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The Vapor Pressures Op Alkali Halides by The

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The Vapor Pressures Op Alkali Halides by The THE VAPOR PRESSURES OP ALKALI HALIDES BY THE METHOD OP SURFACE IONIZATION DISSERTATION Presented in Partial Fulfillment of the Requirements for the Degree Doctor of Philosophy in the Graduate School of the Ohio State University by Henry Edwin Bridgers, B.S. The Ohio State University 1953 Approved by i TABLE OP CONTENTS Page List of Figures ii List of Tables iii I. Introduction 1 II. The Theory of Surface Ionization 5 III. Apparatus 23 IV. Experimental procedure 33 V. Results 50 VI. Discussion of Errors 65 VII. Summary of Results 68 Appendix 69 Bibliography 7 4 Acknowledgement 77 Autobiography 78 A 0 . 9 9 Q S ii LIST OP FIGURES Page 1. Schematic diagram of experimental tube 24 2. Detail of Knudsen cell and oven 26 3. Photograph of apparatus 28 4« Rough electrical schematic 30 5. Richardson plot for electron emission 35 0. Calculated- work function vs. filament temperature 36 7. Ion current vs. filament temperature (oil pump) 36 8. Ion current vs. filament temperature (Kl) 41 9. Ion current vs. filament temperature (Ebl) 41 10. Logarithm of ion current vs. residual pressure 51 11. Vapor pressure of KI (this research) 53 12. Vapor pressure of KI (previous measurements) 54 13. Vapor pressure of Rbl 56 iii LIST OP TABLES Page 1. Hecessary Work Function for 99^> Ionization 12 2. Degree of Conversion of Molecules to Ions 19 3* Variation of Electron Emission with Filament Temperature 38 4. Variation of Ion Current with Filament Temperature for Rbl Using Oil Pump 39 5» Variation of Ion Current with Filament Temperature for KI Using Mercury Pump 42 6. Variation of Ion Current with Filament Temperature for Rbl Using Mercury Pump 43 7. Variation of Ion Current with Pressure of Scattering Gas 50 8. Vapor Pressure of KI 52 9. Vapor Pressure of Rbl 55 10. Molecular Constants of KI and Rbl 58 11. Enthalpy and Entropy cf the Solid Salts 59 12. Heat of Sublimation of KI at the Absolute Zero (this research and data of Zimm and Mayer) 61 13* Heat of Sublimation of KI at the Absolute Zero (data of Cogin and Kimball and of Uiwa) 62 1 4 . Heat of Sublimation of Rbl at the Absolute Zero (this research and data of Niwa) 63 1 I. INTRODUCTION Prior to 1944 the vapor pressures of the solid alkali halides had been studied by three investigators. Deitz'*', employing an electromagnetic manometer, measured the vapor pressure of Csl 2 3 and of KC1; Niwa , using the method of Knudsen , measured the vapor pressures of LiCl, NaCl, KC1, RbCl, CsCl, NaF, KF, NaBr, KBr, CsBr, lLlf and Rbl over a limited temperature interval; Mayer 4 and Wintner , who also employed Knudsen's method, determined the vapor pressures of NaCl, KC1, RbCl, NaBr, KBr, and RbBr. 5 Langmuir and Kingdon observed that a tungsten filament heated in the presence of cesium vapor produced cesium ions which could be collected by a suitable electrode. If the filament temperature is raised above a critical value which depends on the pressure of cesium vapor, they found that the ion current is practically independent of the filament temperature. These authors concluded that above this critical temperature every cesium atom which struck the filament was ionized. These same phenomena were observed by Killian^ for potassium and rubidium 7 and by Morgulis for sodium on an oxygen-coated tungsten filament. Since every atom which strikes the filament is ionized, it is possible to calculate from the observed ion currents the vapor pressures of the alkali metals. The theory of thermal ioniza­ tion, whicia was first presented by Saha in a series of three papers^’^* ^ and amended for this particular application by 5 I"1 Langmuir , will be developed in the next section. Taylor *■, investigating molecular beams of the alkali metals, used this surface ionization on tungsten as a detector. 12 Eodebush and Henry observed that positive ions of the alkali metals are produced when a beam of alkali halide molecules falls on a hot tungsten filament. They concluded that the alkali halide molecule is first dissociated on the incandescent surface and the alkali metal atom produced is subsequently ionized. Copley and Phipps‘S and Hendricks‘S continued the investigation of the surface ionization of alkali halide molecules. They found that if the filament is cleaned by flashing to a high temperature in a good vacuum, free of oxygen, the ion current increases as the filament temperature is lowered until a critical value of the temperature is reached where the current decreases rapidly to zero. If the filament is coated with a film of oxygen, the ion current is practically independent of the filament temperature at temperatures above the same lower critical value. If the temperature is raised above 1800 °K, where the oxygen layer begins to strip off, the ion current is observed to decrease gradually. In this latter case of an oxygen-coated tungsten filament, a plot of ion current versus filament temperature shows a steep increase in ion current, at the critical temperature, to a maximum value which persists over a broad plateau. The plateau is followed by a gradual decrease of ion current upon loss of the oxygen coating. 