Gas Permeability Constants

TABLE 10.5 Gas Permeability Constants (10 P) at 25°C for Polymers and Rubbers The gas permeability constant P is defined as... 

The gas permeability constant is the amount of gas expressed in cubic centimeters passed in 1 s through a 1-cm area of film when the pressure across a film thickness of 1 cm is 1 cmHg and the temperature is 25°C. All tabulated values are multiplied by 10 and are in units of seconds" (centimeters of Hg) k Other temperatures are indicated by exponents and are expressed in degrees Celsius. 

An extensive new Section 10 is devoted to polymers, rubbers, fats, oils, and waxes. A discussion of polymers and rubbers is followed by the formulas and key properties of plastic materials. Eor each member and type of the plastic families there is a tabulation of their physical, electrical, mechanical, and thermal properties and characteristics. A similar treatment is accorded the various types of rubber materials. Chemical resistance and gas permeability constants are also given for rubbers and plastics. The section concludes with various constants of fats, oils, and waxes. 

The gas permeability constants (P) are generally expressed by the amount of the gas at standard temperature and pressure normalized for the thickness, membrane area, time and differential pressure of gas as in the following equation ... 

Fluorinated poly(arylene edier)s are of special interest because of their low surface energy, remarkably low water absorption, and low dielectric constants. The bulk—CF3 group also serves to increase the free volume of the polymer, thereby improving various properties of polymers, including gas permeabilities and electrical insulating properties. The 6F group in the polymer backbone enhances polymer solubility (commonly referred to as the fluorine effect ) without forfeiture of die thermal stability. It also increases die glass transition temperature with concomitant decrease of crystallinity. 

Transport properties have been studied before and after Si deposition using a rig similar to the one for catalytic testings (Figure 2). Pure gas permeabilities (H2, He, N2, normal and isobutane) were studied by measuring the flux passing though the membrane as a function of temperature and pressure for a constant transmembrane differential pressure (no sweep gas). 

The concept of the pH electrode has been extended to include other ions as well. Considerable research has gone into the development of these ion-selective electrodes over the years, especially in studying the composition of the membrane that separates the internal solution from the analyte solution. The internal solution must contain a constant concentration of the analyte ion, as with the pH electrode. Today we utilize electrodes with 1) glass membranes of varying compositions, 2) crystalline membranes, 3) liquid membranes, and 4) gas-permeable membranes. In each case, the interior of the electrode has a silver-silver chloride wire immersed in a solution of the analyte ion. 

When the crystallinity of polyethylenes is increased, the gas permeability through the film decreases. The factors involved are the tortuosity of the gas path through the amorphous phase, and the effect of the crystals in restricting the mobility of the amorphous polymer chains (chain immobilisation factor). The logarithm of the permeability of nitrogen, argon and carbon dioxide decreased almost linearly with increased crystallinity of PE, with the ratio of the gas values remaining almost constant for a particular PE. 

Use an ammonia electrode (Orion Model 95-10, Beckman Model 39565 or equivalent) along with a readout device, such as a pH meter with expanded millivolt scale between -700 mV and +700 mV or a specific ion meter. The electrode assembly consists of a sensor glass electrode and a reference electrode mounted behind a hydrophobic gas-permeable membrane. The membrane separates the aqueous sample from an ammonium chloride internal solution. Before analysis, the sample is treated with caustic soda to convert any NH4+ ion present in the sample into NH3. The dissolved NH3 in the sample diffuses through the membrane until the partial pressure of NH3 in the sample becomes equal to that in the internal solution. The partial pressure of ammonia is proportional to its concentration in the sample. The diffusion of NH3 into the internal solution increases its pH, which is measured by a pH electrode. The chloride level in the internal standard solution remains constant. It is sensed by a chloride ion-selective electrode which serves as the reference electrode. 

The area is an important surface parameter for catalytic studies. It is needed to evaluate the rate constant of the surface reaction from the kinetics as well as to allow a fair comparison to be made of the effectiveness of different catalysts. Areas are commonly determined by nitrogen or krypton gas adsorption interpreted by the Brunauer-Emmett Teller (BET) isotherm [30, 32], A number of other methods has been proposed and utilised including microscopy, isotopic exchange, chromatography, gas permeability, adsorption from solution, and negative adsorption (desorption) of co-ions [30, 33]. 

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