Adsorption of Freon 113

Summary The adsorption of Freon 113 (1,1,2 trichloro-1,2,2 trifluoroethane) at 260–310 K on Graphon was measured and compared with the adsorption of krypton at 104–120 K on the same surface. The adsorption isotherms, and resulting thermodynamics, for both adsorbates were similar over the entire pressure range studied. Surface area analysis of the data suggests that the Freon molecule occupies approximately 2.5 times the area of the krypton molecule on Graphon. Further, the Freon molecules are hindered in their rotational freedom on this surface at these temperatures, with their dipole axes aligning perpendicular to the surface of the Graphon.

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Zusammenfassung Es wurde die Adsorption von Freon 113 (1,1,2 Trichlor-1,2,2 Trifluoräthan) an Graphon bei 260–310 °K gemessen und mit der Adsorption von Krypton bei 104–120 °K auf der gleichen Grenzfläche gemessen. Die Adsorptionsisothermen und die daraus resultierenden thermodynamischen Daten waren für beide Adsorbate im gesamten untersuchten Druckbereich ähnlich. Eine Analyse der Daten legt nahe, daß ein Freonmolekiil annähernd das 2,5fache der Fläche eines Kryptonmoleküls auf Graphon beansprucht. Es ist anzunehmen, daß die Freonmoleküle auf dieser Oberfläche und bei diesen Temperaturen in ihren Rotationsfreiheitsgraden gehindert sind und ihre Dipolachsen senkrecht zur Oberfläche liegen.

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With 9 figures and 2 tables     

Photochemical transformations of cyclic acetal radical cations in Freon matrices at 77 K

The efficiency of photochemical reactions of radical cations of cyclic acetals (1,3-dioxolane, 1,3-dioxane) is measured in different Freon matrices at 77 K and the influence of the latter on the reaction path is discovered. The possible nature of the paramagnetic complexes that form in photochemical reactions of cyclic acetal radical cations in Freon-11 is suggested.     

Interaction of the Azole N‐Sodium Derivatives with Freon‐113: Synthesis of N‐(2,2‐dichlorotrifluoroethyl)azoles

The synthesis of 2,2‐dichlorotrifluoromethyl derivatives of azoles and diphenylamine by the interaction of N‐sodium salts with Freon‐113 has been carried out. The sodium salts of heterocycles, having a one‐ring nitrogen atom, react with Freon‐113 without catalysis. The sodium salts of heterocycles, having two‐ or three‐ring nitrogen atoms, react with Freon‐113 in the presence of tetrabutylammonium iodide as a catalyst.     

Low-temperature EPR study of radical cations of vinyl ethers in a Freon matrix

Using low-temperature EPR the transformations of radical cations of aliphatic vinyl ethers radiolytically generated in a Freon matrix have been investigated. Three-line spectra found at 77 K [hfs constants of 1.5 mT (1H) and 2.2 mT (1H)] and at 95 K [1.9–2.1 mT (2H)] were attributed to the radical cation. A quartet was observed at 130 K, usually with binomial intensities [hfs constants of 1.3 mT (3H)] and a triplet [1.7–1.9 mT (2H)] was found after cooling samples back to 95 K. The conversion of the quartet to the triplet was found to be thermally reversible and both spectra are assigned to different states of a (distonic) dimer cation.     

Electrochemical Catalysis of the Reduction of 1,1,2-Trifluorotrichloroethane (Freon 113) by Outer-Sphere Electron Transfer Mediators

Cyclic voltammetry and preparative electrolysis in DMF were used to study the electrochemical catalytic reduction of 1,1,2-trifluorotrichloroethane with aromatic electron transfer mediators (p-dicyanobenzene, p-diacetylbenzene, fluoranthen, perylene, and (E)-azobenzene), leading to trichloroethylene in high yield. The results of a kinetic study of these systems indicate that the efficiency of other mediators of this class may be estimated relative to their redox properties. In comparison with direct electrochemical reduction of Freon 113, the use of aromatic electron transfer agents significantly raises the efficiency of Freon conversion and permits us to perform the reaction at less negative potentials.     

