Rydberg gas theory of a glow discharge plasma: II. Electrode kinetics (probe theory) and the thermal rate constant for Symmetrical charge transfer involving Rydberg atoms of Ar.

A steady state chemical kinetic model is developed to describe the conduction of electrical current between two probes, of relatively large surface area, immersed in a fast flowing plasma by the mechanism of charge transfer through a gas of Rydberg atoms. It correctly predicts the shape of current-voltage profiles which are similar to those of Langmuir, or floating double probe measurements. The difference is that the plateau current at the probe reflects the transport limited ion current at the cathodic electrode, even when the probe is being scanned in the anodic region. The sharp gradient leading up to the plateau of the I-V curve is associated with the field dependence of the efficiency of Rydberg atom ionisation, not the electron temperature. This approach gives a good qualitative explanation of experimental behaviour over a wide range of probe bias voltages and includes the occurrence of electron impact ionisation at the anode. It also gives a value for the thermal rate coefficient of symmetrical charge transfer between Rydberg atoms of Ar (8.2 x 10(-7) molecule(-1) cm(3) s(-1), at 313 K; plasma density approximately = 10(10) atoms cm(-3), total pressure = 2.7 mbar).

Rydberg gas theory of a glow discharge plasma: I. Application to the electrical behaviour of a fast flowing glow discharge plasma.

Current-voltage (I-V) curves have been measured, independent of the main discharge, for electricity passing through the steady state fast flowing 'afterglow' plasma of a low power dc glow discharge in Ar. Voltage profiles along the axial line of conduction have been mapped using fixed probes and potentiometry, and the mass spectra of cations emerging from the downstream sampling Cone, also acting as a probe anode, were recorded simultaneously. Floating double probe experiments were also carried out. The electrical behavior is consistent with the well established I-V characteristics of such discharges, but does not comply with classical plasma theory predictions. The plasma decays along the line of conduction, with a lifetime of approximately 1 ms, despite carrying a steady state current, and its potential is below that of the large surface area anode voltage; a situation which cannot exist in the presence of a conventional free ion-electron plasma, unless the electron temperature is super cold. Currents, large by comparison with the main discharge current, and independent of it, are induced to flow through the downstream plasma, from the Anode (acting as a cathode) to the anodic ion exit Cone, induced by electron impact ionisation at the anode, but without necessarily increasing the plasma density. It appears to be conducted by direct charge transfer between a part of the anode surface (acting as cathode to the auxiliary circuit) and the plasma, without secondary electron emission or heating, which suggests the direct involvement of Rydberg atom intermediates. The reaction energy defect (= the work function of the electrode surface) fits with the plasma potential threshold observed for the cathodic reaction to occur. A true free ion-electron plasma is readily detected by the observation of cations at the anode surface, when induced at the downstream anode, at high bias voltages, by the electron impact ionisation in the boundary region. In contrast to the classical model, the complex electrical (and mass spectrometric) behaviour fits qualitatively, but can be understood well, with the Rydberg gas model described in papers II and III (R. S. Mason, and R. S. Mason and P. Douglas, PCCP, 2010, DOI: 10.1039/b918081h and b918083d) over a wide range of probe bias voltages. The full cycle of behavior is then described for the development of a true secondary discharge within the downstream plasma.

Rydberg gas theory of a glow discharge plasma: III. Formation, occupied state distributions, free energy, and kinetic control.

