Linear alcohol series

The foaming properties of sodium symmetrical secondary alcohol sulfates, sodium secondary alcohol sulfates, isomeric sodium secondary pentanol sulfates, and sodium linear alcohol sulfates were studied by Dreger et al. [72] via the Ross-Miles test [150] at 46°C. Within the linear series sodium tetradecyl sulfate produces the largest amount of foam. The influence of several electrolytes was also studied. 

In order to go further into the experimental check we constructed Arrhenius plots of the fluorescence quantum yield of BMPC in a few solvents (methanol, ethanol, propanol, hexanol and methylene chloride), all of which showed good linearity. The activation energies and A/kp ratios, calculated from the slopes and intercepts of those plots, are collected in Table 1. The smooth increase of both parameters in the alcohol series is mainly associated with the increase of solvent viscosity. On the other hand, decrease of the solvent dielectric constant from 32.7 (methanol) to 8.9 (dichloromethane) causes a small but significant increase of the activation energy also, this increase is probably somewhat compensated by the decrease of the viscous-flow... 

Table 7.5 also lists the coefficients obtained in the IL-based ATPS for proteins and short-chain linear alcohols [14]. The protein coefficients are two orders of magnitude higher than those obtained in the classical PEG 1000-K2HP04-water ATPS. The short-chain alcohols, a homologous series, have coefficients about one order of magnitude higher than their coefficient. The partitioning of Penicillin G was recently studied in the same ATPS and similar results were obtained (Table 7.5) [15]. These results indicate that the IL-rich phase of the [C4CiIm]Cl-K2HP04-acetonitrile-water system has a polarity much lower than the octanol phase of the reference system and also much lower than the PEG aqueous phase obtained with classical ATPS made with PEG 1000 and the same potassium hydrogeno phosphate salt [10,13,16].

Classical QSAR models were focused on a rather small number of compounds. The basic assumption was that a certain model is specific for a certain chemical class, sharing a common skeleton. Modifications of some simple chemical features were reflected in the property. Thus, for instance, a series of linear alcohols present aquatic toxicity, which varies in a rather linear way with the chain length [3],... 

Marlon B24 Series Terminally blocked linear alcohol ethoxylates... 

In figure 8.11, we also plot the values of G 4 for a series of linear alcohols CH3(CH2) iOH as a function of n at t = 0 °C. We also show the value of G ]ww at the same temperature. Note that the value G( nv is quite near the value that can be extrapolated from the linear plot of G (n) at n = 0 (n = 1 corresponds to methanol, n = 2 to ethanol, and n = 0 correspond to an extrapolated alcohol with no methyl group). This is an important observation and it might indicate that the value of G( vw is not very sensitive to the extent of the structure of water. This is in sharp contrast to the behavior of the entropy of solvation of inert gases in water, and in a series of alcohols. It is known (Ben-Naim 1987) that the value of A6 4 of say, argon or methane in water, is far more negative than the value that one can extrapolate from the solvation entropy in a series of alcohols. 

Figure 1.40 shows the KBI for a series of linear alcohols having the formula CH3(CFl2) -iOH as a function of the number of carbon atoms. It is seen that the values are all negative and... 

In this method, samples of freshly excised tissues were fixed by boiling them in a 10% neutral formaldehyde solution for 5 min. The fixed tissues were then embedded in paraffin and cut into 3 pm thick sections. The sections on glass slides were deparaffinized and dehydrated by passage through xylene and a graded alcohol series. Then they were incubated with a primary antibody against poly(ADP-ribose). The antibody used, IgG monoclonal antibody lOH, recognized the linear structure of poly(ADP-ribose) described previously (3). Bound antibody was stained with die avidin biotin peroxidase complex or by an indirect immunofluorescence technique. 

Anti-Markovnikov addition of H2O to olefins is of enormous importance in view of the production of linear alcohols directly from alkenes. It is a general phenomenon, however, that reaction of water with olefins and alkynes, as in the previous example, gives products of Markovnikov addition. The first anti-Markovnikov hydration of terminal alkynes (Scheme 42) with transition metal catalysis was reported in 1998 (227). A series of aliphatic and aromatic alkynes... 

This wide-spectrum, low-foaming series of biodegradable alkoxylated linear alcohols finds use in such diverse areas as rinse aids and metal cleaning baths, and as foam depressants in hard surface cleaners. 

Spreading velocities v are on the order of 15-30 cm/sec on water [39], and v for a homologous series tends to vary linearly with the equilibrium film pressure, it", although in the case of alcohols a minimum seemed to be required for v to be appreciable. Also, as illustrated in Fig. IV-3, substrate water is entrained to some depth (0.5 mm in the case of oleic acid), a compensating counterflow being present at greater depths [40]. Related to this is the observation that v tends to vary inversely with substrate viscosity [41-43]. An analysis of the stress-strain situation led to the equation... 

If a sample contains one or more members of a homologous series, identifications can be made using a plot of log tR against the number of carbon atoms, previously prepared from standards. The plot, which is valid for one temperature only, is linear and can be used for alkanes, alkenes, alcohols, aldehydes, ketones, esters and ethers. 

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. 

Some information about structure effects on the rate of dehydrogenation of alcohols to aldehydes and ketones on metals is found in the older literature 129-132) from which it follows that secondary alcohols react more easily than the primary alcohols 129) and that the reactivity decreases with the length of the carbon chain 131). Some series can be correlated by the Taft equation using a constants (Ref. 131, series 103, Cu-Cr203 catalyst, 350°C, four points, slope 18 Ref 132, series 104, Cu catalyst, four points, slope 22). Linear relationships have been used in a systematic way by... 

A series of bicyclo[3.3.0]octanols are accessible by electroreductive tandem cyclization of linear allyl pentenyl ketones 189, as shown by Kariv-Miller et al. [189]. The electrolyses are carried out with an Hg-pool cathode and a Pt-flag anode. As electrolyte, tetrabutylammonium tetrafluororborate is used. The reaction is stereoselective, yielding only two isomers 192 and 193. In a competing reaction, a small amount of the monocyclic alcohol is formed. Since all the monocycles have the 1-allyl and the 2-methyl group in trans geometry it is assumed that this terminates the reaction. The formation of a bicyclic product requires that the first cyclization provides the cis radical anion which leads to cis-ring juncture [190] (Scheme 37). 

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. 

There are liquid enthalpy of formation values for the methyl ethers for R = Me, -Pr, w-Bu and w-decyl. Additional enthalpies can be extrapolated for the R = Et and w-Pen species from the linear regression analysis of the enthalpies of formation vs. number of carbons . However, the regression constants from this same analysis immediately reveal that any assumption of thermoneutrality for equation 12 is incorrect. The slope of —25.3 0.1 kJmol for the methyl ethers is much too different from the slope for the peroxide series for there to be a constant difference between enthalpies of formation for two compounds with the same R substitution (the two alcohol enthalpies of formation in equation 12 are constant). As expected, the derived enthalpies of reaction for equation 12 increase with increasing number of carbons 13.9, 21.4, 24.0 and 25.6 kJmol. ... 

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