Water-Surface Effects

I have been carried. .. into the sanctuary of minuteness and of power, where molecules obey the laws of their existence, clash together in fierce collision, or grapple in yet more fierce embrace, building up in secret the forms of visible things. 

In this chapter we address several phenomena involving a solvent, principally water, and a stationary surface. These include various wetting and wall effects, chromatography, and membrane passage. Some of these phenomena have been modeled with cellular automata, and a brief description of those studies will be presented. Each of these examples opens up a wealth of possibilities for future work, and the reader is urged to pursue some studies that these may inspire. 

Studies described in earlier chapters used cellular automata dynamics to model the hydrophobic effect and other solution phenomena such as dissolution, diffusion, micelle formation, and immiscible solvent demixing. In this section we describe several cellular automata models of the influence of the hydropathic state of a surface on water and on solute concentration in an aqueous solution. We first examine the effect of the surface hydropathic state on the accumulation of water near the surface. A second example models the effect of surface hydropathic state on the rate and accumulation of water flowing through a tube. A final example shows the effect of the surface on the concentration of solute molecules within an aqueous solution. 

Example 6.1. Effect of wall hydropathic state on water. 

In these studies the wall hydropathic state is varied to reveal the influence on nearby water molecules. In this example the wall is defined as a polar surface. 

---

Interesting pattern formations also occur in surfactants spreading on water due to a hydrodynamic instability [52]. The spreading velocity from a crystal may vary with direction, depending on the contour and crystal facet. There may be sufficient imbalance to cause the solid particle to move around rapidly, as does camphor when placed on a clean water surface. The many such effects have been reviewed by Stemling and Scriven [53]. 

The Langevin model has been employed extensively in the literature for various numerical and physical reasons. For example, the Langevin framework has been used to eliminate explicit representation of water molecules [22], treat droplet surface effects [23, 24], represent hydration shell models in large systems [25, 26, 27], or enhance sampling [28, 29, 30]. See Pastor s comprehensive review [22]. 

Aquatic Toxicity. The standard tests to measure the effect of substances on the aquatic environment are designed to deal with those that are reasonably soluble ia water. Unfortunately this is a disadvantage for the primary phthalates because they have a very low water solubiUty (ca 50 p.g/L) and this can lead to erroneous test results. The most common problem is seen ia toxicity tests on daphnia where the poorly water-soluble substance forms a thin film on the water surface within which the daphnia become entrapped and die. These deaths are clearly not due to the toxicity of the substance but due to unsuitable test design. 

Rhenium exhibits a greater resistance than tungsten to the water cycle effect, in which lamps and electron tubes become blackened by deposition of metal. This phenomenon involves catalysis by small quantities of water that react with the metal in a hot filament to produce a volatile metal oxide and hydrogen. The oxide condenses on the surface of the bulb and is reduced back to the metal by hydrogen. 

Many of the unique properties of siUcone oils are associated with the surface effects of dimethylsiloxanes, eg, imparting water repeUency to fabrics, antifoaming agents, release liners for adhesive labels, and a variety of poHshes and waxes (343). Dimethylsilicone oils can spread onto many soHd and Hquid surfaces to form films of molecular dimensions (344,345). This phenomenon is greatly affected by even small changes in the chemical stmcture of siloxane in the siloxane polymer. Increasing the size of the alkyl substituent from methyl to ethyl dramatically reduces the film-forming abiUty of the polymer (346). The phenyl-substituted siUcones are spread onto water or soHd surfaces more slowly than PDMS (347). 

Copper Corrosion Inhibitors. The most effective corrosion inhibitors for copper and its alloys are the aromatic triazoles, such as benzotriazole (BZT) and tolyltriazole (TTA). These compounds bond direcdy with cuprous oxide (CU2O) at the metal surface, forming a "chemisorbed" film. The plane of the triazole Hes parallel to the metal surface, thus each molecule covers a relatively large surface area. The exact mechanism of inhibition is unknown. Various studies indicate anodic inhibition, cathodic inhibition, or a combination of the two. Other studies indicate the formation of an insulating layer between the water surface and the metal surface. A recent study supports the idea of an electronic stabilization mechanism. The protective cuprous oxide layer is prevented from oxidizing to the nonprotective cupric oxide. This is an anodic mechanism. However, the triazole film exhibits some cathodic properties as well. 

Surface Applied Surfactants. Antistat agents can be appHed direcdy to the surface of a plastic part. Usually the antistat is diluted in water or in a solvent. The antistat solution is appHed by spraying, dipping, or wiping on the surface. The water or solvent dries leaving a thin film that attracts moisture. Since it is appHed to the surface, migration through the resin is not a factor. In practice, the quaternary ammonium compounds find the most use. They are soluble in water and effective at low concentrations. 

A special form of crevice attack can occur at a waterline or at the edges of water droplets. At the water surface, a meniscus region is present where surface tension causes water to climb up the metal surface it contacts. In effect, a crevice is formed between the air-liquid and liquid-metal interface at the meniscus. Oxygen concentration is high at the meniscus due to the greater accessibility of this region to the air. The meniscus region becomes cathodic to the adjacent metal surface. Corrosion occurs just below the meniscus, and chloride, if present, is... 

Production through much of the year will be subject to other constraints for example, the availability of light beneath the water surface. Seasonal differences in day length and periodic fluctuations in the depth of light penetration by active wavelengths often have an overriding effect on the net production rates and the supportive capacity. 

Among contaminants one of the most objectionable is oil, especially in systems where water is strongly heated. A relatively small amount of oil on a heating surface can produce very rapid failures. An indirect effect of oil, or other contaminants which form films on the water surface, is that the film isolates the water from air so that in polluted water anaerobic conditions may develop with the encouragement of objectionable bacterial activity. 

Adventitious surfactants also have a marked effect on the mechanism of coalescence. In studying the coalescence of curved water surfaces, Lindblad (L8) used aged distilled water that was stored for about 30 h in a polyethylene bottle opened to the air through a narrow polyethylene tube inserted in the water. He found that if fresh distilled water (water exposed not longer than 1 h to the air) was used, the delay time in coalescence was approximately half as long. Consequently, he concluded that this difference is due to some form of contamination which settled into the water or onto the water surface. 

---