Alcohols correlation table

Polar solvents have no effect on the rate constant of the reaction R02 + RH [56], This means that the solvation energies of the peroxyl radical R02 and TS R02 HR are very close. A different situation was observed for the reaction of cumylperoxyl radical with benzyl alcohol (see Table 7.10). The rate constant of this reaction is twice in polar dimethylsulfoxide (s = 33.6) than that in cumene (a 2.25). It was observed that the very important property of the solvent is basicity (B), that is, affinity to proton. A linear correlation... 

IR interpretation can be as simple or as complicated as you d like to make it. You ve already seen how to distinguish alcohols from ketones by correlation of the positions and intensities of various peaks in your spectrum with positions listed in IR tables or correlation tables. This is a fairly standard procedure and is probably covered very well in your textbook. The things that are not in your text are... 

Fig. 5. Correlation of the Taft reaction parameter for the dehydration of secondary alcohols (see Table 4) on four different oxide catalysts with the heat of adsorption, A//ads> °f water and diethylether, with the sensitivity of the rate to pyridine poisoning 7> [55] and with the value of the deuterium kinetic isotope effect [123] for the same catalysts.

The correlation tables for alcohols and phenols are in Appendix 2, Table A2.5. 

As expected, restricting the class of chemicals to structurally similar compounds such as alcohols or PCBs permits an improved correlation, Table 7.1, adapted from Lyman et al. (1982) and Yalkowsky and Banerjee (1992), lists a number of correlations for specific chemical classes. 

Surfactant critical micelle concentration (cmc) may be related to chemical structure using multiple correlation analysis. The cmc value plays an important role in surfactant adsorption, foaming, and interfacial tension properties. The 25 C cmc values of a series of high purity single component highly linear primary alcohol ethoxylates (Table 6) were analyzed using equation 4 ... 

Equation 5 was used to analyze the cmc properties for a series of alcohol ethoxysulfates (Table 8). While a "fair" correlation coefficient of 0.946 was obtained, it should be noted that the range of hydrophobe carbon chain lengths studied was limited. AES surfactants are prepared by sulfation of alcohol ethoxylates and can contain unreacted alcohol ethoxylate. Variation in the concentration of unreacted AE, which is not considered in equation 5, could reduce the correlation coefficient. 

The processes for manufacturing methanol by synthesis gas reduction and ethanol by ethylene hydration and fermentation are very dissimilar and contribute to their cost differentials. The embedded raw-material cost per unit volume of alcohol has been a major cost factor. For example, assuming feedstock costs for the manufacture of methanol, synthetic ethanol, and fermentation ethanol are natural gas at 3.32/GJ ( 3.50/10 Btu), ethylene at 0.485/kg ( 0.22/lb), and corn at 0.098/kg ( 2.50/bu), respectively, the corresponding cost of the feedstock at an overall yield of 60% or 100% of the theoretical alcohol yields can be estimated as shown in Table 11.12. In nominal dollars, these feedstock costs are realistic for the mid-1990s and, with the exception of corn, have held up reasonably well for several years. The selling prices of the alcohols correlate with the embedded feedstock costs. This simple analysis ignores the value of by-products, processing differences, and the economies of scale, but it emphasizes one of the major reasons why the cost of methanol is low relative to the cost of synthetic and fermentation ethanol. The embedded feedstock cost has always been low for methanol because of the low cost of natural gas. The data in Table 11.12 also indicate that fermentation ethanol for fuel applications was quite competitive with synthetic ethanol when the data in this table were tabulated in contrast to the market years ago when synthetic ethanol had lower market prices than fermentation ethanol. Other factors also... 

In light of the difficulties in diagnosing subclinical forms of thiamine deficiency, all patients deemed at risk of encephalopathy should be screened for such possibility. However, there is no clear indicator for laboratory tests or criteria for preclinical thiamine deficiency diagnosis. Decreased TDP levels in blood of alcoholics correlated modestly with worsening of their memory performance (Table 33.2). This may result from large variations in individual susceptibility to low TDP levels. In addition, only 0.5% of the body s whole store of TDP is present in the blood and blood TDP may thus not reflect well its content in the brain and other tissues (Pitel et al. 2011). 

There have been numerous studies on the kinetics of decomposition of A IRK. AIBMe and other dialkyldiazenes.46 Solvent effects on are small by conventional standards but, nonetheless, significant. Data for AIBMe is presented in Table 3.3. The data come from a variety of sources and can be seen to increase in the series where the solvent is aliphatic < ester (including MMA) < aromatic (including styrene) < alcohol. There is a factor of two difference between kA in methanol and k< in ethyl acetate. The value of kA for AIBN is also reported to be higher in aromatic than in hydrocarbon solvents and to increase with the dielectric constant of the medium.31 79 80 Tlic kA of AIBMe and AIBN show no direct correlation with solvent viscosity (see also 3.3.1.1.3), which is consistent with the reaction being irreversible (Le. no cage return). 

