First-stage enrichment in CO2-laser-induced13C separation by a two-stage IRMPD process: IRMPD of CHClF2/Br2 mixtures

We have been studying the practical CO₂-laser-induced¹³C separation by a two-stage IRMPD process. The IRMPD of natural CHClF₂ in the presence of Br₂ mainly produced CBr₂F₂, which was found to be highly enriched with¹³C. The yield and¹³C-atom fraction of CBr₂F₂ were examined as functions of pulse number, laser line, laser fluence, total pressure, and Br₂ pressure using a CO₂ TEA laser with an output less than 1 J pulse^–1 in order to optimize experimental conditions for¹³C separation. For example, we obtained CBr₂F₂ at a¹³C concentration of 55% in the irradiation of the mixture of 100-Torr CHClF₂ and 10-Torr Br₂ with the laser radiation at a wavenumber of 1045.02 cm^–1 and at a fluence of 3.4 J cm^–2. The mechanism for the IRMPD is discussed on the basis of observed results. Using 8-J pulses, we were able to obtain 1.9×10^–4 g of¹³C-enriched CBr₂F₂ (¹³C-atom fraction, 47%) per pulse under selected conditions. It is possible to produce 90% or higher¹³C by the second-stage IRMPD of the CBr₂F₂ in the presence of oxygen.     

13C-selective IRMPD of CBr2F2/Cl2 and CCl2F2/Br2 systems

The CO₂ TEA laser irradiation of CBr₂F₂ in the presence of Cl₂ yielded ¹³C-enriched CBrClF₂ and ¹³C-enriched CCl₂F₂ under selected experimental conditions. As the photolysis proceeded, the ¹³C concentration of CBrClF₂ decreased gradually and that of CCl₂F₂ increased up to 90% or higher. These results can be explained by the mechanism involving the secondary ¹³C-selective IRMPD of the primary product CBrClF₂. On the other hand, the carbon-containing product for a CCl₂F₂/Br₂ system was only CBrClF₂; the further IRMPD of which probably regenerated CBrClF₂ in the presence of Br₂. The decomposition probabilities of ¹²C- and ¹³C-containing molecules in both systems were measured as functions of laser line, laser fluence, and reactant pressures.     

Production of highly concentrated 13C by continuous two-stage IRMPD. CBr2F2/HI,CCl2F2/HI,and CBrClF2/HI mixtures

Difluoromethane CH₂F₂ containing 90–98% ¹³C was obtained in the selective IRMPD of mixtures of CBr₂F₂/HI, CCl₂F₂/HI, and CBrClF₂/HI. In CBr₂F₂/HI mixtures, the intermediate product CHBrF₂ resulting from the reaction between the initial decomposition fragment CBrF₂ and HI underwent secondary selective IRMPD to form highly ¹³C-enriched CH₂F₂ in continuous laser irradiation. The intermediate product in the mixtures of CCl₂F₂/HI and CBrClF₂/HI was found to be CHClF₂, but no significant secondary photodecomposition in CBrClF₂/HI mixtures occurred owing to the low absorption cross section of CHClF₂ at the adopted laser frequencies and fluences. The observed decomposition probabilities and selectivities under different conditions with respect to laser frequency, fluence, and partial pressures of halogenated difluoromethanes and HI suggest that CBr₂F₂ is one of the better candidates for practical ¹³C separation by IRMPD.     

Scaling-up13C separation by infrared multiphoton dissociation of the CHClF2/Br2 system

¹³C separation at a laboratory scaled-up level by the¹³C-selective InfraRed MultiPhoton Dissociation (IRMPD) of CHClF₂ in the presence of Br₂ has been investigated in a flow reactor. With a complete scaled-up system including a flow reactor, an industrially reliable TEA CO₂ laser with longer pulse duration and a product-separation set-up for¹³C separation, it has been attempted to optimize the parameters suitable for large-scale production of the carbon isotope. The optimization of¹³C separation parameters, such as laser fluence, laser frequency and the partial pressure of CHClF₂ and Br₂ was tested under static conditions. By irradiation with longer pulses, a lower optimum pressure for a high¹³C-production rate was determined. Furthermore, the separation process was scaled in the flow system to examine the¹³C-production rates,¹³C atomic fractions in the CBr₂F₂ products and¹³C depletions in the CHClF₂ reactants at different flow rates and laser repetition frequencies. The data obtained from the flow tests demonstrated a 40 mg/h production rate for CBr₂F₂ at 65%¹³C by using a 40 W (4 J, 10 Hz) laser beam focused with a lens of 120 cm focal length. If the reliable TEA CO₂ laser is operated with 100 W (10 J, 10 Hz) output, the production rate of CBr₂F₂ for¹³C at 60% of 200 mg/h can be attained. The measurements of the spatial profile of the focused laser beam imply a 2 g/h production rate for the 60%¹³C product for an incident power of 200 W (20 J, 10 Hz).     

