Langmuir Sorption Capacity Research Articles

O2 and N2 gas permselectivity of alternating copoly(vinylidene cyanide–vinyl acetate)

AbstractThe sorption and permeation of oxygen and nitrogen in and through alternating copoly(vinylidene cyanide–vinyl acetate) [copoly(VDCN–VAc)] (Tg = 176°C) membranes annealed for different periods just below Tg, 160°C, were investigated over the pressure range from 100 to 1000 cmHg. The dual‐mode sorption and mobility models were used to analyze the results. A sub‐Tg annealing of copoly(VDCN–VAc) caused a slight decrease in the amount of sorption in the membranes. This decrease in the amount of oxygen and nitrogen sorption can be attributed to a decrease in the Langmuir sorption capacity term, C′H, with increasing sub‐Tg annealing period. The densification of copoly(VDCN–VAc) membranes caused simultaneously by the annealing remarkably reduced diffusion coefficients for both gases. The reduction in diffusion coefficients of Langmuir mode, DH, for both gases was found to be larger than that of Henry's law mode, DD. Furthermore, permselectivity of oxygen to nitrogen, the ratio of permeability coefficient of oxygen to nitrogen (PO2/PN2), reached to 11.8 for the copoly(VDCN–VAc) annealed for 30 h. Evidently the reduction of DH and DD for nitrogen with increasing annealing period was much larger than that for oxygen.

Gas sorption and transport in substituted polycarbonates

AbstractThe effects of molecular structure manipulation of polycarbonates on sorption and transport of various gases were studied using tetramethyl, tetrachloro, and tetrabromo substitutions onto the aromatic rings of bisphenol A polycarbonate. Solubility and permeability measurements were made at 35°C over the pressure range of 1–20 atm for a variety of gases, namely CO2, CH4, O2, N2, and He. A threefold to fourfold increase in permeability was caused by the tetramethyl substitution, whereas the tetrachloro and tetrabromo substitutions reduced the permeability relative to the tetramethyl substitution. Lower activation energies for transport were found for the tetramethyl polycarbonate relative to the unsubstituted polycarbonate. Permeability coefficients were factored into solubility and diffusion coefficients. Sorption levels increased for all substitutions, but among the substituted polymers the levels remain practically the same. Solubility data were analyzed in terms of the dual sorption model. The Henry's law solubility coefficients obtained from this analysis were found to be consistent with a predictive equation developed for rubbery polymers. The usual correlation for predicting the Langmuir sorption capacity of the model overestimates the values for the substituted polycarbonates, and a proposal for the cause of this is offered. Thermal expansion of these polymers was measured using dilatometry, and the results are used in the interpretation of the sorption data. Diffusion phenomena are explained by segmental mobility and free volume considerations. The effects of CO2 exposure history on sorption and transport were also investigated.

Observations concerning the temperature dependence of the langmuir sorption capacity of glassy polymers

Observations concerning the temperature dependence of the langmuir sorption capacity of glassy polymers

High-pressure sorption of carbon dioxide in solvent-cast poly(methyl methacrylate) and poly(ethyl methacrylate) films

Carbon dioxide sorption isotherms in poly(methyl methacrylate) (PMMA) and poly(ethyl methacrylate) (PEMA) are reported for pressures up to 20 atm. Temperatures between 35 and 80°C were studied for PMMA and temperatures between 30 and 55°C were studied for PEMA. Typical dual mode sorption isotherms concave to the pressure axis were observed in all cases. The measured Langmuir sorption capacities of both polymers extrapolated to zero at the glass transition (Tg) consistent with the behavior of other glassy polymer/gas systems. Sorption enthalpies for CO2 in the Henry's law mode for PMMA and PEMA are in the same range (−2 to −4 kcal/mole) as has been reported for a variety of other glassy polymers such as poly(ethylene terephthalate), polycarbonate, and polyacrylonitrile. Some of the data suggest that postcasting treatment of the PEMA films left a small amount of residual solvent in the film. the presence of the trace residual solvent during quenching from the rubbery to the glassy state after annealing appears to cause a dilation of the Langmuir capacity and an alteration in the apparent Langmuir affinity constant of the PEMA film. These results suggest the possibility of tailoring physical properties of glassy polymers such as sorptivity, permeability, impact strength, and craze resistance by doping small amounts of selected residuals into polymers prior to quenching to the glassy state from the rubbery state.

COLLIDINE SORPTION ON A SILT LOAM SOIL AND A SPENT SHALE

A laboratory study was made to assess the sorption of collidine on a Ritzville silt loam soil and a retorted oil shale from the Laramie Energy Research Center. Collidine sorption was found to fit a Langmuir isotherm type sorption on both the soil and spent shale systems. In the case of the soil, two Langmuir type equations were resolved from the data, though only a single equation was resolved from the retorted shale data. Langmuir sorption capacity and bonding term parameters were determined for both systems by linear regression analysis.