Neat liquids

Photopolymerization reactions of monolayers have become of interest (note Chapter XV). Lando and co-workers have studied the UV polymerization of 16-heptadecenoic acid [311] and vinyl stearate [312] monolayers. Particularly interesting is the UV polymerization of long-chain diacetylenes. As illustrated in Fig. IV-30, a zipperlike process can occur if the molecular orientation in the film is just right (e.g., polymerization does not occur readily in the neat liquid) (see Refs. 313-315). 

Figure C3.5.11. IR-Raman measurements of vibrational energy flow tlirough acetonitrile in a neat liquid at 300 K, adapted from [41], An ultrashort mid-IR pulse pumps the C-H stretch, which decays in 3 ps. Only 1% of the energy is transferred to the C N stretch, which has an 80 ps lifetime. Most of the energy is transferred to the C-H bend plus about four quanta of C-C=N bend. The daughter C-H bend vibration relaxes by exciting the C-C stretch. The build-up of energy in the C-C=N bend mirrors the build-up of energy in the bath, which continues for about 250 ps after C-H stretch pumping.

Surface tension is usually predicted using group additivity methods for neat liquids. It is much more difficult to predict the surface tension of a mixture, especially when surfactants are involved. Very large molecular dynamics or Monte Carlo simulations can also be used. Often, it is easier to measure surface tension in the laboratory than to compute it. 

Using a multiple linear regression computer program, a set of substituent parameters was calculated for a number of the most commonly occurring groups. The calculated substituent effects allow a prediction of the chemical shifts of the exterior and central carbon atoms of the allene with standard deviations of l.Sand 2.3 ppm, respectively Although most compounds were measured as neat liquids, for a number of compounds duplicatel measurements were obtained in various solvents. 

Because dimethyl sulfate looks like water, operations are preferably not performed when water is present, eg, wet floors or rain. Any spills or leaks should not be left unattended they should be contained, and mnoff to sewers should be avoided. Minor spills should be flooded with water to dilute and hydroly2e the dimethyl sulfate. The area should then be covered with a dilute (2—5 wt %) caustic solution or a dilute (2—5 wt %) ammonia solution, or soda ash may be sprinkled over the neat liquid and the mix wetted with a gende spray of water. The neutrafi2ing agent should remain on the affected area for 24 h and then should be washed away. Only personnel wearing protective equipment should perform these operations. The product bulletins should be consulted for procedures to be followed for more severe spills. Concentrated ammonia should not be used with neat dimethyl sulfate because explosions have resulted after their contact (128). 

Neat liquids, unless otherwise specified values for ipso position (carrying substituent) italicized data ... 

N-protonation the absolute magnitude of the Ad values is larger than for Af-methylation <770MR(9)53>. Nuclear relaxation rates of and have been measured as a function of temperature for neat liquid pyridazine, and nuclear Overhauser enhancement has been used to separate the dipolar and spin rotational contributions to relaxation. Dipolar relaxation rates have been combined with quadrupole relaxation rates to determine rotational correlation times for motion about each principal molecular axis (78MI21200). NMR analysis has been used to determine the structure of phenyllithium-pyridazine adducts and of the corresponding dihydropyridazines obtained by hydrolysis of the adducts <78RTC116>. 

A number of studies on the NMR spectra of isoxazole has been compiled and this list includes the coupling constants in various solvents as well as the neat liquid. The N signal for isoxazole appears at 339.6 p.p.m. relative to TTAI and is at much lower field than in other azoles. Reports of spectra of substituted isoxazoles also abound (79AhC(25)147, p. 201). 

In the first example of applications of the theory in this chapter, we made a point with respect to the polarizability of molecules and showed how the problem could have been handled by the RISM-SCF/MCSCF theory. However, the current level of our method has a serious limitation in this respect. The method can handle the polarizability of molecules in neat liquids or that of a single molecule in solution in a reasonable manner. But in order to be able to treat the polarizability of both solute and solvent molecules in solution, considerable generalization of the RISM side of the theory is required. When solvent molecules are situated within the influence of solute molecules, the solvent molecules are polarized differently depending on the distance from the solute molecules, and the solvent can no longer be neat. Therefore, the polarizable model developed for neat liquids is not valid. In such a case, solvent-solvent PCF should be treated under the solute... 

