High-temperature mass spectrometry - Vaporization of group 4-B metal carbides

The high temperature vaporization of the metal-carbon systems TiC, ZrC, HfC, and ThC was studied by the Knudsen effusion - mass spectrometric method. For each system the metal dicarbide and tetracarbide molecular species were identified in the gas phase. Relative ion currents of the carbides and metals were measured as a function of temperature. Second- and third-law methods were used to determine enthalpies. Maximum values were established for the dissociation energies of the metal monocarbide molecules TiC, ZrC, HfC, and ThC. Thermodynamic functions used in the calculations are discussed in terms of assumed molecular structures and electronic contributions to the partition functions. The trends shown by the dissociation energies of the carbides of Group 4B are compared with those of neighboring groups and discussed in relation to the corresponding oxides and chemical bonding. The high temperature molecular beam inlet system and double focusing mass spectrometer are described

Thermodynamics and kinetics of the sulfation of porous calcium silicate

The sulfation of plasma sprayed calcium silicate in flowing SO2/air mixtures at 900 and 1000 C was investigated thermogravimetrically. Reaction products were analyzed using electron microprobe and X-ray diffraction analysis techniques, and results were compared with thermodynamic predictions. The percentage, by volume, of SO2 in air was varied between 0.036 and 10 percent. At 10 percent SO2 the weight gain curve displays a concave downward shoulder early in the sulfation process. An analytical model was developed which treats the initial process as one which decays exponentially with increasing time and the subsequent process as one which decays exponentially with increasing weight gain. At lower SO2 levels the initial rate is controlled by the reactant flow rate. At 1100 C and 0.036 percent SO2 there is no reaction, in agreement with thermodynamic predictions

The role of NaCl in flame chemistry, in the deposition process, and in its reactions with protective oxides as related to hot corrosion

Sodium chloride is believed to be the primary source of turbine engine contamination that contributes to hot corrosion. The behavior of NaCl-containing aerosols ingested with turbine intake air is very complex; some of the NaCl may vaporize during combustion while some may remain as particulates. The NaCl can lead to Na2SO4 formation by several possible routes or it can contribute to corrosion directly. Hydrogen or oxygen atom reaction with NaCl(c) was shown to result in the release of Na(g). Gaseous NaCl in flames can be partially converted to gaseous Na2SO4 by homogeneous reactions. The remaining gaseous NaCl and other Na-containing molecules can act as sodium carriers for condensate deposition of Na2SO4 on cool surfaces. A frozen boundary layer theory was developed to predict the rates of deposition. The condensed phase NaCl can be converted directly to condensed Na2SO4 by reaction with sulfur oxides and O2. Reaction of gaseous NaCl with Cr2O3 results in the vapor phase transport of chromium by the formation of complex Cr-containing gaseous molecules. Similar gaseous complexes are formed with molybdenum. The presence of gaseous NaCl was shown to affect the oxidation kinetics of Ni-Cr alloys. It also causes changes in the surface morphology of Al2O3 scales formed on Al-containing alloys

Computer programs for the interpretation of low resolution mass spectra: Program for calculation of molecular isotopic distribution and program for assignment of molecular formulas

Two FORTRAN computer programs for the interpretation of low resolution mass spectra were prepared and tested. One is for the calculation of the molecular isotopic distribution of any species from stored elemental distributions. The program requires only the input of the molecular formula and was designed for compatability with any computer system. The other program is for the determination of all possible combinations of atoms (and radicals) which may form an ion having a particular integer mass. It also uses a simplified input scheme and was designed for compatability with any system

The dissociation energy of gaseous titanium mononitride

Dissociation energy of gaseous titanium nitrid

Dissociation energies of some high temperature molecules containing aluminum

The Knudsen cell mass spectrometric method has been used to investigate the gaseous molecules Al2, AlSi,AlSiO, AlC2, Al2C2, and AlAuC2. Special attention was given to the experimental considerations and techniques needed to identify and to measure ion intensities for very low abundance molecular species. Second- and third-law procedures were used to obtain reaction enthalpies for pressure calibration independent and isomolecular exchange reactions. Dissociation energies for the molecules were derived from the measured ion intensities, free-energy functions obtained from estimated molecular constants, and auxiliary thermodynamic data. The bonding and stability of these aluminum containing molecules are compared with other similar species

Mass spectrometric determination of the dissociation energies of titanium dicarbide and titanium tetracarbide

Mass spectrometric determination of dissociation energies of titanium dicarbide and titanium tetracarbid

Reactions of chromium with gaseous NaCl in an oxygen environment

Target collection techniques and high pressure mass spectrometric sampling have been used to study the formation of volatile chromium-containing species in the reaction of Cr2O3 with O2 and NaCl gases. Experiments were performed at atmospheric pressure as a function of chromium temperature, oxygen pressure, and NaCl gas concentration. The major chromium-containing vapor species were found to be (NaCl)x CrO3 gas, with x = 1,2, and 3, which are products of heterogeneous reactions on the surface. The kinetics indicate first order dependence on oxygen and sodium chloride pressures

Reactions of NaCl with Gaseous SO3, SO2, and O2

Hot corrosion of gas turbine engine components involves deposits of Na2SO4 which are produced by reactions between NaCl and oxides of sulfur. For the present investigation, NaCl single crystals were exposed at 100 to 850 C to gaseous mixtures of SO3, SO2, and O2. The products formed during this exposure depend, primarily, on the temperatures. The four product films were: NaCl-SO3; Na2S2O7; Na2SO4; and NaCl-Na2SO4. The kinetics of the reactions were measured

Oxidative vaporization kinetics of chromium (III) oxide in oxygen from 1270 to 1570 K

Rates of oxidative vaporization of Cr2O3 on preoxidized resistively heated chromium were determined in flowing oxygen at 0.115 torr for temperatures from 1270 to 1570 K. Reaction controlled rates were obtained from experimental rates by a gold calibration technique. These rates were shown to agree with those predicted by thermochemical analysis. The activation energy obtained for the oxidative vaporation reaction corresponded numerically with the thermochemical enthalpy of the reaction. A theoretical equation is given for calculating the rate from thermodynamic data by using boundary layer theory