A nuclear magnetic resonance study of toluene-polyisobutylene solutions. 3. Spin-lattice relaxation: Rotational and segmental motion

The spin-lattice relaxation times are determined for the methylene carbon of polyisobutylene (PIB), as well as for the ortho carbon of toluene in toluene-polyisobutylene solutions. The Hall-Helfand correlation function combined with restricted anisotropic rotational diffusion was used to treat the T₁ data of the methylene carbon of PIB. A simple exponential correlation function was used to describe the local motion of toluene in the solutions which falls in the extreme narrowing limit for the solutions studied. Both models described satisfactorily the temperature and field dependence of the spin-lattice relation times. From the temperature dependence of the correlation times for the polymer segmental motion, the free volume of the solution at each concentration is extracted and compared with the values obtained from previous studies of the translational motion of the toluene penetrant. The free volume values extracted from the T₁ data for the methylene carbon of PIB and the self-diffusion data for the toluene were found to be in substantial agreement. The interrelationship of the timescale of segmental motion of the polymer and the translational diffusion of the toluene was also examined and it was found that the two types of motion seem to be correlated in high polymer concentrated solutions. The toluene reorientational motion was found to be much faster than both the polymer segmental motion and the toluene translational diffusion leading to the conclusion that the toluene reorientational motion is uncoupled from these two motions. ©1995 John Wiley & Sons, Inc.     

C60-甲苯溶液溶剂化作用

The solvation of the system of C60-toluene is studied by determining UV-Vis absorption spectrum, it is found that the maximum absorption wavelength of C60 exhibits red-shift in toluene medium. Viscosity measurement gives the thickness of the solvation layer as 0.85 nm. At temperature 30℃, the value of the diffusion coefficient is 3.12× 10-10m2•s-1 which is an order of magnitude less than that of small molecules. The results above indicate that C60 is solvated in toluene medium.     

Temperature-Dependent Diffusion Coefficients from 1D Raman Spectroscopy

A setup for the measurement of temperature-dependent diffusion coefficients has been developed based on 1D Raman spectroscopy. The presented setup was used to measure binary diffusion coefficients for mixtures of monoethanolamine + water, cyclohexane + toluene, and methanol + toluene for temperatures between T = 298.15 and 330.15 K. The experimental diffusion coefficients agree well with available literature data. For the mixture methanol + toluene, literature data was only found for T = 298.15 K. The novel setup was therefore used to determine temperature-dependent diffusion coefficients of methanol + toluene up to T = 328.15 K. The experimental data are also compared to a temperature correlation for diffusion coefficients in concentrated solutions. While the correlation describes the temperature dependence well for simple systems, measurement techniques remain indispensable for diffusion in complex mixtures.     

Multicomponent diffusion of methyl ethyl ketone and toluene in polyisobutylene from vapor sorption FTIR-ATR spectroscopy

In this study, diffusion coefficients of toluene/methyl ethyl ketone (MEK) mixtures in polyisobutylene were measured at 50°C using vapor sorption FTIR-ATR (Fourier Transform Infrared Attenuated Total Reflectance) spectroscopy. For three mixture compositions, the diffusion coefficients were determined using a diffusion framework for ternary systems. The “crossterm” diffusion coefficient for MEK was found to be very small under the experimental conditions studied here, while that for toluene was found to increase with increasing MEK concentration. On the basis of this finding, a binary diffusion model was used to determine diffusion coefficients for MEK over a wide range of mixture compositions and the results compared well with those determined from pure MEK transport data. Relative transport rates during integral sorption experiments with mixtures were used to explain the results. © 1998 John Wiley & Sons, Inc. J Polym Sci B: Polym Phys 36 : 337–344, 1998     

Single component and binary diffusion of n-heptane and toluene in SBA-15 materials

In this work, the diffusion properties of single component n-heptane and toluene as well as their binary mixtures in two SBA-15 samples with different structural characteristics were studied by the standard Zero Length Column (ZLC) technique under three different concentration levels. A theoretical ZLC desorption model considering the Generalized Maxwell-Stefan (GMS) formulation was developed. Using the independently measured single component equilibrium and kinetic parameters, the model was able to reasonably predict experimental binary ZLC desorption curve for countercurrent diffusion of toluene in the presence of n-heptane. However, there was a significant deviation between model prediction results and experimental data for countercurrent desorption of n-heptane in the presence of toluene. The diffusion of n-heptane is reduced by the presence of toluene, regardless of the relative content of micropores in the intrawall pores, while that of toluene is virtually unaffected by the counter-diffusion of n-heptane. The observed phenomena cannot be addressed by the simple model considering the cross term diffusion effect. The structural property of material and the molecular characteristics of probe molecules were used to account for the difference in the behavior between n-heptane and toluene.     

