Reducing property

Describing vitamins E and C as having identical anti-oxidant roles in lipid and aqueous cellular locations respectively is almost certainly an over-simplification since they have been shown to interact synergistically and it may be that at the lipid/aqueous interface, ascorbic acid protects vitamin E, or is involved in its restorative reduction after a successful attack on an oxidising free radical. 

The well known phenomenon of ascorbic acid enhancing the absorption of iron from the intestine is probably due to it maintaining the element in the reduced, Fe , state in which it is more easily taken up across the mucosal membrane. 

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According to this concept, a reduced property is expressed as a function of two variables, and I/, and of the acentric factor, cd ... 

The factor enabling interpolation of reduced properties of a pure compound or mixture between two reduced properties calculated on two reference fluids merits attention in order to understand its meaning. 

Silanes are very sensitive to attack by alkalis and will even react with water made alkaline by contact with glass this reaction is in marked contrast to the reactions shown by alkanes. Unlike alkanes, silanes are found to have marked reducing properties and will reduce, for example, potassium manganate(VII) to manganeseflV) oxide, and iron(III) to iron(II). 

Stannate(II) ions are powerful reducing agents. Since, for tin, the stability of oxidation state -b4 is greater than that of oxidation state -b2, tin(II) always has reducing properties, but these are greater in alkaline conditions than in acid (an example of the effect of pH on the redox potential, p. 101). 

Oxygen is unaffected by aqueous acids unless they have powerful reducing properties when the acid is oxidised. For example... 

Hydrogen peroxide has both oxidising properties (when it is converted to water) and reducing properties (when it is converted to oxygen) the half-reactions are (acid solution) ... 

Hydrolysis by acids. Sucrose is readily hydrolysed by dilute acids. Dissolve 0 5 g. of sucrose in 5 ml. of water, add 2 ml. of dil. H2SO4 and heat in a boiling water-bath for 5 minutes. Cool and show that the solution has reducing properties, and will form glucosazone. Note that the excess of acid must be neutralised before carrying out the reduction tests. 

The physical properties of argon, krypton, and xenon are frequendy selected as standard substances to which the properties of other substances are compared. Examples are the dipole moments, nonspherical shapes, quantum mechanical effects, etc. The principle of corresponding states asserts that the reduced properties of all substances are similar. The reduced properties are dimensionless ratios such as the ratio of a material s temperature to its critical... 

Other Borohydrides. Potassium borohydride was formerly used in color reversal development of photographic film and was preferred over sodium borohydride because of its much lower hygroscopicity. Because other borohydrides are made from sodium borohydride, they are correspondingly more expensive. Generally their reducing properties are not sufficiently different to warrant the added cost. Zinc borohydride [17611-70-0] Zn(BH 2> however, has found many appHcations in stereoselective reductions. It is less basic than NaBH, but is not commercially available owing to poor thermal stabihty. It is usually prepared on site in an ether solvent. Zinc borohydride was initially appHed to stereoselective ketone reductions, especially in prostaglandin syntheses (36), and later to aldehydes, acid haHdes, and esters (37). 

Unusual reducing properties can be obtained with borohydride derivatives formed in situ. A variety of reductions have been reported, including hydrogenolysis of carbonyls and alkylation of amines with sodium borohydride in carboxyHc acids such as acetic and trifluoroacetic (38), in which the acyloxyborohydride is the reducing agent. 

Lead (qv) is a member of Group 14 (IVA) of the Periodic Table because it has four electrons in its outer, or valence, shell. However, the usual valence of lead is +2, rather than +4. The two s electrons have higher ionisation energies. As a result, tetravalent lead exists as a free, positive ion only in minimal concentrations. Furthermore, the bivalent or plumbous ion differs from the other Group 14 bivalent ions, such as the starmous ion of tin, because Pb " does not have reducing properties. 

Dextrose in solution or in soHd form exists in the pyranose stmctural conformation. In solution, a small amount of the open-chain aldehyde form exists in equiUbrium with the cycHc stmctures (1) and (2). The open-chain form is responsible for the reducing properties of dextrose. 

