Water attack

Lanthanum is silvery white, malleable, ductile, and soft enough to be cut with a knife. It is one of the most reactive of the rare-earth metals. It oxidizes rapidly when exposed to air. Cold water attacks lanthanum slowly, while hot water attacks it much more rapidly. 

The regioselectivity of addition is established when water attacks one of the car bons of the halonium ion In the following example the structure of the product tells us that water attacks the more highly substituted carbon... 

This suggests that as water attacks the bromonium ion positive charge develops on the carbon from which the bromine departs The transition state has some of the character of a carbocation We know that more substituted carbocations are more stable than less substituted ones therefore when the bromonium ion ring opens it does so by breaking the bond between bromine and the more substituted carbon... 

It must be emphasized that we are not dealing with an equilibrium between two isomeric carbocations There is only one carbocation Its structure is not adequately represented by either of the individual resonance forms but is a hybrid having qualities of both of them The carbocation has more of the character of A than B because resonance struc ture A IS more stable than B Water attacks faster at the tertiary carbon because it bears a greater share of the positive charge... 

The attack of water is related to the leaching mechanism described for acids. Table 4 rates glasses based on their resistance to water attack. Low alkah, high alumina, or borosiUcate glasses generally have high water durabiUty. 

Lead is one of the most stable of fabricated materials because of excellent corrosion resistance to air, water, and soil. An initial reaction with these elements results in the formation of protective coatings of insoluble lead compounds. For example, in the presence of oxygen, water attacks lead, but if the water contains carbonates and siUcates, protective films or tarnishes form and the corrosion becomes exceedingly slow. 

Properties ndReactions. Phosphoms pentachloride, PCl, is a pale, greenish yellow soHd having a pungent odor (see Table 7). It is made from PCl and chlorine. Water attacks PCl and the violent hydrolysis proceeds in two stages. 

The mechanism of subcritical crack growth is the reaction of the corrosive medium with highly stressed bonds at the crack tip. In siUca, in the absence of stressed bonds, the rate of the reaction between the bonds and corrosive media such as water is very low. The introduction of strain energy into crack tip bonds increases the activity of the bond. For siUca glass in water, attack and bond breakage occurs by the following reaction (47) ... 

Other gases which are occasionally present usually arise from pollution. Ammonia, which in various forms may be present in waste waters, attacks copper and copper alloys its presence in estuarine waters is one of the main causes of condenser-tube corrosion. 

The unequal attack which occurs in tap water, condensate and other mild electrolytes may lead to perforations of thin-gauge sheet and even to deep pitting of castings. In stronger electrolytes the effect is variable. In chloride solutions such as sea-water, attack on the metal usually results in the pitting of some areas only, but where the metal surface has been rendered reactive, as by shot blasting, attack may be so rapid that uniform dissolution over the whole surface may occur. In either case magnesium-base alloys are not usually suitable for use in aqueous liquids since they are not intrinsically resistant to these electrolytes. 

As indicated above, the bicarbonate ion inhibits the process, which does not occur, therefore, in many supply waters attack is most likely in waters which by nature or as a result of treatment have a low bicarbonate content and relatively high chloride, sulphate or nitrate content. The number of points of attack increases with the concentration of aggressive anions and ultimately slow general corrosion may occur. During exposure of 99-75% tin to sea-water for 4 years, a corrosion rate of 0-0023 mm/y was observed . Corrosion in soil usually produces slow general corrosion with the production of crusts of oxides and basic salts this has no industrial importance but is occasionally of interest in archaeological work. 

Attack by alkali solution, hydrofluoric acid and phosphoric acid A common feature of these corrosive agents is their ability to disrupt the network. Equation 18.1 shows the nature of the attack in alkaline solution where unlimited numbers of OH ions are available. This process is not encumbered by the formation of porous layers and the amount of leached matter is linearly dependent on time. Consequently the extent of attack by strong alkali is usually far greater than either acid or water attack. 

The mechanism of the reaction will have three steps (1) protonate the alkene to form a carbocation, (2) water attacks the carbocation, and (3) deprotonate to form the product ... 

Which group will end up on the more substituted carbon Br or OH In other words, does water attack the more substituted carbon or the less substituted carbon To answer this question, we need to look at the structure of the bromonium ion more... 