Basic hydrolysis of 6 afforded alcohol 19 and methyl veratrate. The H-NMR spectrum of 19 (Table II) revealed the presence of one methylenedioxy, one N-methyl, and two methoxyl groups. The mass spectrum (Table IV) exhibited the most abundant and significant ion peak at m/z 229 indicative of metaphanine-type cleavage. Treatment of an aqueous THF solution of stephavanine (18) with excess sodium hydride and methyl iodide gave N.O-dimethylstephine, a compound identical to alcohol 19. Thus, the structure of the new alkaloid 6 was established by chemical correlation with stephavanine (79). 

The values of KTS in Tables A5.13 and A5.14 vary significantly with structure but they do so in a manner that strongly parallels Kx for the PI CD complexation. In fact, for both a-CD and /3-CD, and three series of Pis, there are good correlations between p/fxs and pA) (Table 6) the data for a-and /3-CD and alcohols are shown in Fig. 7. The two correlations for alcohols are particularly noteworthy since each includes various structural types (linear, secondary, branched, cyclic, etc.). Thus, the abilities of Pis to bind (and stabilize) the transition state of the reaction of pNPA with CDs is firmly related to their abilities to bind in the CD cavities. 

Fig. 7 Correlation of transition state binding (p/fTS) of alcohols mediating the cleavage of pNPA by a- and /3-CD with their ability to bind to these CDs (pK)). The left and right scales are offset for clarity. Data from Tables A5.13 and A5.14.

Fig. 8 Correlation of the transition state binding (pKjs) of alcohols catalysing the cleavage of p-nitrophenyl hexanoate by /3-CD with their binding in the initial state ternary complexes (pK,) [see (26)]. Data from Table A5.15.

Fig. 1. Correlation of the rates of primary alcohol dehydration (40) (series 1 from Table II) in the coordinates of the Taft equation (8) for different separations of the reactants molecules into the parts substituent-link-reaction center.

Also other Type B and C series from Table II are consistent with the above elimination mechanisms. The dehydration rate of the alcohols ROH on an acid clay (series 16) increased with the calculated inductive effect of the group R. For the dehydrochlorination of polychloroethanes on basic catalysts (series 20), the rate could be correlated with a quantum-chemical reactivity index, namely the delocalizability of the hydrogen atoms by a nucleophilic attack similar indices for a radical or electrophilic attack on the chlorine atoms did not fit the data. The rates of alkylbenzene cracking on silica-alumina catalysts have been correlated with the enthalpies of formation of the corresponding alkylcarbonium ions (series 24). Similar correlations have been obtained for the dehydrosulfidation of alkanethiols and dialkyl sulfides on silica-alumina (series 36 and 37) in these cases, correlation by the Taft equation is also possible. The rate of cracking of 1,1-diarylethanes increased with the increasing basicity of the reactants (series 33). 

At this point it was clear that the highest potential for increased activity was by substitution in the 2-position of the biphenyl alcohol. We prepared the sequence of compounds shown in Table 1. Substituents were again chosen to maximize the parameter space covered within the relatively stringent synthetic limitations of the biphenyl substitution pattern. The application of regression analysis to the data for these compounds provided no clear relationship between structure and activity when the parameters in our standard data base were used. The best linear fit was found for B4, the STERIMOL maximum radius. However, the correlation coefficient was only 0.625. 

Armentrout and Rogers also suggest more suitable anchor points for the LCA scale, e.g. the lithium cation bond energies to methanol or dimethyl ether. They further examined the kinetic energy dependences of the CID of Li+—ROH with and reported that the dominant dissociation process in all cases is the loss of alcohol. The thresholds for Li+—ROH dissociations were determined and converted to enthalpies and free energies at 298 and 373 K for comparison with previous equihbrium data on these systems. LCA values at 298 K for a series of alcohols are summarized in Table 3. The experimental results are compared with enthalpies of binding (PA) at 298 K (Figure 2) and a linear correlation between the LCA and the PA is found. 

Taft and coworkers ° have reported lithium ion affinities, AGu+, for various types of compounds. Values of AGu+ for alkyl thiols, dialkyl sulfides, alcohols and dialkyl ethers (sets CP3, CP4, CPS and CP6, Table 10) were correlated with equation 27. The regression equation for the alkyl thiols is equation 58 ... 

The phenol work has now been extended to a whole series of different alcohols which all have a very substantial number of bases which give rise to constant acid lines, i.e., a series of different — AH vs. Aron lines for different alcohols substituted phenols, 1,1,1,3,3,3 hexafluoro-2-propanol (CF3)2CHOH 81), t-butyl alcohol (52) and trifluoroethanol 83). In addition, the acid pyrrole 84) produced a similar correlation. To be sure, there are exceptions to these correlations, but a very wide range of donor t5 es conform, making the correlations quite general and valuable. The several correlations described above are plotted in Fig. 7, where they are indicated with solid lines. The equations for the straight lines ire given in Table 9. 

---