Alcohols rate constants

Alcohol Rate constant, iT>in Relative rate (CHsQH = 100)... 

Substrate Unrearranged Product(s) Rearranged Alcohol(s) Expected Observed Ratio of Unrearranged to Rerranged Alcohol Rate Constant For Radical Rear-rangement, s-i at45 C... 

Breslow studied the dimerisation of cyclopentadiene and the reaction between substituted maleimides and 9-(hydroxymethyl)anthracene in alcohol-water mixtures. He successfully correlated the rate constant with the solubility of the starting materials for each Diels-Alder reaction. From these relations he estimated the change in solvent accessible surface between initial state and activated complex " . Again, Breslow completely neglects hydrogen bonding interactions, but since he only studied alcohol-water mixtures, the enforced hydrophobic interactions will dominate the behaviour. Recently, also Diels-Alder reactions in dilute salt solutions in aqueous ethanol have been studied and minor rate increases have been observed Lubineau has demonstrated that addition of sugars can induce an extra acceleration of the aqueous Diels-Alder reaction . Also the effect of surfactants on Diels-Alder reactions has been studied. This topic will be extensively reviewed in Chapter 4. 

At ordinary temperatures, formaldehyde gas is readily soluble in water, alcohols, and other polar solvents. Its heat of solution in water and the lower ahphatic alcohols is approximately 63 kJ/mol (15 kcal/mol). The reaction of unhydrated formaldehyde with water is very fast the first-order rate constant... 

The law of mass action, the laws of kinetics, and the laws of distillation all operate simultaneously in a process of this type. Esterification can occur only when the concentrations of the acid and alcohol are in excess of equiUbrium values otherwise, hydrolysis must occur. The equations governing the rate of the reaction and the variation of the rate constant (as a function of such variables as temperature, catalyst strength, and proportion of reactants) describe the kinetics of the Hquid-phase reaction. The usual distillation laws must be modified, since most esterifications are somewhat exothermic and reaction is occurring on each plate. Since these kinetic considerations are superimposed on distillation operations, each plate must be treated separately by successive calculations after the extent of conversion has been deterrnined (see Distillation). 

Continuous esterification of acetic acid in an excess of -butyl alcohol with sulfuric acid catalyst using a four-plate single bubblecap column with reboiler has been studied (55). The rate constant and the theoretical extent of reaction were calculated for each plate, based on plate composition and on the total incoming material to the plate. Good agreement with the analytical data was obtained. 

Here AX is the acetyl compound (acetyl chloride or acetic anhydride), N is N-methylimidazole, I is the intermediate (presumably A -acetyl-A -methylimidazo-lium ion), X is the counterion (chloride or acetate), and ROH is the acetyl acceptor (alcohol or water). A general treatment of Scheme XXIII requires specification of the detailed nature of and k[ and is probably too complicated to be of practical use. However, several important special cases may arise from the operation of the ratio kxlk x, the behavior of apparent rate constants k /. and k, the relative magnitudes of k / and k, the relative concentrations of the reactants, the method of observation, and the nature of ROH. These cases are outlined in Scheme XXIV. 

The rate constant /ct, determined by means of Eq. (6-47) or (6-48), may describe either general base or nucleophilic catalysis. To distinguish between these possibilities requires additional information. For example, in Section 3.3, we described a kinetic model for the N-methylimidazole-catalyzed acetylation of alcohols and experimental designs for the measurement of catalytic rate constants. These are summarized in Scheme XVIIl of Section 3.3, which we present here in slightly different form. 

We have further attempted to suggest a procedure which would make use of the advantages of the method of competitive reactions, i.e. its simplicity and little time demand, and at the same time would yield separately the absolute values of rate constants and adsorption coefficients also for reactions with a more complicated kinetics. Using the values of relative reactivities S from the method of competitive reactions, the adsorption coefficients, for example, of the alcohols (Kb) in the reesterification reaction described by Eq. (26) can be evaluated from the relation... 

Ratios of Rate Constants and of Adsorption Coefficients in Parallel Dehydrogenation (1) and Dehydration (2) of Isopropyl Alcohol on Some Oxide Catalysts (123)... 

By quenching the polymerization with C1402 or Cl40 the determination of the number of propagation rate constants was found to be also possible for the two-component catalytic system TiCl2 + AlEt2Cl 158, 159). In contrast to alcohols, carbon dioxide and carbon monoxide under polymerization conditions react only with titanium-carbon active bonds and do not react with inactive aluminum-polymer bonds. 