Radical products of γ-radiolysis of 12-crown-4 at 77 K

Paramagnetic products of γ-radiolysis of 12-crown-4 and its solutions in CFCl₃ and CFCl₂CF₂Cl at 77 K were studied by ESR spectroscopy. It was found that the ESR spectra of 12-crown-4 irradiated with γ-rays at 77 K contained superimposing signals of at least two species, the radicals resulting from macrocycle opening -?H-C(H) = O and macrocyclic radicals -O-?H-CH₂-, which are formed with nearly equal yields. It was shown that -O-?H-CH₂-radicals rapidly decayed at temperatures above 140 K. However, the -?H-C(H)=O radicals are stable almost up to the matrix softening temperature. The radical cations of 12-crown-4 are not stabilized in the matrices of Freon 11 and Freon 113, since they undergo transformation to macrocyclic radicals -O-?H-CH₂-via the deprotonation reaction.     

Radiation synthesis of tetrafluoroethylene telomers with functional hydroxyl and amino end groups in Freon 113

The kinetics of radiation telomerization of tetrafluoroethylene in Freon 113 with ethanol and ammonia additives have been studied by kinetic calorimetry. Tetrafluoroethylene telomers with terminal hydroxyl and amino groups have been obtained. The molecular structure, properties, and composition of the telomers have been investigated by IR spectroscopy, thermogravimetry, and elemental analysis.     

Stabilization and reactions of tetramethylurea radical cations in Freon matrices at 77 K: Intramolecular hydrogen transfer,ion-molecular reactions,and fragmentation by electron spin resonance study

ESR spectra for -irradiated at 77 K solutions /0.02–16%/ of tetramethylurea /TMU/ in CFCl₃ and Freon-113 have been studied. TMU^+. radical cations radiolytically produced in dilute solutions have been shown to undergo intramolecular hydrogen transfer upon photobleaching resulting in CH₂N= type radical. Evidence for intermolecular proton transfer in TMU^+. radical cations after annealing to phase transition temperature /110–120 K/ in Freon-113 was obtained. Primary radical cations of TMU^+. at their ground state take part in ion-molecular reaction via proton transfer. Molecular cations in their excited states may undergo fragmentation producing Me₂N radicals, which were trapped in liquid phase by t-BuNO as a spin trap.     

CHEMILUMINESCENCE FROM CARBENE OXIDATION

Abstract— The chemiluminescent reaction between carbenes and O₂ in Freon 113 at and above 77 K was investigated. The reaction was found to be general for phenylated carbenes and independent of precursor. Spectra obtained by optical multichannel analyzer (OMA) are consistent with the emission being from the excited ketone formed. Kinetics studies at 77 K indicate that the decay of the chemi-luminescence is significantly faster than the decay of the carbene as monitored by fluorescence and electron paramagnetic resonance.     

Temperature change of OD ESR and freon matrix ESR of the radical cations of 9,10-octalin and cyclohexene

The optical detection (OD) ESR and Freon matrix ESR spectra were observed for the radical cations of 9,10-octalin and cyclohexene from 77 to 300 K. The observed spectral change was attributed to ring inversion in both radical cations based on MO calculations and an analysis by the modified Bloch equation. The activation energy for the inversion of the radical cation of octalin was calculated as 18.8 kJ mol⁻¹.     

Photochemical Reactions of Linear Alkane Radical Cations in Low-Temperature Matrices

The radical cations of linear alkanes (n-pentane, n-heptane) trapped in various matrices (Freon-11, Freon-113, Freon-113a, mixture of Freon-11 and Freon-114B2, and sulfur hexafluoride) were found to undergo the following types of photochemical reactions: (1) charge transfer to the matrix followed by neutralization, (2) isomerization and unimolecular decomposition, and (3) deprotonation. The absorption spectra of the radical cations were characterized, and the quantum yields of reactions occurring in different matrices at 77 K were determined. It was shown that the reaction pathway and efficiency of the photochemical processes observed for a given radical cation in different matrices with similar physical and chemical characteristics could considerably differ.     

An ESR study of free radicals formed in irradiated poly(alpha-methyl styrene) by gamma-radiation

The radiolysis of poly(α-methyl styrene) with γ-radiation has been studied at 77 and 300 K by ESR spectroscopy. The radical intermediates formed at these temperatures have been identified by utilization of the techniques of photobleaching, thermal annealing and simulation. The radical yields were found to be 0.105±0.005 at 77 K and 0.05±0.003 at 298 K.     