The thiosulfate ion, 820 is a stmctural analogue of the sulfate ion where one oxygen atom is replaced by one sulfur atom. The two sulfur atoms of thiosulfate thus are not equivalent. Indeed, the unique chemistry of the thiosulfate ion is dominated by the sulfide-like sulfur atom which is responsible for both the reducing properties and complexing abiUties. The abiUty of thiosulfates to dissolve silver haUdes through complex formation is the basis for their commercial appHcation in photography (qv). 

Some metal thiosulfates are inherently unstable because of the reducing properties of the thiosulfate ion. Ions such as Fe " and Cu " tend to be reduced to lower oxidation states, whereas mercury or silver, which form sulfides of low solubiUty, tend to decompose to the sulfides. The stabiUty of other metal thiosulfates improves in the presence of excess thiosulfate by virtue of complex thiosulfate formation. 

Industrial uses of L-ascorbic acid relate to its antioxidant and reducing properties. It is used as an antioxidant in the commercial preparation of beer, fmit juices, cereals, and caimed and frozen foods, etc. 

In apphcations where vitamin C activity is unimportant, often D-erythorbic acid (D-araboascorbic acid) can also be used, providing the same antioxidant and reducing properties as L-ascorbic acid. 

The alkanoic acids, with the exception of formic acid, undergo typical reactions of the carboxyl group. Formic acid has reducing properties and does not form an acid chloride or an anhydride. The hydrocarbon chain of alkanoic acids undergoes the usual reactions of hydrocarbons except that the carboxyl group exerts considerable influence on the site and ease of reaction. The alkenoic acids in which the double bond is not conjugated with the carboxyl group show typical reactions of internal olefins. All three types of reactions are industrially important. 

Generalized Correlations. Generalized correlations are often the only recourse when a property value cannot be determined from empirical correlations or by other means. Several powerful correlating techniques fall under this category, including the principle of corresponding states (3,17), reduced property models (1), and the Polanyi-type characteristic curve for microporous adsorbents (14). 

An alternative to the use of generalized charts is an analytical equation of state. Equations of state which are expressed as a function of reduced properties and nondimensional variables are said to be generalized. The term generalization is in reference to the wide appHcabiHty to the estimation of fluid properties for many substances. 

Reduced Properties. One of the first attempts at achieving an accurate analytical model to describe fluid behavior was the van der Waals equation, in which corrections to the ideal gas law take the form of constants a and b to account for molecular interactions and the finite volume of gas molecules, respectively. 

The empirical representation of the PVT surface for pure materials is treated later in this section. We first present general equations for evaluation of reduced properties from such representations. 

Recently reductions by a new hydride reagent, sodium bis(2-methoxy-ethoxy)aluminum hydride, have been investigated. This compound is similar to LiAlH4 in its reducing properties but because it is soluble in aromatic hydrocarbons and more stable in air than LiAlH4, it may be more convenient to use. 

Ascorbic acid is a reasonably strong reducing agent. The biochemical and physiological functions of ascorbic acid most likely derive from its reducing properties—it functions as an electron carrier. Loss of one electron due to interactions with oxygen or metal ions leads to semidehydro-L-ascorbate, a reactive free radical (Figure 18.30) that can be reduced back to L-ascorbic acid by various enzymes in animals and plants. A characteristic reaction of ascorbic acid is its oxidation to dehydro-L-aseorbie add. Ascorbic acid and dehydroascor-bic acid form an effective redox system. 

The free acid is monobasic, pA 3.85 it is much more easily hydrolysed than sulfamic acid and has reducing properties comparable with those of hydrazine. Like sulfamic acid it exists as a zwitterion in the solid state H3NNHS03. ... 

All the anhydrous - -3 and +2 halides of iron are readily obtained, except for iron(III) iodide, where the oxidizing properties of Fe and the reducing properties of 1 lead to thermodynamic instability. It has, however, been prepared in mg quantities by the following reaction, with air and moisture rigorously excluded,... 

However, this is not the complete explanation for their reducing properties. Let us analyze the energy requirements of the process... 

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