Expansion solvent

THE MULTIPOLE MOMENT EXPANSION SOLVENT CONTINUUM MODEL A BRIEF REVIEW... 

Abstract The multipole moment expansion solvent continuum model is being developed by our... 

The Multipole Moment Expansion Solvent Continuum Model... 

STR Striolo, A., Elvassore, N., Parton, T., and Bertucco, A., Relationship between volume expansion, solvent power, and precipitation in GAS processes, AIChE-J., 49,2671, 2003. 

Ruiz-Lopez MF (2008) The multipole moment expansion solvent continuum model a brief review. In Canuto S (ed) Solvation effects on molecules and biomolecules, vol 6. Challenges and advances in computational chemistry and physics. Springer, Netherlands, pp 23-38. doi 10.1007/978-l-4020-8270-2 2... 

Figure Bl.11.9. Integrated 250 MHz H NMR spectrum of dilute propan-1-ol in dinrethylsulfoxide solvent. Here, the shift order parallels the chemical order. Arr expansion of the H2-I nrultiplet is included, as is the implicit frequency scale, also referenced here to TMS = 0.

At the beginning of this section we enumerated four ways in which actual polymer molecules deviate from the model for perfectly flexible chains. The three sources of deviation which we have discussed so far all lead to the prediction of larger coil dimensions than would be the case for perfect flexibility. The fourth source of discrepancy, solvent interaction, can have either an expansion or a contraction effect on the coil dimensions. To see how this comes about, we consider enclosing the spherical domain occupied by the polymer molecule by a hypothetical boundary as indicated by the broken line in Fig. 1.9. Only a portion of this domain is actually occupied by chain segments, and the remaining sites are occupied by solvent molecules which we have assumed to be totally indifferent as far as coil dimensions are concerned. The region enclosed by this hypothetical boundary may be viewed as a solution, an we next consider the tendency of solvent molecules to cross in or out of the domain of the polymer molecule. 

In a good solvent, the end-to-end distance is greater than the 1q value owing to the coil expansion resulting from solvent imbibed into the domain of the polymer. The effect is quantitatively expressed in terms of an expansion factor a defined by the relationship... 

Although the emphasis in these last chapters is certainly on the polymeric solute, the experimental methods described herein also measure the interactions of these solutes with various solvents. Such interactions include the hydration of proteins at one extreme and the exclusion of poor solvents from random coils at the other. In between, good solvents are imbibed into the polymer domain to various degrees to expand coil dimensions. Such quantities as the Flory-Huggins interaction parameter, the 0 temperature, and the coil expansion factor are among the ways such interactions are quantified in the following chapters. 

We saw in Sec. 1.11 that coil dimensions are affected by interactions between chain segments and solvent. Both the coil expansion factor a defined by Eq. (1.63) and the interaction parameter x are pertinent to describing this situation. 

Our primary interest in the Flory-Krigbaum theory is in the conclusion that the second virial coefficient and the excluded volume depend on solvent-solute interactions and not exclusively on the size of the polymer molecule itself. It is entirely reasonable that this should be the case in light of the discussion in Sec. 1.11 on the expansion or contraction of the coil depending on the solvent. The present discussion incorporates these ideas into a consideration of solution nonideality. 

The parameter a which we introduced in Sec. 1.11 to measure the expansion which arises from solvent being imbibed into the coil domain can also be used to describe the second virial coefficient and excluded volume. We shall see in Sec. 9.7 that the difference 1/2 - x is proportional to. When the fully... 

What is especially significant about Eq. (9.68) is the observation that the coil expansion factor a definitely increases with M for good solvents, meaning that-all other things being equal longer polymer chains expand above their 0 dimensions more than shorter chains. Even though the dependence of a on... 

SAN resins show considerable resistance to solvents and are insoluble in carbon tetrachloride, ethyl alcohol, gasoline, and hydrocarbon solvents. They are swelled by solvents such as ben2ene, ether, and toluene. Polar solvents such as acetone, chloroform, dioxane, methyl ethyl ketone, and pyridine will dissolve SAN (14). The interactions of various solvents and SAN copolymers containing up to 52% acrylonitrile have been studied along with their thermodynamic parameters, ie, the second virial coefficient, free-energy parameter, expansion factor, and intrinsic viscosity (15). 

Noryl is a rigid dimensionally stable material. Dimensional stabiUty results from a combination of low mold shrinkage, low coefficient of thermal expansion (5.9 x 10 per° C), good creep resistance (0.6—0.8% in 300 h at 13.8 MPa (2000 psi)), and the lowest water absorption rate of any of the engineering thermoplastics (0.07% in 24 h at room temperature). Noryl resins are completely stable to hydrolysis. They are not affected by aqueous acids or bases and have good resistance to some organic solvents, but they are attacked by aromatic or chlorinated aUphatic compounds. 

Solvent name Viscosity, neat, Surface tension. Coeff. of expansion at 20°C, ... 

Pyrolysis of CsjB Hg] at 230°C gives CS2IB2H2] (60%) along with some CS2IB2QH2Q], CS2IB22H22], and CsBH (93). The sensitivity of polyhedral expansion reactions to solvent, temperature, and pressure is further exemplified by the results ia dioxane at 120°C under pressure. To obtain the closo borane, NajB H J is first converted to Cs2[B2 H23], which can be pyrolyzed to give Cs2[B2 H2J (89). 

Benzyl chloride [(chloromethyl)henzene, a-chlorotoluene], CgH CH2Cl, is a colorless Hquid with a very pungent odor. Its vapors are irritating to the eyes and mucous membranes, and it is classified as a powerfljl lacrimator. The physical properties of pure benzyl chloride are given in Table 2 (2—7). Benzyl chloride is insoluble in cold water, but decomposes slowly in hot water to benzyl alcohol. It is miscible in all proportions at room temperature with most organic solvents. The flash point of benzyl chloride is 67°C (closed cup) 74°C (open cup) autoignition temperature is 585°C lower flammability limit 1.1% by volume in air. Its volume coefficient of expansion is 9.72 x. ... 

Supercriticalfluid solvents are those formed by operating a system above the critical conditions of the solvent. SolubiHties of many solutes ia such fluids often is much greater than those found for the same solutes but with the fluid at sub atmospheric conditions. Recently, there has been considerable iaterest ia usiag supercritical fluids as solvents ia the production of certain crystalline materials because of the special properties of the product crystals. Rapid expansion of a supercritical system rapidly reduces the solubiHty of a solute throughout the entire mixture. The resulting high supersaturation produces fine crystals of relatively uniform size. Moreover, the solvent poses no purification problems because it simply becomes a gas as the system conditions are reduced below critical. 

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