Relationship between dehydration

It is known that the qualitative and quantitative composition of the thennal degradation products from polysaccharides can be altered by use of different catalysts [1]. Inorganic acids are not well selective catalysts as they affect both the degradation and condensation reactions in the pyrolysis process. A relationship between dehydration, degradation and condensation reactions is determined by the individual properties of the acid, the characteristics of the cellulose structure and by the pyrolysis conditions... 

Addition and elimination processes are the reverse of one another in a formal sense. There is also a close mechanistic relationship between the two reactions, and in many systems reaction can occur in either direction. For example, hydration of alkenes and dehydration of alcohols are both familiar reactions that are related as an addition-elimination pair. 

When these minerals are heated they dehydrate in a remarkable way by extruding little wormlike structures as indicated by their name (Latin vermiculus, little worm) the resulting porous light-weight mass is much used for packing and insulation. The relationship between the various layer silicates is summarized with idealized formulae in Table 9.10 (on page 357). 

At least four series of periodates are known, interconnected in aqueous solutions by a complex series of equilibria involving deprotonation, dehydration and aggregation of the parent acid H5IO6 — cf. telluric acids (p. 782) and antimonic acids (p. 577) in the immediately preceding groups. Nomenclature is summarized in Table 17.24, though not all of the fully protonated acids have been isolated in the free state. The structural relationship between these acids, obtained mainly from X-ray studies on their salts, are shown in Fig. 17.24. H5IO6 itself (mp 128.5° decomp) consists of molecules of (HO)sIO linked into a three-dimensional array by O-H - O bonds (10 for each molecule, 260-278 pm). 

It yields a phenylurethane if it is heated almost to boiliog-point with phenyl-isocyanate. This compound melts, at 106° to 107°. On dehydration with phosphoric acid it yields the sesquiterpene cedrene. The relationship between cedrene and cedrol is probably as follows —... 

Dehydration reactions. In early studies of dehydration reactions (e.g. of CuS04 5 H20 [400]), the surfaces of large crystals of reactant were activated through the incorporation of product into surfaces by abrasion with dehydrated material. An advantage of this pretreatment was the elimination of the problems of kinetic analysis of the then little understood relationship between a and time during the acceleratory process. Such surface modification resulted in the effective initiation of reaction at all boundary surfaces and rate studies were exclusively directed towards measurement of the rate of interface advance into the bulk. 

Aldoximes are prepared from aldehydes and hydroxylamine by condensation reaction, and the dehydration reaction of aldoxime is one of the most important methods of nitrile synthesis in organic chemistry." We speculated that it would become one of the most important examples in Green Chemistry if the dehydration reaction could be realized by an enzymatic method, and started studies on a new enzyme, aldoxime dehydratase, and its use in enzymatic nitrile synthesis. Furthermore, we clarified the relationship between aldoxime dehydratase and nitrile-degrading enzymes in the genome of the microorganisms and the physiological role of the enzyme. 

Such a classification of technetium cluster compounds, in our opinion, reflects the relationship between the thermal stability and structure of the clusters quite well. Moreover, on the basis of this classification it is easier to follow the mechanism of the main thermochemical transitions of technetium clusters, such as (1) dehydration (2) disproportionation and related processes occurring without changes or with only small changes in mass (3) one-stage processes of thermolysis. We shall now consider these main mechanisms of the thermochemical reactions of technetium clusters in greater detail. 

Among the oxyacids of sulfur the predilection to form an anhydride with a sulfur-sulfur bond, rather than one with an oxygen bridge between the two sulfurs, is not restricted to sulfenic acids. We will see in a subsequent section that sulfinic acids also do this. Their anhydrides have the sulfinyl sulfone structure. RS(0)S02R, rather than RS(0)0S(0)R. What is unique about the sulfenic acid-thiolsulfinate system, however, is the fact that the anhydride (thiolsulfinate) is strongly preferred thermodynamically over the acid at equilibrium. With any other type of common acid the reverse is true, of course. The uniqueness of the sulfenic acid-thiolsulfinate situation can perhaps best be appreciated by realizing that, if the same stability relationship between acid and anhydride were to exist for carboxylic acids, acetic acid would spontaneously dehydrate to acetic anhydride ... 

The transformation of ferrihydrite to hematite by dry heating involves a combination of dehydration/dehydroxylation and rearrangement processes leading to a gradual structural ordering within the ferrihydrite particles in the direction of the hematite structure. This transformation may or may not be facilitated by the postulated structural relationship between the two phases. EXAFS studies have shown, for example, that some face sharing between FeOg octahedra, characteristic of hematite, also exists in 6-line ferrihydrite (see chap. 2). 

