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  • 1975-1979  (896)
  • 1960-1964  (1,189)
  • Industrial Chemistry  (1,581)
  • Nuclear reactions
  • Phosphorus
  • Physical Chemistry
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Material
Years
Year
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  • 1
    Electronic Resource
    Electronic Resource
    Osteomalacia and altered magnesium metabolism in the X-linked hypophosphatemic mouse (1979)
    Springer
    Calcified tissue international 27 (1979), S. 19-26 
    Details
    ISSN: 1432-0827
    Keywords: Bone diseases ; Familial hypophosphatemia ; Magnesium ; Mice ; Phosphorus
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology , Medicine , Physics
    Notes: Summary A new genetic mutant in mice,Hyp, has been proposed as a model for the human disease X-linked hypophosphatemia (the most common form of vitamin D-resistant rickets). The gene is X-linked, dominant, and produces reduced renal tubular reabsorption of phosphate, hypophosphatemia, and dwarfism. Our goal was to evaluate the skeletal changes histologically and to measure chemically the prominant blood and bone minerals to judge the suitability of this mutant as a model for the human disease. Thirteen-week-old hemizygousHyp male mice were compared with their normal littermate controls. TheHyp mice were hypocalcemic, hypophosphatemic, hypermagnesemic, and had elevated plasma alkaline phosphatase. The femur ash weighed less than half the normal ash weight but had a normal Ca:P ratio. The ash composition was high in %Na and K but low in %Mg. The mandibular incisor ash was also low in %Mg. Histologically the femur showed wide osteoid borders and wide epiphyseal plate. Microradiography revealed reduced bone density and enlarged osteocyte lacunae. Skeletal muscle samples, although smaller in theHyp mice, showed no striking alternations in inorganic or total phosphate content, dry weight (as % wet weight), or extracellular fluid space. TheHyp gene in mice seems to produce a condition similar to that of X-linked hypophosphatemia in humans.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02441156
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  • 2
    Electronic Resource
    Electronic Resource
    Determination of phosphorus in copper-phosphorus alloys, by GLC technique (1979)
    Springer
    Chromatographia 12 (1979), S. 212-214 
    Details
    ISSN: 1612-1112
    Keywords: Phosphorus ; Chromatography, gas-liquid ; Alloys, copper
    Source: Springer Online Journal Archives 1860-2000
    Topics: Chemistry and Pharmacology
    Notes: Summary A simple, sensitive, accurate and rapid gas chromatographic method for the quantitative determination of phosphorus in copper-phosphorus alloys is described. The method is based on the chlorination of the sample with carbon tetrachloride in a sealed glass capsule at 550°C. The volatile products are introduced into the gas chromatograph after crushing the capsule in a special device. The method is very quick (ca. 20 min), involves simple manipulations and the error is about ±0.5%.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02411364
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  • 3
    Electronic Resource
    Electronic Resource
    Net changes in element contents of old leaves of two tropical legumes (1979)
    Springer
    Plant and soil 51 (1979), S. 247-256 
    Details
    ISSN: 1573-5036
    Keywords: Nutrient distribution ; Phosphorus ; Tropical legumes
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Changes in absolute contents of nutrient elements of old leaves of two tropical pasture legumes were studied during vegetative growth in order to determine the extent of nutrient reutilization. Over a wide range of P supply, the P contents of old leaves ofDesmodium intortum cv. Greenleaf generally increased slightly with time whereas inMacroptilium atropurpureum cv. Siratro they decreased. In both species, relatively less K than P was retained in old leaves, especially in plants grown at high P supply. In desmodium, contents of N, S, Ca, Mg, B, Zn and Mn in old leaves generally increased with plant age. In Siratro, S content of old leaves decreased, but to a lesser extent than P content, and contents of N, Ca, Mg, B, Zn and Mn either changed little or increased with plant age. The lower net loss of elements from old leaves of desmodium than Siratro was associated with a greater increase over time in dry weight of old desmodium leaves. The losses of elements other than K from old leaves of Siratro and desmodium with time were relatively smaller than those reported for other species. This suggests that these legumes survive restricted supply of such elements from the roots by reducing their growth rather than by reutilizing nutrients in old leaves. By contrast, these plants can continue to grow when K supply from the roots slows or ceases by utilizing K in old tissues for growth of young tissues.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02232887