Photochemical transformations of 1,3,5-trioxane radical cations in freonic matrices at 77 K

It was found that the principal photochemical reaction of 1,3,5-trioxane radical cations in freonic matrices at 77 K is their cycle-opening dissociation yielding the distonic radical cation in which the unpaired electron is preferentially localized on the oxygen atom. The dissociation of the trioxane radical cations at 77 K is characterized by high quantum yields, which vary from 0.24 to 0.36 in different matrices. The distonic radical cations produced during photolysis are unstable at 77 K and undergo further transformations, which occur at different rates in freonic matrices. The structure of the intermediates produced and a possible mechanism of the processes are discussed with the use of quantum-chemical calculation data.     

Reactions of the primary radical cations of carboxylic acids as studied by ESR in freonic matrices

Radical products of radiolysis of frozen solutions of propionic and butyric acids were studied in the matrices of Freon-11, Freon-113, and Freon-113a at 77 K. It was shown that the primary radical cations generated by radiation were not trapped in the freonic matrices (in contrast with the corresponding freonic solutions of acetic acid). The radical cations of propionic and butyric acids decay in concurrent processes of rearrangements yielding terminal-type and ylide-type distonic radical cations and intramolecular proton transfer in the dimeric radical cations resulting in acyloxy radicals. The latter species undergo decarboxylation to yield ethyl and propyl radicals for propionic and butyric acids, respectively. According to mass-spectrometric data, the terminal-type distonic radical cations undergo the McLafferty rearrangement.Translated from Khimiya Vysokikh Energii, Vol. 39, No. 2, 2005, pp. 97–104.Original Russian Text Copyright © 2005 by Belevskii, Belopushkin.This revised version was published online in April 2005 with a corrected cover date.     

Quantitative determination of Freon gas using an electronic nose

This paper reports a quantitative electronic nose (enose) for the quantitative determination of Freon gas within the concentration range 0-1000 ppm in the presence of interfering gases such as water, lubricant and petrol vapours. This quantitative enose is a new type of Freon detection system, composed of an array of four sensors. The artificial neural network (ANN) and fuzzy logic type of ANN (FNN), in combination with the relative error concept in analytical chemistry, are integrated for both quantification and discrimination. The predicted results are satisfied with a pass rate of > 80% within the permitted relative errors. The results show that the Freon enose developed in this study is reliable for both the qualitative and quantitative determination of Freon gas and exhibits the merits of high sensitivity, anti-interference and accuracy.     

Photoadsorption and Photocatalytic Processes Affecting the Composition of the Earth's Atmosphere: II. Dark and Photostimulated Adsorption of Freon 22 (CHF2Cl) on MgO

The interaction of hydrogen-containing Freon 22 (CHF₂Cl) with the surface of MgO that was held in air both before and after heating at 620 K in the dark or under exposure to soft UV radiation, which corresponded to the solar spectrum in the troposphere, is examined. Up to 1% of a Freon 22 monolayer is adsorbed on the surface of MgO in the dark, and more than 10% of a monolayer was adsorbed under UV irradiation. The photoadsorption activity is not associated with the presence of nitrogen-containing compounds formed by the adsorption of nitrogen oxides from air on the surface of MgO. Magnesium oxide does not adsorb hydrogen-free Freon 12 (CF₂Cl₂) either in the dark or under exposure to UV radiation.     

Destruction of Freon HFC-134a Using a Nozzleless Microwave Plasma Source

In this paper, results of the pyrolysis of Freon HFC-134a (tetrafluoroethane C₂H₂F₄) in an atmospheric pressure microwave plasma are presented. A waveguide-based nozzleless cylinder-type microwave plasma source (MPS) was used to produce plasma for the destruction of Freon HFC-134a. The processed gaseous Freon HFC-134a at a flow rate of 50–212 l min⁻¹ was introduced to the plasma by four gas ducts which formed a swirl flow in the plasma reactor (a quartz cylinder). The absorbed microwave power was 0.6–3 kW. The experimental results showed that the Freon was converted into carbon black, hydrogen and fluorine. The total conversion degree of HFC-134a was up to 84% with selectivity of 100% towards H₂, F₂ and C₂, which means that there was no conversion of HFC-134a into other hydrocarbons. The Freon destruction mass rate and corresponding energetic mass yield were up to 34.5 kg h⁻¹ and 34.4 kg per kWh of microwave energy absorbed by the plasma, respectively.     