13C-selective infrared multiple-photon decomposition study of CBrClF2

The infrared multiple-photon single-frequency decomposition (IRMPD) of CBrClF₂ was examined as functions of laser wavenumber, laser fluence, and partial pressure of CBrClF₂. The initial step was the scission of a C-Br bond. In the presence of O₂ the carbon-containing product was CF₂O and its subsequent hydrolysis gave CO₂. The initial dissociation was highly ¹³C selective at wavenumbers below 1014 cm^–1. CBrClF₂ decomposed at relatively low fluences as compared to CHClF₂. However, the decomposition yield rapidly decreased with increasing pressure. In the large-scale irradiation experiment using about 8 J pulse at 1 Hz, we obtained a carbon yield of 0.41 mol per pulse at a ¹³C-atom fraction of 17% for a mixture of 10 Torr CBrClF₂ and 10 Torr O₂, and a carbon yield of 0.17 mol per pulse at a fraction of 29% for a mixture of 20 Torr CBrClF₂ and 20 Torr O₂. The IRMPD of CHClF₂ gave a carbon yield of 0.18 mol per pulse at 48% for 10 Torr neat CHClF₂ and yield of 0.25 mol at 52% for 20 Torr CHClF₂. The large-scale irradiation experiment was also carried out for mixtures of CBr₂F₂ and O₂. CHClF₂ is the most productive of ¹³C.     

13C-selective two-stage IRMPD of mixtures of CHClF2 and HI

The ¹³C-selective infrared multiple-photon decomposition (IRMPD) of mixtures of CHClF₂ and HI was examined in collimated and focused beam geometries using a CO₂TEA laser. The carbon-containing products were CH₂F₂ and CHF₂I. The former product showed remarkably high ¹³C atom concentrations beyond 95% under selected experimental conditions, while the latter contained 25% or less. The observed results can be explained satisfactorily in terms of the consecutive two-stage IRMPD process occurring in a single irradiation procedure, where the first-stage IRMPD of natural CHClF₂ produces ¹³C-enriched CHF₂I via the insertion of the initial decomposition fragment CF₂ into HI, and the second stage is the subsequent ¹³C-selective IRMPD of the CHF₂I to form a CHF₂ radical and an I atom. The CHF₂ radical reacts with HI to form CH₂F₂. Decomposition probabilities of ¹²CHClF₂ and ¹³CHClF₂ were measured as a function of laser fluence to optimize enrichment conditions. Furthermore, partial decomposition probabilities or relative production yields were measured as functions of laser line, pressure of HI, and pressure of CHClF₂. Both stages showed high ¹³C selectivities in the irradiation with the laser radiation around 1040 cm^–1 and at fluences below 4 J cm^–2. This mixture is one of the most promising chemical systems for the production of highly enriched ¹³C.     

Practical separation of silicon isotopes by IRMPD of Si2F6

Large-scale silicon isotope separation based on the IRMPD of natural Si₂F₆ has been carried out using a commercially available high power CO₂ TEA laser and a flow reaction system. The decomposition product SiF₄ containing 19–33% of ³⁰Si was obtained at a production rate of 1.5×10^–2–2.6×10^–2 mol·h^–1, depending on experimental parameters such as laser wavelength, laser fluence, pressure, and flow rate. SiF₄ containing 12% of ²⁹Si was obtained under slightly different conditions, i.e., at a shorter wavelength than that for ³⁰Si. When 39% of Si₂F₆ was decomposed at a slow flow rate, residual Si₂F₆ was found to have 99.7% of ²⁸Si. The production rate was 4.2×10^–2 mol·h^–1.     

Isotopically selective CVD of silicon by IRMPD of Si2F6

The IRMPD of Si₂F₆ by a CO₂ TEA laser was applied to isotopically selective CVD of silicon. A white film, probably consisting of polymers of SiF₂, was deposited on a metal foil during the irradiation of natural Si₂F₆ with the laser radiation at 951.19 cm^–1 and about 1.5 J cm^–2. Upon heating, the film became dark brown, evolving SiF₄. The³⁰Si content was found to be as high as about 20%.     

