Epithermal Electron Ranges and Thermal Electron Mobilities in Liquid Aromatic Hydrocarbons

1974 ◽  
Vol 52 (20) ◽  
pp. 3495-3506 ◽  
Author(s):  
Kyoji Shinsaka ◽  
Gordon R. Freeman

Radiolysis free ion yields were measured as functions of electric field strength and temperature in benzene, toluene, 1,2-, 1,3-, and 1,4-dimethylbenzene, 1,2,3-, 1,2,4-, and 1,3,5-trimethylbenzene, 1,2,3,4- and 1,2,4,5-tetramethylbenzene, pentamethylbenzene, hexamethylbenzene, naphthalene, and anthracene. Secondary electron ranges bGP were estimated from the yields. The density-normalized ranges bGPd were almost constant, 34−38 × 10−8 g/cm2, from benzene up to the tetramethylbenzenes, then increased to 47 × 10−8 in pentamethyl- and 52 × 10−8 in hexamethylbenzene. In naphthalene and anthracene the normalized ranges were 32 and ∼20 × 10−8 g/cm2, respectively. Electron mobilities in the liquids at 293 K, and their activation energies, expressed in (cm2/V s, kcal/mol) were: benzene (0.114, 7.4); toluene (0.063, 3.4); 1,2-dimethylbenzene (0.018, 4.4); 1,3-dimethylbenzene (0.057, 4.5); 1,4-dimethylbenzene (0.062, —); 1,2,3-trimethylbenzene (0.022, 4.8); 1,2,4-trimethylbenzene (0.035, 4.3); 1,3,5-trimethyl-benzene (0.17, 3.2); 1,2,3,4-tetramethylbenzene (∼0.02, 5). The mobilities reflect migration retarding influences of the aromatic ring and molecular asymmetry, and a slight ring-shielding effect of methyl groups that tends to enhance the mobility.

1992 ◽  
Vol 70 (2) ◽  
pp. 327-332
Author(s):  
Takehisa Yoshinari ◽  
Norman Gee ◽  
Gordon R. Freeman

Free ion yields [Formula: see text], were measured at electric field strengths E up to 6.7 MV m−1 in liquid isobutane at 556 ≤ d/kg m−3 ≤ 739 (294.4–114.6 K). The yields decreased with decreasing temperature and increasing density up to 677 kg m−3; further increases in density led to little change in [Formula: see text]. The thermalization distance distribution F(y) was estimated by fitting the field dependence of [Formula: see text] using the extended On sager model. At lower densities F(y) = YGP (three-dimensional Gaussian body with power tail) provided an adequate fit to the results, while at higher densities F(y) = YE (one-dimensional exponential distribution) was better. Thus the electron-scattering properties of liquid isobutane change somewhat with density. The thermalizing ability of liquid isobutane increased with increasing density up to ~660 kg m−3, then decreased at densities > 690 kg m−3. By comparison, the Arrhenius temperature coefficient of mobility of thermal electrons changed in the same density region: Eμ ≈ 7 kJ mol−1 at d < 660 kg m−3, and ≈ 16 kJ mol−1 at d > 690 kg m−3. Keywords: isobutane, electron thermalization distance, free ion yield, liquid, electron mobility, radiolysis.


1975 ◽  
Vol 53 (18) ◽  
pp. 2714-2728 ◽  
Author(s):  
Kyoji Shinsaka ◽  
Jean-Pol Dodelet ◽  
Gordon R. Freeman

Penetration ranges bGp of secondary electrons into 21 X-irradiated liquids were estimated from measured free ion yields. The density normalized ranges bGpd are independent of temperature. Increasing the molecular symmetry by creating one or more cycles in the molecule causes the normalized range to increase, provided that the amount of bond distortion due to strain remains small. Ranges are smaller in compounds that contain strained rings. Energy transfer from the secondary electrons to the molecules is enhanced by the presence of distorted bonds in the molecules. The ranges in olefins are affected by the same factors as those in saturated hydrocarbons, with the addition of a contribution of transient negative ion states to the energy transfer processes. Shielding the double bond by methyl groups is not effective; the effect of the added methyl groups on the molecular symmetry is a more important factor. The magnitude of the energy transfer interaction is an inverse function of molecular symmetry.The general correlation between bGp and thermal electron mobilities ue in liquids contains significant variations within it. For a given value of bGp, ue in different liquids increases in the order n-alkane < cycloalkane < cycloalkene < 1,4-cyclohexadiene or benzene. Arrhenius plots of ue in cyclic olefins curve downwards at low temperatures, due to the formation of a deeper trapped state of the electron. The trap is deepest in 1,4-cyclohexadiene (21 kcal/mol) and is attributed to an equilibrium between solvated electrons and anions at temperatures below about 280 K.


2017 ◽  
Vol 68 (1) ◽  
pp. 116-120
Author(s):  
Iuliean Vasile Asaftei ◽  
Neculai Catalin Lungu ◽  
Lucian Mihail Birsa ◽  
Ioan Gabriel Sandu ◽  
Laura Gabriela Sarbu ◽  
...  

