Hydration reaction

Most of the examples of gold-catalysed hydration of allenes are performed at high temperatures. There has been an interest in reducing the temperature 

Early studies, reviewed by Malquori (M81), showed that natural pozzolanas take up CH, including that produced by Portland cement, with the formation of products similar to those formed on hydration of the latter material. They also showed that the zeolites present in many of them were at least as reactive in this respect as the glassy constituents. Zeolites are cation exchangers, but the amounts of CaO they take up are much greater than can be thus explained moreover, cation exchange could not explain the develop- 

Costa and Massazza (C44) concluded from a study of natural pozzolanas of varied types that reactivity in mixtures with CH at w/s = 2 and 40 C depends during the first 28 days on the specific surface area and at later ages on the contents of Si02 and AI2O3 in the active constituents. A comparative study of five natural pozzolanas and three low-CaO pfas in pastes with cement showed that the CH contents of the pozzolanic cements were considerably lower than those of the pfa cements at 3-60 days, but virtually the same at 90 days, the pozzolanas thus appearing to react more rapidly than the pfas at early ages but more slowly later. Determinations of the unreacted mineral admixture in pastes with CH showed that at 90 days 23-30% of the natural pozzolana had reacted, compared with 11-15% for the pfas. The similarity in CH contents suggests, however, that these values may not apply to mixtures with cement. 

X-ray microanalyses of CjS-pozzolana pastes showed a gradual decrease in Ca/Si ratio on passing from regions near the iinreacted CjS to ones near the pozzolana (021). TMS studies of pastes of C3S, (3-C,S and cement with and without natural pozzolanas (U9,M44) showed that, in the presence of the latter, formation of polymeric anions is accelerated and their mean molecular weight is increased. TMS results and determinations of combined water showed that the hydration of P-CjS is almost completely suppressed in the presence of a pozzolana and that, in pastes with CjS, 16-29% of the pozzolana had reacted in 180 days (M44). The eflect on P-CjS hydration is similar to that found using QXDA for pfa (D12). Chemical extraction showed 10-45% of the pozzolanas in pastes with C3S to have reacted in 28 days, compared with under 10% for a pfa (U9). 

Exploring Chemistry with Electronic Structure Methods 

This term is negligible for these reactions and will be ignored. 

A (AE ) Change in the vibrational energy difference between 0 K and 298 K. Ae298 Difference in the rotational energies of products and reactants. 

Translational energy change between products and reactants. 

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Cyclohexane, produced from the partial hydrogenation of benzene [71-43-2] also can be used as the feedstock for A manufacture. Such a process involves selective hydrogenation of benzene to cyclohexene, separation of the cyclohexene from unreacted benzene and cyclohexane (produced from over-hydrogenation of the benzene), and hydration of the cyclohexane to A. Asahi has obtained numerous patents on such a process and is in the process of commercialization (85,86). Indicated reaction conditions for the partial hydrogenation are 100—200°C and 1—10 kPa (0.1—1.5 psi) with a Ru or zinc-promoted Ru catalyst (87—90). The hydration reaction uses zeotites as catalyst in a two-phase system. Cyclohexene diffuses into an aqueous phase containing the zeotites and there is hydrated to A. The A then is extracted back into the organic phase. Reaction temperature is 90—150°C and reactor residence time is 30 min (91—94). 

The concentration of tme carbonic acid (H2CO2) is negligible in comparison to dissolved carbon dioxide, eg, only 0.3% of the latter is hydrated to carbonic acid at 25°C. The ionization constant is a composite constant representing both the CO2 hydration reaction, iC, and ionization of tme H2CO2, ifj = ifjj QQ /(I + K). Temperature-dependent equations for and are (29)... 

Fig. 5. The early hydration reactions of tricalcium aluminate in the presence of gypsum and calcium hydroxide. Initial molar proportions l-C A ...

Hydration at Ordinary Temperatures. Pordand cement is generally used at temperatures ordinarily encountered in constmction, ie, from 5 to 40°C. Temperature extremes have to be avoided. The exothermic heat of the hydration reactions can play an important part in maintaining adequate temperatures in cold environments, and must be considered in massive concrete stmctures to prevent excessive temperature rise and cracking during subsequent cooling. 

The kinetics of the ethylene hydration reaction have been investigated for a tungstic oxide—siHca gel catalyst, and the energy of activation for the reaction deterrnined to be 125 kJ/mol (- 30 kcal/mol) (106,120). The kinetics over a phosphoric acid-siHca gel catalyst have been examined (121). By making some simplifying assumptions to Taft s mechanism, a rate equation was derived ... 

