Partial pressure analysis

M. J. Drinkwine and D. Lichtman, Partial Pressure Analysis, American Vacuum Society, New York, 1977. 

Partial pressure analysis using a mass spectrometer or the pressure rise method may be used to differentiate between these two causes. Since the pressure rise method will only prove the presence of a leak without Indicating Its location In the apparatus. It Is advisable to use a helium leak detector with which leaks can, in general, also be located much more quickly. 

Because the system likely is nonisothermal, the analysis of a closed-desiccant system requites knowledge of the temperature of the desiccant as well as the dew point (ice point) or water concentration (partial pressure) specification. Indeed, the whole system may undergo periodic temperature transients that may compHcate the analysis. Eor example, in dual-pane windows the desiccant temperature is approximately the average of the indoor and outdoor temperatures after a night of cooling. However, after a day in the sun, the desiccant temperature becomes much warmer than the outdoor temperature. When the sun sets, the outdoor pane cools quickly while the desiccant is still quite warm. The appropriate desiccant for such an appHcation must have sufficient water capacity and produce satisfactory dew points at the highest temperatures experienced by the desiccant. 

To make the actual analysis simple and fast, a large amount of precomputed information is utilized. By using library spectra of pure molecular gases together with a special mathematical multicomponent analysis, it is possible to calculate the partial pressures of the gases in a gas mixture. 

Carbon dioxide devices were originally developed by Severinghaus and Bradley (59) to measure the partial pressure of carbon dioxide in blood. This electrode, still in use today (in various automated systems for blood gas analysis), consists of an ordinary glass pH electrode covered by a carbon dioxide membrane, usually silicone, with an electrolyte (sodium bicarbonate-sodium chloride) solution entrapped between them (Figure 6-17). When carbon dioxide from the outer sample diffuses through the semipermeable membrane, it lowers the pH of the inner solution ... 

It is important to consider the complex nature of the vapors in both oxide systems. Any analysis which considers only the dioxide partial pressures, or approximates the total pressures as a dioxide pressure, will be seriously in error. 

Figure 1 Is a flow sheet showing some significant aspects of the Iterative analysis. The first step In the program Is to Input data for about 50 physical, chemical and kinetic properties of the reactants. Each loop of this analysis Is conducted at a specified solution temperature T K. Some of the variables computed In each loop are the monomer conversion, polymer concentration, monomer and polymer volume fractions, effective polymer molecular weight, cumulative number average molecular weight, cumulative weight average molecular weight, solution viscosity, polymerization rate, ratio of polymerization rates between the current and previous steps, the total pressure and the partial pressures of the monomer, the solvent, and the nitrogen.

This study presents kinetic data obtained with a microreactor set-up both at atmospheric pressure and at high pressures up to 50 bar as a function of temperature and of the partial pressures from which power-law expressions and apparent activation energies are derived. An additional microreactor set-up equipped with a calibrated mass spectrometer was used for the isotopic exchange reaction (DER) N2 + N2 = 2 N2 and the transient kinetic experiments. The transient experiments comprised the temperature-programmed desorption (TPD) of N2 and H2. Furthermore, the interaction of N2 with Ru surfaces was monitored by means of temperature-programmed adsorption (TPA) using a dilute mixture of N2 in He. The kinetic data set is intended to serve as basis for a detailed microkinetic analysis of NH3 synthesis kinetics [10] following the concepts by Dumesic et al. [11]. 

Another point that one has to observe from analysis of Figure 10, is that despite the different precursor atmospheres, and consequently different N precursor partial pressures in the deposition, there is a coincidence of the deposition rate behavior upon nitrogen content (for mixtures other than C2H-N2). This points to a strong dependence of growth kinetics with nitrogen content. 

Here Pe and pH are the partial pressures of ethane and hydrogen, respectively, and the parameter a is equal to (6 — x)/2. This analysis was subsequently generalized to include cases in which equilibrium is not established between adsorbed C2H and gas phase ethane (16). Provided that surface coverage by adsorbed species is low, and that equilibrium is maintained between the surface species C2H5 and C2Hx, and H2 in the gas phase, a kinetic analysis leads to the rate expression... 

For a first chemical model, we calculate the distribution of species in surface seawater, a problem first undertaken by Garrels and Thompson (1962 see also Thompson, 1992). We base our calculation on the major element composition of seawater (Table 6.2), as determined by chemical analysis. To set pH, we assume equilibrium with CO2 in the atmosphere (Table 6.3). Since the program will determine the HCOJ and water activities, setting the CO2 fugacity (about equal to partial pressure) fixes pH according to the reaction,... 

FIGURE 74-1. Analysis of arterial blood gases. (HC03, bicarbonate Pco2, partial pressure of carbon dioxide.)... 

---