Note that all the zero-order rate constants are essentially equivalent except those for the poly-hydric alcohols which are exactly half the value of the others. Ingold et al (Ref 49a) interpret this to mean that the rate of attack of nitronium is the same for both OH groups of the glycol molecule. Since there are two such groups the overall rate constant k0 is Vi that for monohydric alcohols. The explanation for the observed k0 for glycerol is more complex. In essence it consists of postulating that the two outside OH s are readily nitrated, ie, the 1-OH is nitrated at the same rate as the 3-OH, but the middle OH is nitrated much more slowly... 

By varying the alcohol concentration, the two rate constants can be determined. Then, with added RH, the experimental rate constant acquires a third term... 

At its best, the study of solvent kies by the formalism given can be used to learn about proton content and activation in the transition state. For this reason it is known as the proton inventory technique. The kinetics of decay of the lowest-energy electronic excited state of 7-azaindole illustrates the technique.25 Laser flash photolysis techniques (Section 11.6) were used to evaluate the rate constant for this very fast reaction. From the results it was suggested that, in alcohol, a double-proton tautomerism was mediated by a single molecule of solvent such that only two protons are involved in the transition state. In water, on the other hand, the excited state tautomerism is frustrated such that two water molecules may play separate roles. Diagrams for possible transition states that can be suggested from the data are shown, where of course any of the H s might be D s. 

No systematic studies of a number of compoimds have yet appeared to discover correlations suggestive of mechanism. This paper presents the fractional conversions and reaction rates measured under reference conditions (50 mg contaminants/m ) in air at 7% relative humidity (1000 mg/m H2O), for 18 compounds including representatives of the important contaminant classes of alcohols, ethers, alkanes, chloroethenes, chloroalkanes, and aromatics. Plots of these conversions and rates vs. hydroxyl radical and chlorine radical rate constants, vs. the reactant coverage (dark conditions), and vs. the product of rate constant times coverage are constructed to discern which of the proposed mechanistic suggestions appear dominant. 

Figure 1 kci vs. koH- Second order gas phase rate constants for the reaction of Cl atoms vs. the corresponding OH radicals rate constants for the reactions with a. n-alkanes [11] b. n-alcohols [12] c. n-ethers [12] d. chloroethenes [13] and e. 1-chloroalkanes [14],... 

Figure 1 present kci versus koH values for families of compoimds where both rate constants were found in the literature for n-alcohols, n-alkanes, n-ethers, chloroethenes, 1-chIoroalkanes, aromatics, aldehydes, and ketones. This graph demonstrates that ... 

Gratzel and co-workersfound that the 600 nm absorption of MV is built up after the laser flash. The colloid was stabilized by polyvinyl alcohol. The laser flash produced a large number of electrons in each colloidal particle. The build-up followed a first order rate law, the rate constant being proportional to the MV concentration, and the final amount of MV formed also increased with the MV concentration. Figure 23 shows the final MV concentration as a function of the pH of the solution. Below pH = 2, MV is not reduced. The electron transfer from the colloidal particles proceeds until electrochemical equilibrium is reached between the Ti02 particles and the MV /MV system in solution. At low pH values thisequilib-... 

At this temperature the reaction rate constant is equal to 0.082 liters/mole-min. If the reaction takes place in a constant pressure reactor, starting with pure gaseous alcohol at a pressure of 2 atm, find the time necessary to reach 20% decomposition ... 

Rate constants and equilibrium constants have been determined for the acid catalyzed reaction of siloxanes (XMe2Si)20 with alcohols. The results are discussed with respect to substituent dependence and compared with those of similar investigations at linear and cyclic methylsiloxanes. 

The rate constants are given in Table 1 for reactions under the following conditions 0.1-0.6 mol/L siloxane, 4 mol/L alcohol, 0.002-0.006 mol/L HCIO4, 0.05 mol/L H20 in dioxane. Also in Table 1 are given the equilibrium constants, determined for the same reaction series. 

Under conditions similar to those for (XMe2Si)20, the acid catalyzed cleavages with alcohols of linear and cyclic methylsiloxanes have been investigated. The rate constants of the primary reaction, the cleavage of the first Si-O-Si-bond, determined by GLC and HPLC, are given in Table 2. 

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