Photophysical and photochemical processes of 9,10-dihydro-9-silaphenanthrene derivatives: photochemical formation and electronic structure of 9-silaphenanthrenes

Photophysical and photochemical processes of 9-methyl- and 9-phenyl-9,10-dihydro-9-silaphenanthrene derivatives have been studied at room temperature and 77 K in comparison with the carbon analogue, 9,10-dihydrophenanthrene. These 9,10-dihydro-9-silaphenanthrene derivatives show smaller fluorescence quantum yield and remarkably larger Stokes shifts than those of the carbon analogue. In contrast, their phosphorescence quantum yields are two times larger than those of the carbon analogue, although the absolute value is not so large (approximately 0.1). Reaction products and intermediates produced by the 266 nm light photolysis have been studied, and it has been confirmed that 9-methyl- and 9-phenyl-9-silaphenanthrenes have been photochemically formed in methylcyclohexane at 77 K, in addition to the formation of radical cations of 9,10-dihydro-9-silaphenanthrene derivatives and the carbon-centered radical: 9-hydro-9-silaphenanthrenyl radical.     

Single crystals of L-O-serine phosphate X-irradiated at low temperatures: EPR, ENDOR, EIE, and DFT studies

Single crystals of the phosphorylated amino acid L-O-serine phosphate were X-irradiated and studied at 10 K and at 77 K using EPR, ENDOR, and EIE techniques. Two radicals, R1(10 K) and R1(77 K), were detected and characterized as two different geometrical conformations of the protonated reduction product >CH-C(OH)(2). R1(10 K) is only observed after irradiation at 10 K, and upon heating to 40 K, R1(10 K) transforms rapidly and irreversibly into R1(77 K). The transition from R1(10 K) to R1(77 K) strongly increases the isotropic hyperfine coupling of the C-CH(beta) coupling (Delta = 32 MHz) and the major C-OH(beta) coupling (Delta = 47 MHz), in sharp contrast to the their much reduced anisotropic hyperfine couplings after the transition. An umbrella-like inversion of the carboxylic acid center, accompanied by minor geometrical adjustments, explains the changes of these observed isotropic and anisotropic couplings. DFT calculations were done on the reduced and protonated L-O-serine phosphate radical at the B3LYP/6-311+G(2df,p)//B3LYP/6-31+G(d) level of theory in order to support the experimental observations. Two different conformations of the anion radical, related by an inversion at the carboxylic center, could be found within the single molecule partial energy-optimization scheme. These two conformations reproduce the experimental hyperfine couplings from radicals R1(10 K) and R1(77 K). A third radical, radical R2, was observed experimentally at both 10 and 77 K and was shown to be due to the decarboxylated L-O-serine phosphate oxidation product, a conclusion fully supported from the DFT calculations. Upon thermal annealing from 77 to 295 K, radicals R1(77 K) and R2 disappeared and all three previously observed room-temperature radicals could be observed. No phosphate-centered radicals could be observed at any temperatures, indicating that the phosphate-ester bond break for one of the room-temperature radicals does not occur by dissociative electron capture at the phosphate group.     

Ion-molecule reactions and thermal isomerization of tricyclo[4.3.0.0]nona-4,8-diene radical cations to tricyclo[4.2.1.0]nona-2,7-diene radical cations in a γ-irradiated frozen Freon matrix

A four-step mechanism of isomerization of tricyclo[4.3.0.0^3,7]nona-4,8-diene radical cations to tricyclo[4.2.1.0^4,9]nona-2,7-diene radical cations in γ-irradiated frozen Freon-113 (CFCl₂CF₂Cl) matrix was suggested on the basis of ESR data. The rearrangement was found to occur via distonic form of the radical cations with spin and charge separation. Furthermore, it was shown that the primary radical cations abstracts hydrogen atom from methylene group of the parent molecule, whereas distonic radical cations reacts via attachment to the C=C bond at 110–119 K.