Rate of hydrolysis

The half-lives for these four compounds taken from the literature allowed the estimation of the Four reaction rates necessai to model their degradation [18], As a first approximation, the rate of hydrolysis of the C-Cl bond of all Four, -triazine compounds was assumed to be the same and to be 5.0 x 10 s on the basis of literature precedence. This approximation seems reasonable as the four structures differ only in the alkyl groups at a site quite remote from the C-CI bond. Furthermore, among the Four reaction steps hydrolysis is the slowest anyway. 

The rate of hydrolysis depends upon the solubUity of the acetal m the hydrolysis medium. Acetals of low molecular weight are completely hydrolysed by refluxing for 5-10 minutes those of higher molecular weight, and therefore of small solubility, may require 30-60 minutes, but... 

Pairwise hydrophobic interactions can be used to alter the reactivity of organic molecules in water. For instance, the rate of hydrolysis reactions may be influenced significantly by the presence of hydrophobic cosolutes. The effect on reactivity has been analysed by comparirg the interactions between initial state and cosolute with those between transition state and cosolute. ... 

They found that the rate of hydrolysis depends only on the concentration of tert butyl bromide Adding the stronger nucleophile hydroxide ion moreover causes no change m... 

Neither formic acid nor water is very nucleophilic and so 8 2 substitution is suppressed The relative rates of hydrolysis of a group of alkyl bromides under these conditions are presented m Table 8 5... 

FIGURE 20 3 An acid cat alyzes the hydrolysis of a carboxylic acid anhydride by increasing the rate of the first stage of the mecha nism The faster the tetra hedral intermediate is formed the faster the rate of hydrolysis... 

In one of the earliest kinetic studies of an organic reaction earned out m the nine teenth century the rate of hydrolysis of ethyl acetate m aqueous sodium hydroxide was found to be first order m ester and first order m base... 

The hydrolysis of urea is strongly temperature-dependent, with the rate being negligible at room temperature. The rate of hydrolysis, and thus the rate of precipitate formation, can be controlled by adjusting the solution s temperature. Precipitates of BaCr04, for example, have been produced in this manner. 

Noncatalytic Reactions Chemical kinetic methods are not as common for the quantitative analysis of analytes in noncatalytic reactions. Because they lack the enhancement of reaction rate obtained when using a catalyst, noncatalytic methods generally are not used for the determination of analytes at low concentrations. Noncatalytic methods for analyzing inorganic analytes are usually based on a com-plexation reaction. One example was outlined in Example 13.4, in which the concentration of aluminum in serum was determined by the initial rate of formation of its complex with 2-hydroxy-1-naphthaldehyde p-methoxybenzoyl-hydrazone. ° The greatest number of noncatalytic methods, however, are for the quantitative analysis of organic analytes. For example, the insecticide methyl parathion has been determined by measuring its rate of hydrolysis in alkaline solutions. 

The important feature is that a three-dimensional gel network comes from the condensation of partially hydroly2ed species. Thus, the microstmcture of a gel is governed by the rate of particle (cluster) growth and their extent of crosslinking or, more specifically, by the relative rates of hydrolysis and condensation (3). 

The rate of hydrolysis of DMAC is very low, but increases somewhat in the presence of acids or bases. DMAC is a stable compound, but is mildly hygroscopic and desiccation and/or dry nitrogen blanketing of storage vessels are sometimes used to reduce water pick-up. In the absence of water, acids, or bases, DMAC is stable at temperatures up to its hoiling point at atmospheric pressure. Its greater stability enables more economical recovery by distillation relative to that of other similar solvents. 

Formamide is hydroly2ed very slowly at room temperature. The rate of hydrolysis increases rapidly in the presence of acids or bases and is further accelerated at elevated temperatures. 

Water hydroly2es pure diketene only slowly to give acetoacetic acid [541-50-4] which quickly decomposes to acetone and carbon dioxide, but increasing the pH or adding catalysts (amines, palladium compounds) increases the rate of hydrolysis. The solvolysis of diketene in ammonia results in aceto acetamide [5977-14-0] if used in stoichiometric amounts (99), and P-arninocrotonarnide [15846-25-0] if used in excess (100). 