It has been suggested that Rydberg gas atoms are involved in conducting electricity through a steady state flowing afterglow (FAG) discharge plasma (R. S. Mason, D. J. Mitchell and P. M. Dickinson, Phys. Chem. Chem. Phys., 2010, DOI: ). From known properties of Rydberg atoms, a statistical model is developed here to find the distribution of levels (principal quantum number n) occupied in such a hypothetical Rydberg gas. It behaves non-ideally at positive column plasma densities, predicting 30 < n < 150, peaking at n approximately = 85. These values depend on assumptions concerning the power of n dependency of 'pressure ionization' and the free charge density. The occupied states are very long-lived and almost completely separated from the low n states by the low probability of intermediate levels. The effects of Rydberg gas (N(R)) and free charge densities are examined. The gas can exist in a deep free energy well (> 120 kJ mol(-1) below ionisation level when 10(10) < or = N(R) < or = 10(11) atoms cm(-3)) but this is approximately 11 kJ mol(-1) higher than that of the equivalent free ion-electron gas; therefore if it exists in preference to the classical form of the plasma, it is controlled by kinetic factors. A mechanism is suggested by which this could occur. Thus, whilst ionization by high energy electron impact occurs at the Cathode Fall-Negative Glow (NG) boundary as usual, excitation of Rydberg atoms becomes more probable, by electrons slowed by collision and deceleration at the opposite NG-Positive Column (PC) plasma boundary. The atoms become stabilized after passing into the PC, by collisionally induced (nlm) mixing of states and the removal of free charge by charge transfer (and hence the passage of electric current through the Rydberg gas). The coupling of Rydberg states with the ionization continuum is poor; therefore, if the rate of their charge transfer is greater than that of their ionization, the Rydberg gas will remain relatively charge free and hence stable when it is conducting a current. When applied to the FAG plasma, the model provides a self-consistent interpretive framework for all its electrical, mass spectrometric and chemical behaviour. The effect on the optical spectroscopy of these plasmas is considered briefly.

A cryogenic machine for selective recovery of xenon from breathing system waste gases.

BACKGROUND: Xenon has many characteristics that make it very attractive as an anesthetic and therapeutic drug. Unfortunately, the supply of xenon is fixed, and therefore reclamation and recovery from even the most efficient breathing circuits is desirable. We built and evaluated a cryogenic device to recover xenon from waste anesthetic gases. METHODS: Xenon was selectively frozen to -139.2 degrees C from test gas mixtures at ambient pressure (STP). The machine ran on standard 240 V 13 A electrical current without refrigerants that required replenishing, e.g., liquid nitrogen. A wide range of xenon/oxygen mixtures were processed over a range of freezing chamber temperatures. Efflux gas and thawed reclaimed xenon were collected separately. Xenon purity and yield (fraction recovered) were measured and calculated on each occasion. RESULTS: Gas was processed at 300 mL/min, and the operating temperature was -139.2 (0.096) degrees C [Mean (sd)]. Purity and yield were >90% and >70% for gas mixtures containing > or =20% xenon, increasing to >95% and >85%, respectively, with an input gas xenon fraction > or =40%. Efficiency improved linearly with reducing temperature. CONCLUSIONS: Xenon of high purity (>90%) and yield (>70%) for such a machine was recovered from all gas mixtures containing > or =20% xenon. The operating temperature of the freezing chamber is a major influence on the efficiency of recovery.

Organic mass spectrometry and control of fragmentation using a fast flow glow discharge ion source.

Representative organic vapors have been introduced into the flowing afterglow of a low power (<5 W) dc-glow discharge, coupled to a quadrupole mass spectrometer. When a positive bias was applied to the ion sampling orifice, the very surprising result was that molecular mass spectra were obtained with a high sensitivity. When a negative bias was applied to the ion sampling orifice, fragmentation of the analyte was observed with an increase in the extent of ion dissociation as the voltage was increased. The breakdown pattern is compound-specific and would be useful in confirming the identity of an unknown sample. When combined with chromatographic separation, the FFGD-MS technique could be used for chemical speciation studies at the sub-picogram level.

Positive-column plasma studied by fast-flow glow discharge mass spectrometry: could it be a "Rydberg gas?".

Ions created from the fast-flowing positive column plasma of a glow discharge were monitored using a high voltage magnetic sector mass spectrometer. Since the field gradient and sheath potentials created by the plasma inside the source opposed cation transfer, it is inferred that the ions detected were the field-ionized Rydberg species. This is supported by the mass spectral changes which occurred when a negative bias was applied to the sampling aperture and by the contrasting behavior when attached to a quadrupole analyzer. Reaction with H2 (titrated into the flowing plasma) quenched not only the ionization of discharge gas Rydberg atoms but also the passage of electric current through the plasma, without significant changes to the field and sheath potentials. Few "free" ions were present and the lifetimes of the Rydberg atoms detected were much longer than seen in lower pressure experiments, indicating additional stabilization in the plasma environment. The observations support the model of the flowing plasma, given previously [R. S. Mason, P. D. Miller, and I. P. Mortimer, Phys. Rev. E 55, 7462 (1997)] as mainly a neutral Rydberg atom gas, rather than a conventional ion-electron plasma.