Radioluminescence quenching of toluene scintillators by methyl methacrylate

It was established that singlet electronic excited state of toluene is quenched by MMA /but is not quenched by PMMA/. The value of quenching rate constant k_g=0.6×10⁹ l.mol^–1.s^–1 indicates that the quenching is a diffusion controlled process. It is assumed that the excitation energy of toluene sensitizes the polymerization process of MMA. The increase of radioluminescence intensity and quantum yield of excitation energy transfer is the result of diminishing the quantity of MMA in the solution during polymerization time.     

Application of mass spectrometer-inverse gas chromatography to study polymer-solvent diffusivity and solubility

The application of a mass spectrometer detector in capillary column inverse gas chromatography is shown to be a valuable tool in the measurement of diffusion and solubility in polymer-solvent systems. The component specific detector provides excellent results for binary polymer-solvent systems, but it is particularly valuable because it can be readily applied to multicomponent systems. Results for a number of infinitely dilute solvents in poly(vinyl acetate) (PVAc) are reported over a range of temperature from 60 to 150 degrees C. Results are also reported for finite concentrations of toluene and methanol in PVAc from 60 to 110 degrees C. Finally, the technique was applied to study the effect of finite concentrations of toluene on the diffusion coefficients of THF and cyclohexane in PVAc. The experimental data compare well with literature values for both infinite and finite concentrations, indicating that the experimental protocol described in this work is sound.     

A nuclear magnetic resonance study of toluene-polyisobutylene solutions. 2. Vrentas-Duda theory

The self-diffusion coefficients of toluene in polyisobutylene have been analyzed using the Vrentas-Duda free volume diffusion model. The diffusion coefficients were determined at different temperatures and concentrations, using the pulsed field gradient nuclear magnetic resonance technique. The data were satisfactorily described by the model and the size of the polymer jumping unit was extracted. Comparisons were made with the Fujita free volume theory and the Fujita free volume parameters were extracted from the Vrentas-Duda free volume parameters. From the diffusion data that now available, it can be concluded that for most polymers the jumping unit is about 1.5 times the polymer monomer molecular weight. The activation energy of the toluene diffusion in polyisobutylene is compared with the activation energies of other penetrants in the same polymer. The diffusion data presented in this work show that the energy per mole required to overcome the attractive forces which constrain a diffusing species to its neighbors should be considered to be zero, in order to be able to extract the free volume parameters (from viscosity and diffusion data) with an acceptable uncertainty. ©1995 John Wiley & Sons, Inc.     

Quenching platinum octaethylporphine phosphorescence in solution by poly(ferrocenylsilane)

We describe experiments that determine the quenching kinetics by poly(ferrocenylsilane) (PFS) for platinum octaethylporphine (PtOEP) phosphorescence in toluene solution. The phosphorescence quenching process was interpreted in terms of diffusion-controlled kinetics. Pulsed-gradient spin-echo nuclear magnetic resonance (PGSE NMR) and dynamic light scattering (DLS) were used to characterize the diffusion behavior of PFS and PtOEP in toluene solution. We found that the ferrocene group present in the repeat unit of polymer backbone is a good quencher for PtOEP phosphorescence. Quenching by the polymer involves the entire PFS polymer chain instead of individual ferrocene groups. The intrinsic quenching ability of PFS was found to be higher than that of a model compound, Bu-FS, that contains a single ferrocene group.     

Approaches to deal with the issue of plastic packages and the environment

Methods of treating the solid plastic waste are reviewed. The diffusion coefficients of toluene and benzyl alcohol in PET were determined from sorption experiments. For toluene, desorption (into water) experiments were also carried out and the diffusion coefficients were determined for various initial toluene concentrations in the polymer. The diffusion coefficients from the latter experiments were significantly lower than those determined from the sorption studies. In migration of toluene from the contaminated PET into water, a reduction of two orders of magnitude in the level of migration was achieved by sandwiching the contaminated PET between two layers of the virgin polymer. In another study, properties of Nylon 6/PE blends reprocessed at various shear rates were evaluated. The results showed that after minimum mixing of the blend obtained from a Nylon 6/PE laminate, the low oxygen permeability of the original film was preserved.     