The final steps to a synthetic blood depend completely upon good chemistry tailored to meet the exact needs of the body Fluorocarbons, such as perfluorodecalin, recently have been found to induce hypennflated lungs when given either intravenously as an emulsion or mtratracheally as a neat liquid [18, 19] But this and other physiological side effects are now understood, and research is well advanced to prevent undesirable side effects in medical applications of fluorocarbon liquids... 

So far, there have been few published simulation studies of room-temperature ionic liquids, although a number of groups have started programs in this area. Simulations of molecular liquids have been common for thirty years and have proven important in clarifying our understanding of molecular motion, local stmcture and thermodynamics of neat liquids, solutions and more complex systems at the molecular level [1 ]. There have also been many simulations of molten salts with atomic ions [5]. Room-temperature ionic liquids have polyatomic ions and so combine properties of both molecular liquids and simple molten salts. 

The modihcation of polymer surfaces by graft copolymerization of a monomer or monomers from active sites has been reported in numerous references [165-169]. The most common techniques are y- and EB radiations, which generate surface radicals. Monomers can be present in gas phase (sublimed solid), in solution or as neat liquid. 

The last state in Fig. 11.1 that has not yet been discussed is the state of the neat liquid compound X. For liquid compounds this is the relevant initial state for solubility, but almost aU drug-Uke compounds are solid at room temperature. In this case the neat liquid is a virtual state of a supercooled liquid which can hardly be accessed experimentally. However, it is an interesting intermediate state because it allows us to split the calculation of solubility into two separate steps, which are conceptually and for some methods computationally easier to handle than the complete step from the crystaUine state of the drug to the liquid state of the drug dissolved in water. In the first step we only have to transfer the compound from its neat crystalline state to its neat liquid state. The free energy of this fusion transfer is usually called AG s (or if considered in the opposite direction). 

Since 4 has a high inclusion ability for a wide variety of organic compounds 46), it might be useful for various reaction controls. For example, 4 was found to be useful for a selective synthesis of the P-lactam 89 from N,N-diisopropylaeetylformamide (88). Irradiation of 88 in benzene solution and in neat liquid has been reported to give the oxazolidinone derivative 90 exclusively in 86 and 65% yields, respectively, but not any 89 Control of the photocyclization of 88 has been attempted by irradiation... 

If you don t want to contaminate your sample, you can use a small tube, filled with a deuterated solvent, inside your main tube, as mentioned earlier. This is particularly useful if you are running a neat liquid or if the deuterated solvent is immiscible with your sample. This is probably the most common approach to this problem. 

As it is potentially explosive in neat liquid or solid forms, it is best handled in solution. 

Unpredictably explosive as the neat liquid, it may be handled safely in solution. 

A number of new approaches to the way in which precursors are delivered to a substrate have been developed in which the precursor is dispersed into the gas phase without having to be volatile. These new systems each have their own advantages for a particular precursor depending on its physical state. Most of the delivery systems in use can be classified as one of the following a liquid injection system (LIS), where a precursor is vaporized directly from a neat liquid or solution containing the precursors a solid delivery system (SDS), where the precursor is vaporized... 

G values refer to the neat liquids, although in most cases energy transfer to solutes is used to establish the values. 

Tris(dimethylamino)arsine (d2o 1.1248 nd 1.4848)3 is a colorless liquid which is readily hydrolyzed to form arsenic (III) oxide and dimethylamine when brought into contact with water. The compound is soluble in ethers and hydrocarbons. The product is at least 99.5% pure (with respect to hydrogen-containing impurities) as evidenced by the single sharp peak at —2.533 p.p.m. (relative to tetramethylsilane) seen in the proton nuclear magnetic resonance spectrum of the neat liquid. 

The organic phase can be a nonpolar organic solvent (e.g., benzene, toluene, hexane, dichloromethane, chloroform, etc.) or a neat liquid substrate, usually the electrophilic reagent, which acts both as a reactive substrate and the liquid phase. 

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