The hydration reaction has been extensively studied because it is the mechanistic prototype for many reactions at carbonyl centers that involve more complex molecules. For acetaldehyde, the half-life of the exchange reaction is on the order of one minute under neutral conditions but is considerably faster in acidic or basic media. The second-order rate constant for acid-catalyzed hydration of acetaldehyde is on the order of 500 M s . Acid catalysis involves either protonation or hydrogen bonding at the carbonyl oxygen. 

MO (STO-3G) calculations on the gas-phase hydration reaction of formaldehyde suggest a concerted process involving two water molecules as a low-energy mechanism for hydration. 

The equilibrium constants for addition of alcohols to carbonyl compounds to give hemiacetals or hemiketals show the same response to structural features as the hydration reaction. Equilibrium constants for addition of metiianoHb acetaldehyde in both water and chloroform solution are near 0.8 A/ . The comparable value for addition of water is about 0.02 The overall equilibrium constant for formation of the dimethyl acetal of... 

The following data give the dissociation constants for several acids that catalyze hydration of acetaldehyde. Also given are the rate constants for the hydration reaction catalyzed by each acid. Treat the data according to the Bronsted equation, and comment on the mechanistic significance of the result. 

Subsequent investigations proved that identical hydration reactions occur on bare aluminum surfaces and bonded surfaces, but at very different rates of hydration [49]. An Arrhenius plot of incubation times prior to hydration of bare and buried FPL surfaces clearly showed that the hydration process exhibits the same energy of activation ( 82 kJ/mole) regardless of the bare or covered nature of the surface (Fig. 11). On the other hand, the rate of hydration varies dramatically, de-... 

M s , in agreement with independent measurements of the rate of hydration. Thus, it appears that the oxygen exchange rate can be completely accounted for by the hydration reaction. 

Extension of the hydration reaction to hydrogen peroxide has shown that stable peroxides are formed from enamines and the imonium salts derived from secondary amines and ketones (506,507). 

The computed value for AH is in excellent agreement with the experimental value. We ll look at two similar hydration reactions in Exercise 8.1. 

Silicon Cluster Reactions S t 2 Reaction Hydration Reactions... 

The TCA cycle can now be completed by converting succinate to oxaloacetate. This latter process represents a net oxidation. The TCA cycle breaks it down into (consecutively) an oxidation step, a hydration reaction, and a second oxidation step. The oxidation steps are accompanied by the reduction of an [FAD] and an NAD. The reduced coenzymes, [FADHg] and NADH, subsequently provide reducing power in the electron transport chain. (We see in Chapter 24 that virtually the same chemical strategy is used in /3-oxidation of fatty acids.)... 

In mammalian erythrocytes (red blood-cells) the forward (hydration) reaction occurs during the uptake of CO, by blood in tissue, while the backward (dehydration) reaction takes place when the CO, is subsequently released in the lungs. The enzyme increases the rates of these reactions by a factor of about one million. 

Hydroxy-8-azapurine was shown by rapid-reaction techniques (see Section II, E) to be anhydrous in the anion and hydrated in the neutral species. The hydration reaction has a half-time of about 0.5 second, which is too rapid for exact measurements with existing apparatus. The cation of 2-amino-8-azapurine was shown to have an anomalous value and ultraviolet spectrum, although its 6-methyl derivative is quite normal. Hydration in this case proved to be too fast to register in the rapid-reaction apparatus. 

The hydration reaction is carried out in a reactor at approximately 300°C and 70 atmospheres. The reaction is favored at relatively lower temperatures and higher pressures. Phosphoric acid on diatomaceous earth is the catalyst. To avoid catalyst losses, a water/ethylene mole ratio less than one is used. Conversion of ethylene is limited to 4-5% under these conditions, and unreacted ethylene is recycled. A high selectivity to ethanol is obtained (95-97%). 

The production of isopropanol from propylene occurs by either a direct hydration reaction (the newer method) or by the older sulfation reaction followed by hydrolysis. 

The hydroboration/oxidation sequence is complementary to the direct, mercury(ll)-catalyzed hydration reaction of a terminal alkyne because different products result. Direct hydration with aqueous acid and mercury(IJ) sulfate leads to a methyl ketone, whereas hydroboration/oxidation of the same terminal alkyne leads to an aldehyde. 

Aldehydes and ketones react with water to yield 1,1-diols, or geminal (gem) diols. The hydration reaction is reversible, and a gem diol can eliminate water to regenerate an aldehyde or ketone. 

The nucleophilic addition of water to an aldehyde or ketone is slow under neutral conditions but is catalyzed by both base and acid. The base-catalyzed hydration reaction takes place as shown in Figure 19.4. The nucleophile is the... 

The acid-catalvzed hydration reaction begins with protonation of the carbonyl oxygen atom, which places a positive charge on oxygen and makes the carbonyl group more electrophilic. Subsequent nucleophilic addition of water to the protonated aldehyde ot ketone then yields a protonated gem diol, which loses H+ to give the neutral product (Figure 19.5). 

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