P-A4 = 7.7 (47). The rates of hydrolysis of the peroxodiphosphate ion are dependent on both pH and temperature, eg, as the hydrogen ion concentration iacreases, the rate iacreases (48). Peroxodiphosphoric acid hydroly2es to peroxomonophosphoric acid according to the foUowiag equation ... 

The rates of hydrolysis for the peroxophosphoric acids are more rapid than the corresponding reactions of the peroxosulfiiric acids. The peroxodiphosphate ion is extremely resistant to decomposition by oxidation of water ... 

Hydrolysis and Polycondensation. As shown in Figure 1, at gel time (step C), events related to the growth of polymeric chains and interaction between coUoids slow down considerably and the stmcture of the material is frozen. Post-gelation treatments, ie, steps D—G (aging, drying, stabilization, and densification), alter the stmcture of the original gel but the resultant stmctures aU depend on the initial stmcture. Relative rates, of hydrolysis, (eq. 2), and condensation, (eq. 3), determine the stmcture of the gel. Many factors influence the kinetics of hydrolysis and... 

In the second procedure, calcium nitrate was replaced by calcium alkoxide (60). Calcium and sificon alkoxides have very different rates of hydrolysis. To avoid the production of inhomogeneities, a slow and controlled hydrolysis of a mixture of sificon, calcium, and phosphorous alkoxide was performed. The resulting materials were highly homogenous, and monolithic pieces could be produced. The bioactivity of the gel-derived materials is equivalent or greater than melt-derived glasses. 

Alkali metal sulfamates are stable in neutral or alkaline solutions even at boiling temperatures. Rates of hydrolysis for sulfamic acid in aqueous solutions have been measured at different conditions (Table 4) (8,10)-... 

Conditions for hydrolysis (82) of the intermediate sultone mixture also help modify the ratio of alkenesulfonate to -hydroxyalkanesulfonate, distribution of alkenesulfonate positional isomers, and completeness of conversion. Caustic hydrolysis using a slight stoichiometric excess of base is employed to ensure alkaline conditions throughout the hydrolysis phase of AOS production. The rate of hydrolysis depends a great deal on temperature. The 5-sultone requires the most time for conversion to 4-hydroxyalkanesulfonate. P-Sultones and y-sultones hydrolyze so rapidly to 2-hydroxyalkanesulfonate and 3-hydroxyalkanesulfonate that temperatures below 100°C can be used. 5-Sultone completely hydrolyzes between 120 and 175°C in 1—30 minutes. The quaUty of the final product mixture is ultimately determined by the choice of conditions. 

Hydrolysis of dialkyl sulfites under acidic and alkaline conditions, which is followed by the use of OH2, proceeds by attack at sulfur to give S—O cleavage (72). The rate of hydrolysis is generally faster for cycHc and aryl sulfites than for dialkyl sulfites (73). Activation parameters of hydrolysis are known for some sulfites, and the increased rate for ethylene sulfite results from a reduced entropy of activation which results from a rigid ring stmcture (74). 

The mono- and dialkan olamine titanates are water-soluble and slowly hydrolyze at pH 9.0. Loweting the pH iacreases the rate of hydrolysis, which is shown by the development of turbidity. Turbidity also occurs above pH 11. The tetrahydroxyalkylethylenediarnine titanate complexes form much more stable water solutions and can be used as dispersiag agents for aqueous Ti02 slurries (114). 

The poly(vinyl alcohol) made for commercial acetalization processes is atactic and a mixture of cis- and /n j -l,3-dioxane stereoisomers is formed during acetalization. The precise cis/trans ratio depends strongly on process kinetics (16,17) and small quantities of other system components (23). During formylation of poly(vinyl alcohol), for example, i j -acetalization is more rapid than /ra/ j -acetalization (24). In addition, the rate of hydrolysis of the trans-2iQ. -A is faster than for the <7 -acetal (25). Because hydrolysis competes with acetalization during acetal synthesis, a high cis/trans ratio is favored. The stereochemistry of PVF and PVB resins has been studied by proton and carbon nmr spectroscopy (26—29). 