Efficient production of13C2F4 in the infrared laser photolysis of CHClF2

We report the isotopically selective decomposition of chlorodifluoromethane. Chlorodifluoromethane is used industrially in high volume for the production of tetrafluoroethylene and its polymers; thereby it is an attractive working substrate for a medium scale isotope separation process, both in terms of its price and availability.We have studied the infrared multiphoton decomposition of carbon-13 substituted chlorodifluoromethane molecules present at their natural abundance (1.11%). A well defined CO₂ laser pulse (80 ns FWHM) was used and both the yield of carbon-13 enriched product and the net absorption of laser radiation were measured. These measurements were made as a function of substrate pressure (10-800 Torr), CO₂ laser line (9P 12–9P 32) and fluence (2–8 J cm^–2) and were used to determine the energy expenditure per carbon atom produced () at specified product carbon-13 content in the range 30%–96%. The results of these parametric studies were interpreted in terms of the kinetics of multiphoton absorption and dissociation, and allowed an initial optimization of the experimental conditions to minimize .Optimum results were obtained at 1046.9 cm^–1, 69 cm^–1 to the red of the¹²CHClF₂ v ₉ band center. Irradiation of 100 Torr of chlorodifluoromethane at 3.5 J cm^–2 gave tetrafluoroethylene containing 50% carbon-13 for an absorption of 140 photons (0.017 keV) per carbon atom produced. This efficiency compares favourably with existing carbon-13 enrichment technologies and would require an absorption pathlength of only 2 m to absorb half the incident photons.Issued as NRCC 20112     

Infrared multiple photon decomposition of CHBrF2 induced by a free-electron laser

2 . The laser generates an intense infrared macropulse with a duration of 17 μs; the macropulse consists of a train of 380 micropulses, each of which has a duration of a few picoseconds. The fluence of a macropulse was estimated to be about 16 Jcm^-2 at a beam waist. Peak wavelengths were set in the range of 9–10 μm. The macropulse induced the IRMPD of 1 and 5 Torr CHBrF₂; most of molecules in the focal region seemed to decompose at a wavelength of 9.3 μm. The mechanism is the initial decomposition of CHBrF₂ to CF₂ and HBr, followed by the dimerization of CF₂ to form C₂F₄. The decomposition was found to be isotopically selective at 9.7 μm; the final product C₂F₄ had a ¹³C atomic fraction of 6%. Th e addition of CO₂ to CHBrF₂ significantly decreased the yield of C₂F₄. vibrationally excited CHBrF₂ molecules produced by laser pulses were efficiently deactivated by CO₂ molecules. Received: 7 October 1996     

Parametric study of the IRMPD of CF2HCl molecules with the 9P22 CO2 laser line

The separation of ¹³C by infrared multiple photon decomposition (IRMPD) of CF₂HCl has been parametrically studied in relation with some key parameters such as the laser fluence, the number of laser pulses, and the gas pressure. The process selectivity, the depletion of the ¹³C isotope in the residual gas, the relative amount of ¹³C separated per pulse, and the energy expenditure were determined as a function of the above mentioned parameters, and conclusions were drawn concerning the efficiency of the separation process. An isotopic selectivity of about 40 was obtained in the investigated range of pressure. At 10 Torr of pure CF₂HCl, the ¹³C depletion in the residual gas was 45% when only 300 laser pulses were used. A maximum amount of 4.6×10^–10 kg ¹³C separated per pulse was obtained.     

Fluence and wavelength dependence of the IRMPA and IRMPD of CDCl3 with a CO2 laser

A TEA CO₂ laser was used to study the infrared multiple-photon absorption (IRMPA) and dissociation (IRMPD) spectra of CDCl₃ in the fluence ranges 0.01–1.4 and 7–45 J/cm², respectively, for different sample pressures. Experimental results were modeled with a master equation formulation which includes rotational and anharmonic bottlenecks and collisional effects. Experimental and calculated results show that CDCl₃ has great rotational and anharmonic restrictions at the first stages of excitation. The IRMPD spectrum falls more slowly than the linear absorption spectrum at the blue wing due to intramolecular vibrational relaxation at the quasi-continuum level of excitation.     

X-ray preionized CO2 laser

A short pulse (100 ns) high-energy x-ray source has been used to preionize a transversely excited carbon dioxide gas discharge laser of 600 cm³ active volume. The maximum output power of 60 MW in a 50 ns FWHM pulse was achieved from a CO₂–N₂–He–CO–Xe static gas mixture at 600 Torr pressure. The energy conversion efficiency was 6%.     

Infrared multiphoton dissociation of13CF3Cl induced by CO2 laser pulses

Selective infrared multiphoton dissociation of¹³CF₃Cl induced by CO₂ laser pulses adjusted on = 1071.9 cm^–1 has been studied in the energy rangeE between 0.5 and 2 J per laser pulse or fluence range between 5 and 25 J per cm², and in the pressure range between 0.10 and 60 Torr. The effect of these parameters on the isotopic selectivity of the dissociation gives information on the rotational relaxation constants. As for the dissociation probabilities, they vary exponentially withE ^–1. The applicability of such an Arrhenius-type relation is discussed and semi-quantitatively justified.     

