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     

Highly selective and efficient multiphoton dissociation of polyatomic molecules in multiple-frequency IR-laser fields

An ir multiphoton dissociation (MPD) process in multiple-frequency ir-laser fields has been experimentally realized. A selectivity ofS=10⁴ was obtained in separating¹³C/¹²C isotopes upon multiple-frequency ir multiphoton dissociation (MFMPD) of the CF₂HCl molecule, the dissociation yield¹³ for the¹³CF₂HCl molecule amounting to around 1%. A yield of¹³ was reached at a selectivity ofS=10², and the total laser fluence required for the process was reduced. A new mechanism—sticking of molecules on the lower discrete vibrational levels—responsible for the low MPD yields observed for some molecules is discussed and a technique to eliminate it and thus maximize the dissociation yields is proposed. Ways to improve the selectivity by MFMPD are analyzed and a simple method for obtaining from a single TEA CO₂ laser a multiple-frequency radiation suitable for experimental realization of MFMPD is suggested.     

Isotopically selective infrared multiphoton dissociation of 2-chloro-1,1,1-trifluoroethane: 13C selectivity and mechanism

13 C-selective infrared multiphoton dissociation of CF₃CH₂Cl has been studied by analyzing the distribution of ¹³C concentrations of the main products CF₂=CHCl, CF₂=CH₂, CF₂=CHF, C₂F₆, and the trace products CF₃CH₂CF₃ and CF₃CH=CHF₃. The mechanism mainly concerns the dissociation of energized CF₃CH₂Cl, the collisional stabilization of excited CF₃CH and CF₃CH₂ and the recombination of the nascent radicals. No significant radical–molecule reactions degrade the intrinsic ¹³C dissociation selectivity. High ¹³C production yield and ¹³C concentration can be attained at a laser fluence of 1.6 J/cm². Such low fluence can be used to improve focus condition and enhance photon utilization efficiency for practicable ¹³C separation. Received: 10 March 1998/Revised version: 17 September 1998     

Effect of rotational relaxation on the yield of the multiphoton dissociation of CF3Cl and CF3Br under TEA-CO2 laser pulses

The yield of the multiphoton dissociation of CF₃Cl and CF₃Br induced by TEA-CO₂ laser pulses has been studied in the pressure range between 0.25 and 8 Torr, the laser wavelength being chosen so as to excite preferentially the minor isotopic components¹³CF₃Cl and¹³CF₃Br. For both compounds the dissociation probability is found either to increase almost linearly or to decrease monotonously with gas pressure, according as the laser beam is focused or unfocused, respectively. This behaviour is explained by rotational relaxation effects, and a value of 22ns·Torr for the rotational self-relaxation time of CF₃Cl is obtained.     

Efficient, highly selective laser isotope separation of carbon-13

We recently demonstrated an original approach to highly selective laser isotope separation of carbon-13 that employs vibrational overtone pre-excitation of CF₃H together with infrared multiphoton dissociation [O.V. Boyarkin, M. Kowalczyk, T.R. Rizzo, J. Chem. Phys. 118, 93 (2003)]. The practical implementation of this approach was complicated by the long absorption path length needed for the overtone excitation laser beam. In the present work, we employ a low overtone level for the pre-excitation that shortens this pathway, facilitating engineering of the process. We propose an optimal configuration of the isotope separation scheme and consider a realistic example of a separation unit for isotopic enrichment of carbon-13 to 94–98%. The photon energy expenditure of 97 eV per separated atom is much lower than that of the current commercial laser technology, making this process economically feasible.PACS 82.30.Lp; 89.90.+n     

Simultaneous measurements of absorption and vibrational relaxation time in CF2HCl molecules

Summary We describe in this paper a simple interferometric technique which allows a direct and simultaneous determination of energy absorption and of the vibrational-translational relaxation time of polyatomic molecules strongly excited by reasonant, infrared (10.6 μm) laser radiation. In particular, we have applied this method to the study of freon-22 (CF₂HCl), a medium-size molecule that, apart from its potential application in¹³C isotope separation, shows interesting absorption features in the 10 μm region. The results are also compared with our previous findings in SF₆. To speed up publication, the authors of this paper have agreed to not receive the proofs for correction.     

