Interface acids

Degradation of paint occurs by reaction at the surface and at the paint interface. Acid deposition can cause paint peeling on wood. (Photo by R. S. Williams.)... 

Polymer Surfaces and Interfaces Acid-Base Interactions and Adhesion in Polymer-Metal Systems... 

Polymer Surfaces and Interfaces Acid-Base Interactions and Adhesion in Polymer-Metal Systems Irina A. Starostina, DSc, Oleg V. Stoyanov, DSc, and Rustam Ya. Deberdeev, DSc... 

The structure (B) is actually interfaced acid and as the results of poten-siometric titrations show, amides of carbonyl acids are more weak acids, than bases [4], As basicity and nucleophility are the values, mutually connected with each other, the decrease of basicity leads to the decrease of nucleophilic reactional ability of amino group of urea. The effective atomic charges and lengths of bonds in molecules of derivatives of the urea received by optimization a of geometrical parameters by semi-empirical, quantum-chemical method MNDO are shown in Fig. 2. 

B. Solid/liquid interface acid-base reactions in interlayers of... 

Characterization and interfacial properties of solid surfaces, solid-fluid interfaces, acid-base interactions, and colloidal dispersions... 

Though adsorption need not be followed by absorption, absorption depends upon the concentration of the molecules at the surface or interface. Acidic and basic dyes which can be distinguished by their staining power are important tools not only in histological studies, but also In experimental physiology, where they serve to trace the pathway and distribution of dissolved substzinces across cells and tissues. The rate of their entrance into cells depends to some extent on their accumulation on cell surfaces prior to penetration. The cell colloids contain... 

It was determined, for example, that the surface tension of water relaxes to its equilibrium value with a relaxation time of 0.6 msec [104]. The oscillating jet method has been useful in studying the surface tension of surfactant solutions. Figure 11-21 illustrates the usual observation that at small times the jet appears to have the surface tension of pure water. The slowness in attaining the equilibrium value may partly be due to the times required for surfactant to diffuse to the surface and partly due to chemical rate processes at the interface. See Ref. 105 for similar studies with heptanoic acid and Ref. 106 for some anomalous effects. 

Mixtures of polymers at surfaces provide the interesting possibility of exploring polymer miscibility in two dimensions. Baglioni and co-workers [17] have shown that polymers having the same orientation at the interface are compatible while those having different orientations are not. Some polymers have their hydrophobic portions parallel to the surface, while others have a perpendicular disposition. The surface orientation effect is also present in mixtures of poly(methyl methacrylate), PMMA, and fatty acids. 

The behavior of insoluble monolayers at the hydrocarbon-water interface has been studied to some extent. In general, a values for straight-chain acids and alcohols are greater at a given film pressure than if spread at the water-air interface. This is perhaps to be expected since the nonpolar phase should tend to reduce the cohesion between the hydrocarbon tails. See Ref. 91 for early reviews. Takenaka [92] has reported polarized resonance Raman spectra for an azo dye monolayer at the CCl4-water interface some conclusions as to orientation were possible. A mean-held theory based on Lennard-Jones potentials has been used to model an amphiphile at an oil-water interface one conclusion was that the depth of the interfacial region can be relatively large [93]. 

There is a fair amount of work reported with films at the mercury-air interface. Rice and co-workers [107] used grazing incidence x-ray diffraction to determine that a crystalline stearic acid monolayer induces order in the Hg substrate. Quinone derivatives spread at the mercury-n-hexane interface form crystalline structures governed primarily by hydrogen bonding interactions [108]. 

Among the many applications of LB films, the creation or arrangement of colloidal particles in these films is a unique one. On one hand, colloidal particles such as 10-nm silver sols stabilized by oleic acid can be spread at the air-water interface and LB deposited to create unique optical and electrooptical properties for devices [185]. 

A large variety of organic oxidations, reductions, and rearrangements show photocatalysis at interfaces, usually of a semiconductor. The subject has been reviewed [326,327] some specific examples are the photo-Kolbe reaction (decarboxylation of acetic acid) using Pt supported on anatase [328], the pho-... 

Raduge C, Pfiumio V and Shen Y R 1997 Surface vibrational spectroscopy of sulfuric acid-water mixtures at the liquid-vapor interface Chem. Phys. Lett. 274 140... 

In moist enviromnents, water is present either at the metal interface in the fonn of a thin film (perhaps due to condensation) or as a bulk phase. Figure A3.10.1 schematically illustrates another example of anodic dissolution where a droplet of slightly acidic water (for instance, due to H2SO4) is in contact with an Fe surface in air [4]. Because Fe is a conductor, electrons are available to reduce O2 at the edges of the droplets. 

When concentrated sulphuric acid is added to a nitrate in the presence of aqueous iron(II) sulphate, the nitrogen oxide liberated forms a brown complex [Fe(H20)5N0] which appears as a brown ring at the acid-aqueous interface (test for a nitrate, p 243). 

The mixture of ethanol and concentrated sulphuric acid required in this and several subsequent preparations should always be prepared by adding the heavy acid to the ethanol. If the ethanol is added to the acid, it will tend to float on the surface of the acid, and the heat generated at the interface may blow the upper liquid out of the flask... 

To our knowledge, the results presented in this chapter provide the first example of enantioselective Lewis-acid catalysis of an organic reaction in water. This discovery opens the possibility of employing the knowledge and techniques from aqueous coordination chemistry in enantioselective catalysis. This work represents an interface of two disciplines hitherto not strongly connected. 

The solvent used m catalytic hydrogenation is chosen for its ability to dissolve the alkene and is typically ethanol hexane or acetic acid The metal catalysts are insoluble m these solvents (or indeed m any solvent) Two phases the solution and the metal are present and the reaction takes place at the interface between them Reactions involving a substance m one phase with a different substance m a second phase are called het erogeneous reactions... 

As with polyesters, the amidation reaction of acid chlorides may be carried out in solution because of the enhanced reactivity of acid chlorides compared with carboxylic acids. A technique known as interfacial polymerization has been employed for the formation of polyamides and other step-growth polymers, including polyesters, polyurethanes, and polycarbonates. In this method the polymerization is carried out at the interface between two immiscible solutions, one of which contains one of the dissolved reactants, while the second monomer is dissolved in the other. Figure 5.7 shows a polyamide film forming at the interface between an aqueous solution of a diamine layered on a solution of a diacid chloride in an organic solvent. In this form interfacial polymerization is part of the standard repertoire of chemical demonstrations. It is sometimes called the nylon rope trick because of the filament of nylon produced by withdrawing the collapsed film. 

Chloroacetyl chloride [79-04-9] (CICH2COCI) is the corresponding acid chloride of chloroacetic acid (see Acetyl chloride). Physical properties include mol wt 112.94, C2H2CI2O, mp —21.8 C, bp 106°C, vapor pressure 3.3 kPa (25 mm Hg) at 25°C, 12 kPa (90 mm Hg) at 50°C, and density 1.4202 g/mL and refractive index 1.4530, both at 20°C. Chloroacetyl chloride has a sharp, pungent, irritating odor. It is miscible with acetone and bensene and is initially insoluble in water. A slow reaction at the water—chloroactyl chloride interface, however, produces chloroacetic acid. When sufficient acid is formed to solubilize the two phases, a violent reaction forming chloroacetic acid and HCl occurs. 

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