The conversion of n-heptanes into aromatic hydrocarbons benzene, toluene and xylenes (BTX), by the chromatographic pulse method in the temperature range of 673 - 823K was performed over the HZSM-5 and Ag-HZSM-5 zeolites modified by ion exchange with AgNO3 aqueous solutions. The catalysts, HZSM-5 (SiO2/Al2O3 = 33.9), and Ag-HZSM-5 (Ag1-HZSM-5 wt. % Ag1.02, Ag2-HZSM-5 wt. % Ag 1.62; and Ag3-HZSM-5 wt. % Ag 2.05 having different acid strength distribution exhibit a conversion and a yield of aromatics depending on temperature and metal content. The yield of aromatic hydrocarbons BTX appreciably increased by incorporating silver cations Ag+ into HZSM-5.


In the first paper of this series (Burgoyne 1937) the kinetics of the isothermal oxidation above 400° C of several aromatic hydrocarbons was studied. The present communication extends this work to include the phenomena of ignition in the same temperature range, whilst the corresponding reactions below 400° C form the subject of further investigations now in progress. The hydrocarbons at present under consideration are benzene, toluene, ethylbenzene, n -propylbenzene, o-, m - and p -xylenes and mesitylene.


1977 ◽  
Vol 55 (11) ◽  
pp. 2050-2062 ◽  
Author(s):  
J.-P. Dodelet

Free ion yields have been measured in four hydrocarbon liquids: n-pentane, cyclopentane, neopentane, and neohexane. Each liquid has been studied from room temperature or below up to the critical temperature. Theoretical curves have been calculated using the relation between the free ion yields and the external field strength derived by Terlecki and Fiutak on the basis of an equation by Onsager. Two popular electron range distribution functions, Gaussian and exponential, have been shown not to be an adequate representation of the reality as far as the model used for the calculations is concerned. In order to fit experimental points, both range distribution functions would require a drastic increase in the total ionization yield, Gtot, with temperature increase. This would mean an unrealistic decrease of the ionization potential of the molecule from the melting point up to the critical temperature.It is possible to keep Gtot quite constant and within the range of values obtained by other techniques by extending the Gaussian range distribution function with a (range)−3 probability tail. The most probable range can be normalized for the liquid density. This parameter has been used to obtain information about the behaviour of epithermal electrons in the four alkane liquids from the melting point up to the critical temperature.(1) Normalized penetration ranges of epithermal electrons are dependent on the structure of the molecule in the entire liquid range but differences are smaller at critical than at low temperatures.(2) Normalized penetration ranges of epithermal electrons pass through a maximum in the liquid phase for neopentane, neohexane, and cyclopentane. No maximum is observed for n-pentane.(3) There is no drastic change in the behaviour of epithermal electrons in these alkanes at the critical temperature.


2001 ◽  
Vol 183 (18) ◽  
pp. 5441-5444 ◽  
Author(s):  
Hikaru Suenaga ◽  
Mariko Mitsuoka ◽  
Yuko Ura ◽  
Takahito Watanabe ◽  
Kensuke Furukawa

ABSTRACT Biphenyl dioxygenase (Bph Dox) catalyzes the initial oxygenation of biphenyl and related compounds. Bph Dox is a multicomponent enzyme in which a large subunit (encoded by the bphA1 gene) is significantly responsible for substrate specificity. By using the process of DNA shuffling of bphA1 of Pseudomonas pseudoalcaligenes KF707 and Burkholderia cepaciaLB400, a number of evolved Bph Dox enzymes were created. Among them, anEscherichia coli clone expressing chimeric Bph Dox exhibited extremely enhanced benzene-, toluene-, and alkylbenzene-degrading abilities. In this evolved BphA1, four amino acids (H255Q, V258I, G268A, and F277Y) were changed from the KF707 enzyme to those of the LB400 enzyme. Subsequent site-directed mutagenesis allowed us to determine the amino acids responsible for the degradation of monocyclic aromatic hydrocarbons.


1965 ◽  
Vol 43 (5) ◽  
pp. 1272-1278 ◽  
Author(s):  
J. F. Murphy ◽  
D. E. Baker

Spectrophotometric measurements on solutions of stannic iodide were found to provide evidence for complex formation with aromatic hydrocarbons. Calculations, based on spectra for mixed solutions of benzene and stannic iodide in carbon tetrachloride, yield values of 0.26 for the equilibrium constant (mole fraction), 28 400 1/mole cm for the molar extinction coefficient of the benzene – stannic iodide complex. Kinetic evidence indicates that the order of decreasing complex stabilities is from xylene to toluene to benzene. The formation of stannic iodide – aromatic hydrocarbon complexes provides an explanation for the discrepancy between measured solubilities of stannic iodide in benzene, toluene, and xylene, and the solubilities predicted by the Hildebrand theory of regular solutions.


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