Laser isotope separation of 13C: A comparative study

IR laser chemistry of (CF₃Br/Cl₂) mixture and neat CF₂HCl are examined in the context of ¹³C enrichment. Decomposition extent, enrichment factor and energy absorbed are measured for both systems at their respective optimum conditions. A direct comparison is obtained by keeping extraneous factors such as laser, its pulse duration, cell, irradiation geometry etc. the same. The halogen scavenged CF₃Br MPD requires lower fluence compared to neat CF₂HCl irradiation. Overall throughput for a product with 60–65% ¹³C content in a single stage is the same for both systems requiring a similar amount of energy. However, at lower enrichment levels, CF₂HCl MPD is better than (CF₃Br/Cl₂) photolysis in terms of both product yield and energy absorption.     

Scheibe-aggregates of Pseudoisocyanine in solution and in molecular monolayers

A new working molecule 1,1,1,3,3,3-hexafluoro-2-(trifluoromethyl)-propane-2-t (CF₃)₃CT, is reported for the isotope separation of tritium by TEA CO₂-laser-induced multiphoton dissociation (MPD). Selective and efficient dissociation of (CF₃)₃CT was observed by irradiation at about 980 cm^–1 where (CF₃)₃CH was nearly transparent. The critical fluence for dissociation of (CF₃)₃CT at 10R(28) 980.9 cm^–1 was estimated to be as low as 4.6 J/cm², which is the lowest of the tritiated halocarbons that we have ever reported. A detailed study was made of the pressure dependence of the dissociation rate constants for (CF₃)₃CT and (CF₃)₃CH to clarify the collisional effects in their MPD. The hydrogen isotope exchange between (CF₃)₃CH and HTO was found to be extremely rapid, which is advantageous in the practical laser separation cycle for tritium removal from water.     

Absorption of CO 2 laser emission by freon-12

The infrared (IR) absorption of freon-12 (CF₂Cl₂) was studied in the emission range of a 3-W tunable CW CO₂ laser by using a brass cell with KBr windows that was located outside the laser resonator. The results show that CF₂Cl₂ absorbs all CO₂ laser emission lines in the ranges of 1073–1083 cm^-1 and 937–943 cm^-1. The most strongly absorbed laser line was 10P (28) ( 937.21 cm^-1). Absorption coefficient values were obtained for all available wavelengths of the CO₂ laser as the CF₂Cl₂ pressure was varied from 5 to 1000 mbar. By using the HITRAN database for freon-12, the absorption coefficients were calculated at the 10P (28) and 9R (28) lines as functions of the gas pressure and compared with the experimental values. The calculated results are in reasonable agreement with the experiment. PACS 33.20.Ea; 42.55.-f; 42.55.Lt     

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.     

Excitation and dissociation of polyatomic molecules under the action of femtosecond infrared laser pulses

The effect of high-intensity femtosecond laser pulses (100–200 fs) in the near (0.8–1.8 μm) and medium (4.6–5.8 μm) IR ranges on the CF₂HCl, CF₃H, (CF₃)₂C=C=O, and C₄F₉COI molecules is examined. Irradiation of CF₂HCl and CF₃H molecules by 0.8-to 1.8-μm laser pulses with intensities of >40 TW/cm² (>4 × 10¹³ W/cm²) makes them dissociate to yield CF₃H and CF₄, respectively. The key mechanism of the dissociation of these molecules is field ionization and fragmentation. The excitation of the stretching vibrations of the C=O bond in the (CF₃)₂C=C=O and C₄F₉COI molecules by 4.5-to 5.8-μm femtosecond pulses produced no detectable dissociation up to a fluence of ∼0.5 J/cm² (or a intensity of ∼2.5 TW/cm²). Probable explanations of this observation are discussed. Original Russian Text ? V.M. Apatin, V.O. Kompanets, V.B. Laptev, Yu.A. Matveets, E.A. Ryabov, S.V. Chekalin, V.S. Letokhov, 2007, published in Khimicheskaya Fizika, 2007, Vol. 26, No. 4, pp. 18–25.     

The frequency,fluence and pressure dependence of the absorption of pulsed CO2-laser radiation by CF2HCl

Absorption measurements in the CF₂HCl fundamental vibrational band v₃, and combination band v₅ + v₉, for laser energy fluence between 0.1–1.2 cm⁻² and 1–100 Torr gas pressure, are reported. Three distinct regions are experimentally observed for the fluence dependence of the absorption cross section σ and the average number of absorbed photons <n>. Adding Ar buffer gas to CF₂HCl enhances the absorption efficiency only in the v₃ band.     

Isotope-selective infrared multiphoton dissociation of CF3Br in a supersonic free jet

The carbon-isotope selectivity in the multiphoton dissociation of CF₃Br is studied in the collisional region of supersonic free jet. The isotopic abundance of¹²C and¹³C in C₂F₆ formed by recombination of the dissociation products is measured with a quadrupole mass spectrometer. An enrichmet factor of 9.4 is obtained for¹²C with the 9R(30)CO₂ laser line while the factor of 6.9 is obtained for¹³C with the 9P(16) line.     