Hydrolysis of vinyl acetate is catalyzed by acidic and basic catalysts to form acetic acid and vinyl alcohol which rapidly tautomerizes to acetaldehyde. This rate of hydrolysis of vinyl acetate is 1000 times that of its saturated analogue, ethyl acetate, ia alkaline media (15). The rate of hydrolysis is minimal at pH 4.44 (16). Other chemical reactions which vinyl acetate may undergo are addition across the double bond, transesterification to other vinyl esters, and oxidation (15—21). 

Buffers are frequently added to emulsion recipes and serve two main purposes. The rate of hydrolysis of vinyl acetate and some comonomers is pH-sensitive. Hydrolysis of monomer produces acetic acid, which can affect the initiator, and acetaldehyde which as a chain-transfer agent may lower the molecular weight of the polymer undesirably. The rates of decomposition of some initiators are affected by pH and the buffer is added to stabilize those rates, since decomposition of the initiator frequently changes the pH in an unbuffered system. Vinyl acetate emulsion polymerization recipes are usually buffered to pH 4—5, eg, with phosphate or acetate, but buffering at neutral pH with bicarbonate also gives excellent results. The pH of most commercially available emulsions is 4—6. 

Conversion of the nitrile to the amide has been achieved by both chemical and biological means. Several patents have described the use of modified Raney nickel catalysts ia this appHcation (25,26). Also, alkaH metal perborates have demonstrated their utiHty (27). Typically, the hydrolysis is conducted ia the presence of sodium hydroxide (28—31). Owiag to the fact that the rate of hydrolysis of the nitrile to the amide is fast as compared to the hydrolysis of the amide to the acid, good yields of the amide are obtained. Other catalysts such as magnesium oxide (32), ammonia (28,29,33), and manganese dioxide (34) have also been employed. 

The rate of hydrolysis has a steep minimum at a solution pH of 4.5—5.0, and increases drastically with temperature. 

The triaLkoxy(aryloxy)boranes are typically monomeric, soluble in most organic solvents, and dissolve in water with hydrolysis to form boric acid and the corresponding alcohol and phenol. Although the rate of hydrolysis is usually very fast, it is dependent on the bulk of the alkyl or aryl substituent groups bonded to the boron atom. Secondary and tertiary alkyl esters are generally more stable than the primary alkyl esters. The boron atom in these compounds is in a trigonal coplanar state with bond hybridization. A vacantp orbital exists along the threefold axis perpendicular to the BO plane. 

Reaction with Water. The alkyl carbonate esters, especially the lower ones, hydroly2e very slowly in water when compared to the carbonochloridic esters (chloroformates). Under alkaline conditions, the rates of hydrolysis are similar to those of the corresponding acetic acid esters. 

The acetylation reaction is stopped by the addition of water to destroy the excess anhydride, causing rapid hydrolysis of the combined sulfate acid ester (Eig. 7). This is followed by a much slower rate of hydrolysis of the acetyl ester groups. The rate of hydrolysis is controlled by temperature, catalyst concentration, and, to a lesser extent, by the amount of water. Higher temperatures and catalyst concentrations increase the rate of hydrolysis. Higher water content slightly iacreases the hydrolysis rate and helps minimize degradation (85). The amount of water also influences the ratio of primary to secondary... 

The rate of hydrolysis of cellulose acetate can be monitored by removing samples at intervals during hydrolysis and determining the solubiUty of the hydrolyzed acetate. When the desired DS is reached, the hydrolysis is stopped by neutralizing the catalyst with magnesium, calcium, or sodium salts dissolved in aqueous acetic acid. 

Discrimination between exposed and unexposed areas in this process requires the selection of thia zolidine compounds that do not readily undergo alkaline hydrolysis in the absence of silver ions. In a study of model compounds, the rates of hydrolysis of model /V-methyl thia zolidine and A/-octadecyl thiazolidine compounds were compared (47). An alkaline hydrolysis half-life of 33 min was reported for the /V-methyl compound, a half-life of 5525 min (3.8 days) was reported for the corresponding V/-octadecyl compound. Other factors affecting the kinetics include the particular silver ligand chosen and its concentration (48). Polaroid Spectra film introduced silver-assisted thiazolidine cleavage to produce the yellow dye image (49), a system subsequentiy used in 600 Plus and Polacolor Pro 100 films. 

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