Determining the permeability of organic solvents through PVC pipes using a direct SPME model

The permeability of aromatic hydrocarbons, i.e. BTEX and styrene, through PVC pipes was investigated using a 6-cm pipe-bottle model with direct solid-phase microextraction (SPME) sampling. It was found that an aromatic hydrocarbon with a large molecular size or low polarity may be less permeable through PVC pipes. In addition, the diffusion coefficients of BTEX and styrene in PVC pipes ranged from 4.87 to 7.64 × 10⁻⁸ cm²/s. According to the simulation results of a one-dimensional diffusion model, it is speculated that diffusion transport of benzene and toluene in PVC pipes may have non-Fickian behavior. The advantage of using the innovated test model is that SPME provides a nondestructive analytical means to monitor the concentrations of organic compounds in pipe-water. Therefore, the pipe-bottle model developed herein has potential applications in determining the resistance of polymeric pipes to permeation by solvents in the aqueous solution.     

The influence of solvent polarity and metalation on energy and electron transfer in porphyrin-phthalocyanine heterotrimers

Heteroporphyrin and -phthalocyanine arrays represent an attractive class of light harvesters and charge-separation systems exhibiting an easy route of synthesis and high chemical stability. In the present work, we report the results of photophysical investigations of two novel non-sandwich-type porphyrin-phthalocyanine heterotriads, in which two meso-tetraphenylporphyrin rings (H2TPP or ZnTPP) are linked to the central silicon atom of a silicon(IV) phthalocyanine core. It was found that the photophysical properties of the triads (H2Tr and ZnTr) in N,N-dimethylformamide (DMF) and toluene are strongly affected by two different types of interaction between the porphyrin (P) and the phthalocyanine (Pc) parts, namely excitation energy transfer (EET) and photoinduced charge transfer. The first process results in appearance of the Pc fluorescence when the P-part is initially excited, and plays a dominant role in fast depopulation of the first excited singlet state of the P moiety. If the first excited singlet state of the Pc-part is populated (either directly or via EET), it undergoes fast depopulation by hole transfer (HT) to the charge-separated (CS) state. In polar DMF, the CS state is the lowest excited state, and the charge recombination occurs directly to the ground state. Using transient absorption spectroscopy, the lifetime of the CS state was estimated to be 30 and 20 ps for H2Tr and ZnTr, respectively. In nonpolar toluene, the energy gap between the first excited singlet state of the Pc-part and the CS state is very small, and back HT occurs in both triads, resulting in appearance of "delayed fluorescence" of the Pc-part with a decay time similar to the lifetime of the CS state (190 and 280 ps for H2Tr and ZnTr, respectively). Since the energy of the CS state of ZnTr in toluene is lower than that of H2Tr, the probability of back HT for ZnTr is lower. This was clearly proved by decay-associated fluorescence spectral measurements.     

Diffusion Coefficients of Three Organic Solutes in Aqueous Sodium Dodecyl Sulfate Solutions

Tracer diffusion coefficients of phenol, toluene, and benzoic acid in aqueous solutions of sodium dodecyl sulfate (SDS) were measured by the Taylor dispersion technique. In addition, the viscosities and densities of the SDS solutions were measured. For phenol and toluene, the effect of micelle formation on the diffusion coefficient is pronounced. When the SDS concentration is below the critical micelle concentration (cmc), the diffusion coefficients are almost independent of the SDS concentration. However, above the cmc there is a rapid decrease in the diffusion coefficients, and the apparent diffusion coefficients of the two solutes are the weighted average of free solute diffusion and the micelle diffusion. A model is presented to describe the diffusion behavior of the two solutes in aqueous micellar solutions of SDS. The interaction between the two solutes and the micelles has been investigated and the fraction of each solute that is solubilized by the micelles is estimated from the measured apparent diffusion coefficient. For benzoic acid, the diffusion coefficient is dependent on the joint contribution of the benzoic acid molecules that are solubilized by the micelles as well as the corresponding benzoate ions. The effect of micelle formation on the diffusion coefficient of benzoic acid is not as pronounced as for phenol and toluene. Copyright 2000 Academic Press.     

Structure of microemulsions with gemini surfactant studied by solvatochromic probe and diffusion NMR

The structure of microemulsions prepared by the anionic gemini surfactant didodecyl diphenyl ether disulfonate (C12-DADS) was investigated by a solvatochromic probe and nuclear magnetic resonance (NMR) diffusion measurements. The NMR measurements indicate the presence of bicontinuous and oil-in-water microemulsions depending on microemulsion composition. The absorbance spectra of the solvatochromic probe, Nile red, indicate the solubilization of the probe in different sites, in agreement with the NMR findings. It was also found that the microemulsions were capable of dissolving the hydrophobic probe, Nile red, up to four times better than expected if it were simply dissolved in the toluene phase.     

