Long Chains

Maddrell salt, NaP03. A long chain phosphate obtained by heating Na2H2P407 to 230 300 C. 

Additives acting on the pour point also modify the crystal size and, in addition, decrease the cohesive forces between crystals, allowing flow at lower temperatures. These additives are also copolymers containing vinyl esters, alkyl acrylates, or alkyl fumarates. In addition, formulations containing surfactants, such as the amides or fatty acid salts and long-chain dialkyl-amines, have an effect both on the cold filter plugging point and the pour point. 

While the long chain hydrocarbons (above 18 carbon atoms) may exist in solution at reservoir temperature and pressure, they can solidify at the lower temperatures and pressures experienced in surface facilities, or even in the tubing. The fraction of the longer chain hydrocarbons in the crude oil are therefore of particular interest to process engineers, who will typically require a detailed laboratory analysis of the crude oil oomposition, extending to the measurement of the fraction of molecules as long as C3Q. 

Fig. IV-20. Film pressure-area plots for cerebronic acid (a long-chain a-hydroxy carboxylic acid) and cholesterol (see insert) and for an equimolar mixture. At low pressures the r-a plot is close to that of the average (dashed line), an unanticipated kink then appears, and finally, the horizontal portion probably represents ejection of the cholesterol. (From Ref. 239.)...

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. 

Photopolymerization reactions of monolayers have become of interest (note Chapter XV). Lando and co-workers have studied the UV polymerization of 16-heptadecenoic acid [311] and vinyl stearate [312] monolayers. Particularly interesting is the UV polymerization of long-chain diacetylenes. As illustrated in Fig. IV-30, a zipperlike process can occur if the molecular orientation in the film is just right (e.g., polymerization does not occur readily in the neat liquid) (see Refs. 313-315). 

As mentioned in Section IX-2A, binary systems are more complicated since the composition of the nuclei differ from that of the bulk. In the case of sulfuric acid and water vapor mixtures only some 10 ° molecules of sulfuric acid are needed for water oplet nucleation that may occur at less than 100% relative humidity [38]. A rather different effect is that of passivation of water nuclei by long-chain alcohols [66] (which would inhibit condensation note Section IV-6). A recent theoretical treatment by Bar-Ziv and Safran [67] of the effect of surface active monolayers, such as alcohols, on surface nucleation of ice shows the link between the inhibition of subcooling (enhanced nucleation) and the strength of the interaction between the monolayer and water. 

Fuerstenau and co-workers observed in the adsorption of a long-chain ammonium ion RNH3 on quartz that at a concentration of 10 Af there was six-tenths of a mono-layer adsorbed and the f potential was zero. At 10 M RNH3, however, the f potential was -60 mV. Calculate what fraction of a monolayer should be adsorbed in equilibrium with the 10 M solution. Assume a simple Stem model. 

A beautiful and elegant example of the intricacies of surface science is the formation of transparent, thermodynamically stable microemulsions. Discovered about 50 years ago by Winsor [76] and characterized by Schulman [77, 78], microemulsions display a variety of useful and interesting properties that have generated much interest in the past decade. Early formulations, still under study today, involve the use of a long-chain alcohol as a cosurfactant to stabilize oil droplets 10-50 nm in diameter. Although transparent to the naked eye, microemulsions are readily characterized by a variety of scattering, microscopic, and spectroscopic techniques, described below. 

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]. 

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