HF Laser Based on Thermal- and Photon-Branched Chain Reactions Initiated by IR Laser Radiation

A chemical H₂–F₂ laser (oscillator and amplifier) initiated by means of IR radiative excitation of vibrational levels of HF molecules is studied under the conditions of development of a thermal-branched chain reaction caused by thermal dissociation of gaseous additions to the laser mixture. It is shown that, using F₂SO₃ addition at a partial pressure of 40 Torr, an H₂–F₂ laser with a mixture pressure of 1~bar initiated by a pulsed hydrogen fluorine laser can provide an output exceeding 120–200 J/liter in 20–50 ns laser pulses.     

Chemical reactions following the IRMPD of C2F3Cl

C₂F₃Cl is photolyzed with a TEA-CO₂ laser at 1050.44 cm^–1 with focussed fluences up to 280 J/cm². The stable products in the IRMPD of C₂F₃Cl are determined for up to 10 Torr of C₂F₃Cl being photolyzed both neat and with added O₂. C₂F₄ and trans-C₂F₂Cl₂ are found to occur in the greatest yield though C₃F₅Cl, C₃F₄Cl₂, C₄F₇Cl, and C₂F₃Cl₃ also appear to be primary products. When O₂ is present F₂CO, FClCO, and CF₂ClCOF are the exclusive products. The formation of these products are for the most part consistent with a carbene formation dissociation mechanism for C₂F₃Cl IRMPD. C₂F₃Cl₃ may best be explained by another mechanism competitive with carbene formation. Many products attributed to secondary photolysis mechanisms are observed for long photolysis times.This work was performed at Department of Chemistry and chemical Engineering, Michigan Technological University, Houghton, MI 49931, USA     

Tritium isotope separation by CO2-laser irradiation at low temperatures

Tritium isotope separation by CO₂-laser induced multiphoton dissociation of CTF₃ is investigated. For the optimization of the performance of this working substance, trifluoromethane, the conditions to yield high-selectivity at high-operating pressure and low-critical fluence for complete dissociation are studied using our deconvolution procedure. The irradiation conditions are varied over the following ranges; wavenumber: 1052–1087 cm^–1, gas temperature: 25°C to –78°C, CHF₃ pressure: 5–205 Torr. The selectivities exceeding 10⁴ are observed for 85–205 Torr CHF₃ at –78°C by the irradiation at 1057 cm^–1.     

T/D isotope selectivity in CO2 laser induced multiple-frequency multiphoton dissociation of trifluoromethane-T

Isotope-selective multiphoton dissociation of CTF₃ in the presence of CDF₃ by TEA CO₂ laser is studied. The highest T/D selectivity of 58 was observed at a sample pressure of 2 Torr in the presence of 20 Torr of argon on excitation by the 9P(24) CO₂ laser line. The effect of multiple-frequency irradiation on selectivity is studied in the P and Q branches of the v ₂ absorption band of CTF₃. No improvement in the selectivity is noticed on going from single- to multiple-frequency irradiation. These results are compared with previous multiple-frequency work on the CTF₃/CHF₃ system, and explained in terms of strong spectroscopic interference from ¹³CDF₃ in the present case.     

Characterization of a Br(2P1/2)–CO2(1001-1000) transfer laser driven by photolysis of iodine monobromide

2 laser operating on the 10⁰1-10⁰0 transition at λ=4.3 μm and pumped by E –V energy transfer from Br(²P_1/2) has been demonstrated. The dynamics and performance of this device were characterized by observing the time-resolved stimulated emission and the steady-state spontaneous side fluorescence after photolysis of IBr or Br₂ by a frequency-doubled Nd:YAG laser or Ar⁺ laser, respectively. Although the E –V excitation kinetics are favorable, rapid vibrational relaxation limits laser action to CO₂ pressures of less than 1 Torr. Numerical modeling of laser pulse shapes and the dependence on IBr and CO₂ pressure and photolysis energy establish a relatively high gain of 0.33%/cm, a CO₂-pressure-dependent optical loss of 0.04–0.06%/cm, and an efficiency of 2×10^-5 4.3-μm-laser photons per incident photolysis photon. The CO₂ fluorescence after photolysis of a fixed Br₂/CO₂ gas mixture decreases as a function of photolysis time by about 30%/h, indicating the photolytic production of an important quencher. Received: 23 June 1997/Revised version: 23 September 1997     

Systematic experimental study of instabilities in the sealed CO2 laser

A systematic pressure-current experimental study of the wave instability regions in glow-discharge of different CO₂ laser mixtures has been accomplished. The forward ionization wave F^– has been found to be the main instability. At low currents (< 30 mA) and higher pressures (> 550 Pa) the laser discharge becomes stable. The highest output power at a given mixture ratio was achieved in these quiet regions. The normalized electric field dependences of wavenumber, phase and group velocities of the F^– wave are presented.