The first step consists in the attack of a proton on the W-H bond to yield a labile dihydrogen intermediate (Eq. (3)) that rapidly releases H2 to form a coordi-natively unsaturated complex (Eq. (4)). This complex adds water in the next step to form an aqua complex (Eq. (5)) that completes the reaction by substituting the coordinated water by the X anion (Eq. (6)). Steps (3)-(6) are repeated for each W-H bond and the factor of 3 in the rate constants appears as a consequence of the statistical kinetics at the three metal centers. The rate constants for both the initial attack by the acid (ki) and water attack to the coordinatively unsaturated intermediate (k2) are faster in the sulfur complex, whereas the substitution of coordinated water (k3) is faster for the selenium compound. 

The first possibility, (11), clearly is concerned with a dissociative mode of activation (d). The second, (12), mxghihsassociative led by water attack. But, this interpretation of (12) involves commitment to the proposition that no nucleophile (possibly excepting OH ) has been discovered which is better than water, i.e. the associative attack must always involve water in the first instance. The proposition... 

The basicities of some phosphinamides (84) have been measured and the acid-catalysed hydrolysis studied. Unsubstituted and A -alkyl derivatives follow an A2 mechanism of reversible protonation followed by ratedetermining water attack. However, the rates for the A -aryl derivatives follow Hq (but with a slope of 0.5), and an A mechanism was suggested as most consistent with this fact and the solvent isotope effect. The anomalous dependence on Ho, together with the large negative value of A5, while not necessarily excluding an ionization mechanism, leaves the question in some doubt. 

Silver white, relatively soft metal that is only applied in alloys. Oxygen and water attack pure Ca. The most prominent compound is the oxide (CaO) = burnt calcium, which hardens to calcium carbonate in mortar. Annual production of about 120 million tons. Burnt gypsum (CaS04 0.5 H20) hardens with water. A great step in evolution was the replacement of hard shells of brittle calcium carbonate by an internal skeleton of tough calcium phosphate (hydroxylapatite)-protein composite. Calcium is essential for all life forms. The daily requirement is 0.7-1.0 g. Humans (70 kg) contain 1 kg of calcium. Calcium silicate is the main component of cement. Marble is calcium carbonate in polycrystalline form and the favorite material of sculptors. 

On the other hand, it is found that only partial racemization occurs on alkaline hydrolysis of optical active 198 in aqueous methanol136) and no racemization takes place in the hydrolysis of 199 in dioxane/water137). Moreover, the latter reaction is only ca. 80 times faster at 29 °C than that of the analogous morpholide 200, for which a metaphosphorimidate mechanism is precluded a priori by the absence of an NH function and whose hydrolysis is likewise stereospecific,37). Clearly a free metaphosphorimidothioate of type 191 cannot be involved in this case. The experimental findings are compatible, however, with the hypothesis that the nucleophile water attacks a metaphosphorothioimidate/phenolate associate 201. The question of how free metaphosphates occur in solution is of a general nature it has also been considered in the previous Section. 

Studies using either molecular oxygen-18 or oxygen-18 water indicated that the 4R,5R-dihydrodiol is derived by water attack at the C-4 position of the metabolically formed 4,5-epoxide intermediate (15.21), These results established that 4S,5R-epoxide is formed as the metabolic precursor of the 4R,5R-dihydrodiol. Hydration studies of the optically pure BaP 4,5-epoxide enantiomers indicated that the 4S,5R-epoxide is hydrated exclusively at the S-center (C-4 position) whereas 85% of the 4R,5S-epoxide is hydrated at the S-center (C-5 position) (22 and Figure 4). 

The hydration of simple ketenes (RCH=C=0—> RCH2COOH) also shows relatively constant values of oh w which are quite low (100-1000) (Tidwell, 1990 Allen et al., 1992), implying p/fj = 11 to 12 for the transition state for water attack. Corresponding to this, the Leffler index and the /3nuc are both about 0.25. Whether these low values really indicate an early transition state or arise because water and hydroxide ion react quite differently is not yet clear. However, it appears possible that water attack proceeds through a cyclic mechanism involving two (or more) water molecules (Allen et al., 1992) whereas hydroxide ion probably attacks conventionally as a nucleophile (Tidwell, 1990). Of course, any mechanism for the water reaction which is superior to simple nucleophilic attack will elevate kw and necessarily lead to low kOH/kw ratios. 

Bender and Glasson (1959), in studies of alcoholysis and hydrolysis of idkyl esters in aqueous alcohol, found that the rate of disappearance of ester is decreased by increasing alcohol concentration. However, product analysis led to the conclusion that both methanolysis and ethanolysis are faster than hydrolysis in alcohol-water mixtures. It was calculated that in pure water attack by hydroxide, methoxide and ethoxide ions would occur at about the same rates. 

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