用渗流理论计算高分子溶液中溶剂的自扩散系数

基于微观渗流理论建立了溶剂小分子在高分子溶液中的自扩散模型,并据此模型对不同温度和浓度下的聚苯乙烯(PS)-苯、PS-甲苯、PS-乙苯和PS-四氢呋喃4个体系中小分子的自扩散系数进行了关联,计算出在不同温度下溶剂分子扩散所需的临界浓度。结果表明,在PS玻璃化温度以下,本模型对于温度和浓度具有很好的适用性和关联精度。     

Determination of Activation Energy for the Diffusion of Fe<Superscript>3+</Superscript> Ions in Agar Gel Medium Containing Various Transition Metal Sulfates

The study of the diffusion of ferric ions in agar gel containing transition metal sulfates was carried out. The effect of gel concentration, electrolyte concentration and temperature on the diffusion of Fe³⁺ ions in various transition metal sulfates was studied with a view to verify Wang’s model of diffusion and the applicability of transition state theory to diffusion in a gel medium. The diffusion coefficients were measured using the zone diffusion technique. For a given concentration of electrolyte the activation energy (E) is found to decrease with an increase in the charge density of the cation of the supporting electrolyte and for a given system it is found to decrease with increasing electrolyte concentration in agreement with Wang’s model. This observation is explained on the basis of the distortion in the water structure caused by ions and agar molecules. At a given electrolyte concentration the magnitude of the Arrhenius parameters, E and D _o, is found to decrease with increasing gel concentration in agreement with the transition state theory of diffusion.     

Characterization of thermal diffusion in polymer solutions by thermal field-flow fractionation: Dependence on polymer and solvent parameters

The thermal diffusion coefficient D_T has been obtained for 17 polymer-solvent combinations, each of them spanning a range of polymer molecular weights, using thermal field-flow fractionation. The polymers examined include polystyrene, poly(alpha-methyl)styrene, polymethylmethacrylate, and polysioprene. The solvents include benzene, toluene, ethylbenzene, tetrahydrofuran, methylethylketone, ethylacetate, and cyclohexane. Although D_T was confirmed as essentially independent of polymer molecular weight, it was found to vary substantially with the chemical composition of polymer and solvent. The results were used to evaluate several thermal diffusion theories; the agreement with theory was generally found to be unsatisfactory. Attempts were then made to correlate the measured thermal diffusion coefficients with various physicochemical parameters of the polymers and solvent. A good correlation was found in which D_T increases with the thermal conductivity difference of the polymer and solvent and varies inversely with the activation energy of viscous flow of the solvent.     

离子液体BMIMBF4中对甲氧基甲苯的电化学氧化

以离子液体1-丁基-3-甲基咪唑四氟硼酸盐(BMIMBF4)为电解质,采用循环伏安法(CV)、计时电流法(CP)、原位傅里叶变换红外光谱(in situ FTIRS)法等手段研究了对甲氧基甲苯(p-MT)在铂电极上的电氧化行为.实验结果表明:对甲氧基甲苯在离子液体中的电化学氧化反应是受扩散控制的四电子不可逆过程,估算了其扩散系数D=3.4×10-7cm2.s-1,主要电氧化产物为茴香醛,加入适量的水或适当提高温度有利于电氧化反应向生成相应醛的方向进行.     

咪唑型离子液体对4–甲氧基甲苯的电氧化性能研究

通过紫外光谱研究了EMIMBF₄、BMIMBF₄、BMIMHSO₄和BMIMAc四种咪唑型离子液体(ILs)与4–甲氧基甲苯（p-MT）之间的相互作用,采用循环伏安法（CV）和计时电流法（CP）研究了p-MT在四种离子液体中的电化学氧化行为,探讨了咪唑型离子液体对反应的影响. 实验结果表明,在离子液体水溶液中p-MT的紫外光谱出现明显的红移,其溶剂分子和反应底物p-MT之间相互作用,这有利于p-MT产生相对稳定的激发态. p-MT在离子液体水溶液中的电氧化受扩散控制,且p-MT在EMIMBF₄水溶液中的扩散系数和电解产物的产率和选择性最佳.     

Diffusivity of asphaltene molecules by fluorescence correlation spectroscopy

Using fluorescence correlation spectroscopy (FCS) we measure the translational diffusion coefficient of asphaltene molecules in toluene at extremely low concentrations (0.03-3.0 mg/L): where aggregation does not occur. We find that the translational diffusion coefficient of asphaltene molecules in toluene is about 0.35 x 10(-5) cm(2)/s at room temperature. This diffusion coefficient corresponds to a hydrodynamic radius of approximately 1 nm. These data confirm previously estimated size from rotational diffusion studied using fluorescence depolarization. The implication of this concurrence is that asphaltene molecular structures are monomeric, not polymeric.