed in fonning a corrosion layer. Corrosion reactions have many industrial applications, such as dry etching of semiconductor surfaces. An example of a volatilization reaction is the etching of Si by fluorine [43]. In this case, fluorine reacts with the Si surface to fonn SiF gas. Note that the crystallinity of the remaining surface is also severely disrupted by this reaction. An example of corrosion layer fonnation is the oxidation of Fe metal to fonn mst. In this case, none of the products are volatile, but the crystallinity of the surface is dismpted as the bulk oxide fonns. Corrosion and etching reactions are discussed in more detail in section A3.10 and section C2.9. 

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