Multiphoton fragmentation and ionization of CF2HCl molecules and clusters by UV radiation

The results of experimental studies of multiphoton ionization of CF₂HCl molecules and clusters by UV laser radiation in the wavelength range 217–236 nm are reported. In the case of molecules, the main reaction products are CF₂H⁺ and CF⁺ ions as well as atomic chlorine. It is found that the spectra of the products of ionization of free molecules and molecules condensed into clusters differ qualitatively: multiphoton ionization of clusters does not yield CF₂H⁺ ions. The dependences of the ion yield on the intensity of laser radiation and its wavelength are measured. The effect of a constant electric field and the radiation spectral width on the multiphoton ionization process is demonstrated. The shape of the velocity distributions is determined for a number of products. A strong anisotropy is detected in the reaction of formation of CF₂H⁺ ions. Possible mechanisms for these processes are discussed.     

Macroscopic enrichment of12C by a high-power mechanically Q-switched CO2 laser

The isotope-selective multiphoton dissociation of CHClF₂ in a multipass refocusing Herriott cell was used to enrich more than 4 moles of chlorodifluoromethane to 99.99% of¹²C isotopic purity. It is the largest isotope quantity ever separated by a laser process. A cw excited mechanically Q-switched CO₂ laser, which delivers 16 mJ pulses at 5 kHz was used. The enrichment controlled by a mass-spectrometer and guided by a PC was run with a rate of 25 g¹²C per 24 h.     

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.     

18O-selective IR MPD of perfluorodimethyl ether

The ¹⁸O-selective IR MPD of perfluorodimethyl ether (CF₃)₂O has been studied. The dissociation yields of (CF₃)₂ ¹⁸O (₁₈) and (CF₃)₂ ¹⁶O (₁₆) and the isotope selectivity (18/16) have been measured as functions of TEA CO₂-laser frequency, laser fluence and ether parent pressure. The (CF₃)₂O molecule has been found to provide highly efficient ¹⁸O separation. The MPD yield of the desired isotope ¹⁸O varies in the range 3–13%; the selectivity (18/16) achieves a value of 95 at the laser line 10P22, at moderate fluence Ø=4 J/cm² and at P _{(CF 3)2 O}=0.5 Torr.     

Chemical reactions between CF2HCl and NH3 induced by IR double-beam excitation

Infrared multiphoton dissociation experiments with two wavelengths in different mixtures of chlorodifluoromethane and ammonia have been carried out. It is shown that the presence of ammonia in the sample induces a decrease in the chlorodifluoromethane dissociation yield. It has been observed that the distinct chemical reaction channels are differently activated as the time delay between the two laser pulses is varied. The ratio of the obtained products in the infrared multiphoton dissociation changes with the composition of the initial mixture and are not compatible with the mechanism suggested by Sugita and Arai for this reaction in single IR wavelength excitation if it is assumed to be the only contributing mechanism other than that for direct CF₂HCl dissociation and subsequent C₂F₄ formation from the resulting CF₂ radicals. It appears that, although for simultaneous two-wavelength irradiation the presence of an accumulated solid NH₄Cl deposit does not significantly influence the reaction, this is no longer the case when time delays are introduced between the two beams.     

Infrared multiphoton dissociation of difluorosilane

Infrared (IR) multiphoton absorption and dissociation of difluorosilane molecules under the action of a pulsed transversely excited atmospheric CO₂ laser were experimentally studied. It has been found that the multiphoton absorption is strongly saturated due to the rotational bottleneck effect. Isotope-selective IR multiphoton dissociation of difluorosilane was performed at 977.2 cm^-1. The dissociation rate for ²⁸SiH₂F₂ isotopomer has been found to be about twice as high as for the other isotopomers at this wavelength. PACS 82.50.Bc; 82.30.Lp     

Laser isotope separation of tritium using CF3CTBrF/CF3CHBrF

A new working molecule 2-bromo-1,1,1,2-tetrafluoroethane is reported for laser isotope separation of tritium. The multiphoton dissociation rate of CF₃CTBrF is studied as a function of irradiation wavenumber, using a CO₂ or NH₃ laser. In a tightly focused irradiation geometry where the dissociation saturates both for CF₃CTBrF and CF₃CHBrF, their threshold fluences of dissociation and the geometrically biased selectivity are measured near the maximum of the dissociation rate of CF₃CTBrF. When the irradiation geometry is optimized, a high selectivity exceeding 2700 is obtained.