Chemical oxidative degradation

The durability of a material or structure has been defined as its ability to resist cracking, oxidation, chemical degradation, delamination, wear, and/... 

Chemical degradation (141), whether thermally or photo-iaduced, primarily results from depolymerization, oxidations, and hydrolysis. These reactions are especially harmful ia objects made from materials that coataia ceUulose, such as wood, cottoa, and paper. The chemistry of these degradation processes is quite complex, and an important role can be played by the reaction products, such as the acidic oxidation products which can catalyze hydrolysis. 

Chemical degradation studies carried out on streptovaricias A and C, which are the primary components of the cmde complex, yielded substances shown ia Figure 1. Streptovaricia A (4), consumes two moles of sodium periodate to yield variciaal A [21913-68-8] (1), 0 2 200, which accounts for the ahphatic portion of the molecule, and prestreptovarone [58074-37-6] (2), C2C)H2C)N02, which accounts for the aromatic chromophore of the streptovaricias (Fig. 2). Streptovaricia G (9) is the only other streptovaricia that yields prestreptovaroae upoa treatmeat with sodium periodate. Treatmeat of streptovaricias A (4), B (5), C (6), E (8), and G (9) with sodium periodate and osmium tetroxide yields streptovarone [36108-44-8] (3), C24H23NO2, which is also produced by the reaction of prestreptovarone with sodium periodate and osmium tetroxide (4,65). A number of aliphatic products were isolated from the oxidation of streptovaricia C and its derivatives (66). 

Many tracer chemicals are inherently unstable even as the unlabeled forms. Susceptibility of a chemical to hydrolysis, oxidation, photolysis, and microbiological degradation needs to be evaluated when designing suitable storage conditions for the labeled compound. Eactors that reduce radiolytic degradation, such as dispersal in solution, are apt to increase chemical degradation or instability. 

Polypropylene differs from polyethylene in its chemical reactivity because of the presence of tertiary carbon atoms occurring alternately on the chain backbone. Of particular significance is the susceptibility of the polymer to oxidation at elevated temperatures. Some estimate of the difference between the two polymers can be obtained from Figure 1J.7, which compares- the rates of oxygen uptake of eaeh polymer at 93°C. Substantial improvements can be made by the inclusion of antioxidants and such additives are used in all commercial compounds. Whereas polyethylene cross-links on oxidation, polypropylene degrades to form lower molecular weight products. Similar effects are noted... 

Acrylate polymers also have fully saturated polymer backbones free of any heteroatoms in the main chain. This makes the polymers highly resistant to oxidation, photo-degradation and chemical attack. The acrylate groups are esters, which could be hydrolyzed under severe conditions. However, the hydrophobic nature of most acrylic polymers minimizes the risk for hydrolysis and, even if this reaction happened to some extent, the polymer backbone would still be intact. Other desirable acrylate properties include the following ... 

Endosulfan undergoes hydrolysis to endosulfan diol in surface water and groundwater. The rate of hydrolysis is influenced by pH. Half-life values reported in the literature vary somewhat. The chemical degradation of a- and P-endosulfan was studied under both anaerobic and aerobic environments. Under aerobic conditions, both hydrolysis and oxidation of endosulfan can occur, while under anaerobic conditions, only hydrolysis can occur. The hydrolytic half-lives for a- and P-endosulfan under anaerobic conditions at pH 7 were 35 and 37 days, respectively (Greve and Wit 1971). At pH 5.5 the half-lives were 151 and 187 days, respectively. Under aerobic conditions, the half-lives decreased. At pH 7, the half-lives of the chemical degradation (hydrolysis and oxidation) of both a- and P-endosulfan were 23 and 25 days, respectively, while at pH 5, the half-lives were 54 and 51 days, respectively. At T=20 and pHs of 5.5 and 8.0, the half-lives of a-endosulfan in distilled water were 11.3 and 5.3 days. 

The pollutant or solute cycle — that may encompass the processes of advection, diffusion, volatilization, adsorption and desorption, chemical degradation or decay, hydrolysis, photolysis, oxidation, cation or anion exchange, complexation, chemical equilibria, nutrient cycles, and others (see section 3.0). 

First order rate constants are assumed for all degradative processes soil and water microbial degradation, hydrolysis, oxidation, photodegradation in air and water and any other mechanisms of transformation that may apply. The rate at which the chemical degrades will then be equal to the summation of the rate constants acting on the amount of chemical in each compartment summed over all compartments. 

Desizing by chemical decomposition is applicable to starch-based sizes. Since starch and its hydrophilic derivatives are soluble in water, it might be assumed that a simple alkaline rinse with surfactant would be sufficient to effect removal from the fibre. As is also the case with some other size polymers, however, once the starch solution has dried to a film on the fibre surface it is much more difficult to effect rehydration and dissolution. Thus controlled chemical degradation is required to disintegrate and solubilise the size film without damaging the cellulosic fibre. Enzymatic, oxidative and hydrolytic degradation methods can be used. 

Volatile silicones are broken down by oxidative chemical processes on entering the atmosphere. The partially oxidised degradation products are less volatile and these are scrubbed out of the atmosphere by rain or deposited on the ground to be further diluted and degraded, the final products being natural silica, carbon dioxide and water. 

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