As already mentioned, in spite of the widespread use of alumina in industry as adsorbent, catalyst, or catalyst support, there is only a limited understanding about the relationship between its surface properties and dehydroxylation-rehydroxylation behavior. The rehydration-dehydration behavior of transition aluminas containing controlled amounts of pentahedral A1 has been investigated by Coster et al. [185],... 

A convenient route to 2-alkylthio-4-alkyl-4-hydroxy-5,6-dihydro-4/7-l,3-thiazine derivatives 176 is the reaction of A-alkyldithiocarbamates with a,/3-unsaturated ketones in the presence of boron trifluoride etherate at 0°C (Scheme 15) <2002HAC377>. The predominant diastereomer displayed a m-relationship between the hydroxyl group and the C-4 substituent. Subsequent dehydration led to two isomeric products 177 and 178 with an equilibrium mixture resulting in a ratio of 94 6 in the case of 2-benzylthio-4-hydroxy-4-methyl-5,6-dihydro-4/7-l,3-thiazine. 2-Phenyl-4-alkyl-4-hydroxy-5,6-dihydro-4/7-l,3-thiazine derivatives are similarly prepared by reacting thio-benzamide with o ,/3-unsaturated ketones at room temperature <2002EJP307>. 

The final dehydration reaction (MTPI, DMPU, 18 h) on the alcohol 105 produced (+)-PHB (81) in 79% yield. This substance proved to be identical to the natural product by comparison of the H and 13C NMR spectra, mobility on TLC, IR spectra, mass spectra, and UV spectra. Comparison of the CD spectra of the natural (-)-PHB (6) and the synthetic (+)-PHB (81) confirmed the expected enantiomeric relationship between these two products. 

A number of recent developments in 129Xe NMR spectroscopy are presented with direct applications to the study of mesopore space in solids. This includes the establishment of a relationship between pore size and chemical shifts for a number of controlled pore glasses and the exploration of hyperpolarized (HP) xenon for a number of NMR and microimaging applications to porous solids. With HP xenon, the increase in experimental sensitivity is remarkable. Experiments illustrated include the rapid characterization of the void space in porous solids, including the in-situ study of processes such as diffusion and dehydration, and imaging with chemical shift resolution. 

Exercise 30-6 Reduction of the ketone group of (—)-menthone, which has its alkyl groups trans to one another, gives two products, known as (—(-menthol and (+)-neomenthol. These two substances differ considerably in their reactions. (+)-Neomenthol undergoes dehydration either in methanoic acid or when treated with phosphorus pentachloride, whereas (—(-menthol gives a methanoate ester with methanoic acid and a chloride with phosphorus pentachloride. What is the relationship between neomenthol and menthol, and why do they behave differently with methanoic acid and phosphorus pentachloride What is the likely structure of the menthene from dehydration of neomenthol (Review Sections 8-8D, 12-3D, and 12-5.)... 

Fig. 44. Relationships between catalytic activity and bulk acidity, (a) (O) Dehydration of 2-propanol, (A) decomposition of formic acid, ( ) conversion of methanol, (ta) ( ) Isomerization of cjs-2-butene after treatment at 423 K, ( ) isomerization of m-2-butene after treatment at 573 K. (From Ref. 46b.)...

The surface area is a function of the temperature of preparation of the oxides [169, 486]. Thus, the apparent electrocatalytic activity decreases with increasing temperature of calcination (which is usually in the range 350°-500 °C) [227, 475]. However, if the calcination is carried out at too high temperature, the electrode surface is deactivated probably as a consequence of some dehydration, and the observed Tafel slope can be very high [487], The important relationship between the acid-base properties of an oxide surface in solution and its electrocatalytic properties has been pointed out by the present author [488]. 

This chapter has focused on heterogeneous catalysis in supercritical media, but the relationship between supercritical fluids and catalysis is much broader. There have been numerous studies of homogeneous catalysis in SCFs. Examples include hydroformylation via cobalt carbonyl complexes in supercritical CO2, oxidation via metal salts dissolved in supercritical water, and acid-catalyzed dehydration of alcohols in supercritical water. 

The ionic resistance of a polymer electrolyte membrane is an important parameter in determining the mobility of protons through the membrane and the corresponding voltage loss across the membrane. Currently, the most commonly used membranes in PEM fuel cells are Nafion membranes produced by DuPont. However, these membranes are limited to low-temperature uses (usually below 80°C) because membrane dehydration at high temperatures can lead to reduced water content and then a lower proton transfer rate, resulting in a significant decrease in conductivity. The relationship between conductivity and the diffusion coefficient of protons can be expressed by the Nemst-Einstein equation ... 

The reason why some metal oxides are more selective for dehydrogenation over dehydration is not completely understood [12]. Semiempirical relationships between the Madelung potentials (of the metal and the oxygen ions of the lattice),... 

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