5 This behavior is analogous to that reported by Langmuir for cesium 3 6 and by Killian for potassium and rubidium on an oxygen-coated filament. In the region of the broad plateau Copley‘S concluded that, not only does every atom of alkali metal produced on the filament surface ionize, but also the extent of dissociation of the alkali halide molecule is effectively complete. When the ion current shows temperature dependence, it is concluded that the work function of the metal is too low for complete ionization of the metal atoms produced. The observations of Copley et a l . ^ ’^ give curves similar to those shown in Figure 7» Zimm and Mayer15 combined the method of Knudsen 3 and the phenomena observed by Copley^ to measure the vapor pressures of Had, KOI, KBr, and KI. A suitably collimated beam of alkali halide molecules from a Knudsen oven was allowed to impinge on a tungsten filament whose work function had been increased by adsorption of an oxygen film. The ions produced by dissociation and ionization on the filament wefce collected by a metal cylinder arranged coaxially with the filament and measured by a suitable galvanometer. If the filament conditions, i.e. its temperature and work function, were so adjusted that the ion current was in the region of the afore-mentioned plateau, then every alkali halide molecule which struck the filament produced a positive ion. From the geometry of the apparatus, the ion current, and the Knudsen cell temperature, the vapor jaessure of the alkali halide at the temperature of the Knudsen cell could be calculated from gas kinetics. Cogin and Kimball'*'*’ employed this method to measure the vapor pressures of CsCl, NaBr, CsBr, Nal, KI, and Csl. This is an elegant method for the measurement of vapor pressures hut unfortunately it is limited to alkali metal compounds having sufficiently low dissociation energies and probably not including compounds of lithium which has a rather high ioniza­ tion potential (5*36 v). The method is very sensitive, thus permitting the measurement of low vapor pressures with relative ease. The method affords instantaneous measurements as compared with the conventional Knudsen method, where a single measurement must be made over a prolonged period, during which the cell temperature must remain constant. The rapidity of the method permits more measurements with a given sample and therefore greater reliability. It is possible to measure the vapor pressure at a given temperature several times after repeatedly heating and cooling the charge. In this fashion a guarantee of the constancy of composition of the sample is obtained. In the present investigation the vapor pressures of KI and Rbl have been determined by the method of surface ionization over the temperature range TOO - $00 °K. II. THE THEORY OP SURFACE IONIZATION Consider the ionization of a metal atom, M, effected thermally on an incandescent tungsten filament. Following Langmuir 5 17 and 18 Reimann let us assume that in close proximity to the filament surface, i.e. at the reaction scene, neutral atoms and ions as well as electrons are in equilibrium with the filament and with each other in accordance with the following equation, M = M + + e(in metal). (l) This assumption applies even in the presence of an electron retarding or ion collecting field. ¥/e shall further assume that the accommodation coefficients of metal atoms, metal ions, and electrons are all unity. This has been shown to be the case for cesium on tungsten* 19 . The equilibrium constant for reaction (l) is given by Kp - (PM+)(Pe ^ (PM) “ e*P(-4F°/RTf) (2 ) where the P's refer to the partial pressures of the reactant and products at the temperature of the filament, ^F° is the standard free energy change of the reaction, R is the gas constant, and T^ is the filament temperature in degrees Kelvin, with the above assumption of unit accommodation coefficient and by application of gas kinetics it is possible to relate the pressure of electrons to the electron current density, as whore ig is the electron current density in amperes per cm , M is the molecular weight of electrons in grams per mole, R is the gas constant in ergs per mole per degree, H is the filament temperature in degrees Kelvin, F is the Faraday constant in coulombs per mole, and P 6 is the partial pressure of electrons 2 in dynes per cm . The current density of electrons is given by 18 20 21 the Richardson-Dushman equation ’ ’ as ie = U-r)AoTf2exp(-0o/kTf), (4) in which r is the reflection coefficient, is the work function, and A q , the thermionic emission coefficient, has the theoretical value (41) A O = (41tta 6k2e/h3) s 120.1 amp/cm2/deg2.
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