Rates viscosity effects

Concentration and Molecular Weight Effects. The viscosity of aqueous solutions of poly(ethylene oxide) depends on the concentration of the polymer solute, the molecular weight, the solution temperature, concentration of dissolved inorganic salts, and the shear rate. Viscosity increases with concentration and this dependence becomes more pronounced with increasing molecular weight. This combined effect is shown in Figure 3, in which solution viscosity is presented as a function of concentration for various molecular weight polymers. 

Thixotropy and Other Time Effects. In addition to the nonideal behavior described, many fluids exhibit time-dependent effects. Some fluids increase in viscosity (rheopexy) or decrease in viscosity (thixotropy) with time when sheared at a constant shear rate. These effects can occur in fluids with or without yield values. Rheopexy is a rare phenomenon, but thixotropic fluids are common. Examples of thixotropic materials are starch pastes, gelatin, mayoimaise, drilling muds, and latex paints. The thixotropic effect is shown in Figure 5, where the curves are for a specimen exposed first to increasing and then to decreasing shear rates. Because of the decrease in viscosity with time as weU as shear rate, the up-and-down flow curves do not superimpose. Instead, they form a hysteresis loop, often called a thixotropic loop. Because flow curves for thixotropic or rheopectic Hquids depend on the shear history of the sample, different curves for the same material can be obtained, depending on the experimental procedure. 

Some GPC analysts use totally excluded, rather than totally permeated, flow markers to make flow rate corrections. Most of the previously mentioned requirements for totally permeated flow marker selection still are requirements for a totally excluded flow marker. Coelution effects can often be avoided in this approach. It must be pointed out that species eluting at the excluded volume of a column set are not immune to adsorption problems and may even have variability issues arising from viscosity effects of these necessarily higher molecular weight species from the column. 

Properties of the solvent. Reaction rates will differ with the solvent s polarity, viscosity, donor number etc. Added electrolytes may lower or raise the rates ( salt effects ), and buffer components may do so as well. 

The uncertainty of calculating the Poiseuille number from the measurements must be taken into account. The viscosity-pressure relationship of certain liquids (e.g., isopropanol, carbon tetrachloride) must be kept in mind to obtain the revised theoretical flow rate. The effect of evaporation from the collection dish during the mass flow rate measurement must be taken into consideration. The effect of evaporation of collected water into the room air may not be negligible, and due to the extremely low mass flow rates through the micro-channel this effect can become significant. 

Very similar variations in average copolymer composition with conversion have recently been observed in the styrene methyl methacrylate system by both Johnson et al ( and by Dionisio and O Driscoll (. The reason for the variation may be due to a viscosity effect on propagation rate constants QO). 

Viscosity Effect The infiltration and redistribution of two hydrocarbons in moist silt loam and loamy sand soils, with viscosities of 4.7 (soltrol) and 77 (mineral oil) times greater than that of water, was reported by Cary et al. (1989). The spatial distribution of the two hydrocarbons and water is presented Fig. 12.12 the infiltration rate of... 

Selected entries from Methods in Enzymology [vol, page(s)] Anisotropy effects, 261, 427-430 determination by dynamic laser light scattering (quasi-elastic light scattering), 261, 432-433 determination for nucleic acids by NMR [accuracy, 261, 432-433 algorithms, 261, 11-13, 425, 430 carbon-13 relaxation, 261, 11-12, 422-426, 431, 434-435 cross-relaxation rates, 261,419-422, 435 error sources, 261, 430-432 phosphorus-31 relaxation, 261, 426-427, 431 proton relaxation, 261,51,418-422 relaxation matrix calculations, 261,12] deuterium solvent viscosity effects, 261,433 effect... 

The surface viscosity effect on terminal velocity results in a calculated drag curve that is closer to the one for rigid spheres (K5). The deep dip exhibited by the drag curve for drops in pure liquid fields is replaced by a smooth transition without a deep valley. The damping of internal circulation reduces the rate of mass transfer. Even a few parts per million of the surfactant are sometimes sufficient to cause a very radical change. 

Missing values correspond to very ill-defined patterns. The potential sweep rate is 100 mV s T napp. is the apparent electron number for the first voltammetric wave, ncorr. is the same value corrected for viscosity effects. 

Fig. 30a-d. Polymerization of methyl methacrylate by high speed stirring of polyethylene oxide solution, a) effect of monomer concentration on polymerization rate (PEO 4 g/100 ml, stirring speed 30000 rpm. b) effect of monomer (MMA) concentration on intrinsic viscosity of reaction mixture (PEO 4 g/100 ml, stirring speed 30000 rpm, solvent benzene, c) effect of PEO concentration on polymerization rate, d) effect of PEO concentration on intrinsic viscosity of reaction mixture (Stirring speed 30000 rpm)... 

The status of current theories of the low shear-rate viscosities (rj0) of polymer melts (and concentrated solutions) was reviewed by Berry and Fox in 1968 (52), since when there has been little development. The viscosity of linear polymers of low MW at constant temperature (or more precisely constant free volume is proportional to Mw, but at high MW it is proportional to a higher power M, where x is empirically about 3.4-3.5 the change of slope of a ogt]0/logMw plot is fairly abrupt The high exponent 3.4—3.5 is attributed to the effects of chain... 

At present, it cannot be said that there is a satisfactory theory of even the low shear-rate viscosities of branched polymers, since no existing theory accounts for the observed enhancement of melt viscosity in the cases referred to. Treatments that do not even predict the sign of an effect reliably can hardly be expected to predict its magnitude. 

The experimental evidence concerning the effects of LCB on the non-Newtonian behaviour of polyethylene melts is not as extensive as might be wished. Guillet and co-workers (167) studied fractions of both linear and branched polyethylenes and found that, for a given low shear-rate viscosity. 

Mendelson (169) studied the effect of LCB on the flow properties of polyethylene melts, using two LDPE samples of closely similar M and Mw plus two blends of these. Both zero-shear viscosity and melt elasticity (elastic storage modulus and recoverable shear strain) decreased with increasing LCB, in this series. Non-Newtonian behaviour was studied and the shear rate at which the viscosity falls to 95% of the zero shear-rate value is given this increases with LCB from 0.3 sec"1 for the least branched to 20 sec"1 for the most branched (the text says that shear sensitivity increases with branching, but the numerical data show that it is this shear rate that increases). This comparison, unlike that made by Guillet, is at constant Mw, not at constant low shear-rate viscosity. 

The reaction of barbiturate and 1,3 -dimethylbarbiturate ions with 2- and 4-nitrobenzaldehyde and 2,4-dinitrobenzaldehyde represented generally in Scheme 5 involves a diffusion-controlled (viscosity effects on rates) proton transfer from hydronium ion to an addition intermediate T in the slow step.14 The addition of water and ring-opening reactions of the protonated benzoxazines (14) involves the cyclic intermediate (15). At low buffer concentrations buffer-catalysed collapse of the intermediate is rate limiting but, at high buffer concentrations, the addition of water is the rate-limiting step.15 The anionic tetrahedral intermediate (16) is involved in the hydrolysis of the 2, 2, 2,-trifluoroethyl monoester of 1,8-naphthalic acid (17).16... 

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