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  • 4
    Electronic Resource
    Electronic Resource
    Effect of selenium and phosphorus on the growth and chemical composition of raya (Brassica Juncea cos.) (1979)
    Springer
    Plant and soil 51 (1979), S. 485-490 
    Details
    ISSN: 1573-5036
    Keywords: Crude protein ; Fodder ; Nitrogen ; N/S ratio ; Phosphorus ; Protein ; Raya ; Selenium ; S-amino acids
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The effects of Se and P on the dry matter yield and chemical composition of Raya (Brassica juncea Cos. var. R.L. 18) were studied in the green-house. The dry matter yield in P treated and untreated pots increased with Se application upto 2.5 ppm. With further increase in Se dose upto 10 ppm, dry matter yield decreased. The increase in P dose from 0 to 50 ppm increased dry matter yield in all Se treated and untreated pots but 100 ppm P rather showed decrease in dry matter yield as compared to 50 ppm P. The Se concentration increased by about 100 fold with the application of 10 ppm Se over 0 ppm Se where P was not added whereas increase was 258 and 336 times when 50 ppm and 100 ppm P was added, respectively. Inorganic, organic and total P increased with increasing Se and P. The increase in inorganic P was more than organic and total P. S and N concentration decreased with increasing Se application and increased with P application. Crude protein showed the same behaviour as N. The total sulphur-containing amino acids (which ranged from 39 to 49% of crude protein) and individual sulphur-containing amino acids like methionine (16.9 tot 20%) cysteine (9.8 to 13%) and cystine (12.3 to 15.9%) decreased with the increasing selenium but increased with increasing phosphorus. N/S ratio in the plant showed significant negative correlation with total sulphur-containing amino acids (r=−0.940**), methionine (r=−0.951**), cysteine (r=−0.929**) and cystine (r=−0.920*) whereas total sulphur in the plant showed positive significant correlation with methionine (r=0.805**), cysteine (r=0.924**) and cystine (r=0.821**).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02277570
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  • 5
    Electronic Resource
    Electronic Resource
    Changes in phosphorus concentrations in a eutrophic lake as a result of macrophyte-kill following herbicide application (1979)
    Springer
    Hydrobiologia 66 (1979), S. 105-111 
    Details
    ISSN: 1573-5117
    Keywords: Phosphorus ; herbicide ; diquat ; nutrient cycling ; sediment
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract Phosphorus (P) concentrations in water and sediment of a highly eutrophic lake were monitored before and after application of diquat to control the macrophyte Potamogeton crispus. Only a relatively small and short-term increase in P concentration in water occurred shortly after plant die-off resulting from herbicide application. Phosphorus concentrations in shallow water sediments decreased during the summer, and those in deep water sediments increased. Although a large increase in P concentration in the water occurred in late summer, it was not attributed to diquat. No major secondary effects of herbicide application were found during this study.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00032039
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  • 6
    Electronic Resource
    Electronic Resource
    Uptake and distribution of phosphorus in tomato plants (1979)
    Springer
    Plant and soil 51 (1979), S. 331-340 
    Details
    ISSN: 1573-5036
    Keywords: Deficiency ; Distribution ; Fruit ; Glasshouse ; Laminae ; Leaves ; Nitrogen ; Peat ; Petioles ; Phosphorus ; Plant ; Superphosphate ; Symptoms ; Tomato ; Uptake
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The uptake and distribution of phosphorus was examined in tomato plants, cv. Kirdford Cross, grown in peat to which phosphate was added (P2) or omitted (P1). The plants received a liquid feed containing either a high (N2) or low (N1) concentration of ammonium nitrate. Initially, all plants were grown in peat containing an intermediate level of phosphate. There was a rapid net export of P from the leaves of plants transferred to the P1 medium resulting in deficiency symptoms before the fruit on the first truss had ripened. Most of the P absorbed by 11-week-old plants in the N1P2 and N2P2 treatments was located in the developing fruit, in the laminae of the mature leaves and in the lower parts of the stem. In the P1 treatments, the lowest fruit truss was the dominant sink for the limited supply of P, but there was also a significant concentration of P in the shoot apex and in the laminae. Increasing the supply of N to plants in the P2 treatment promoted the transport of P to the shoot and to the fruit trusses and also increased the total P uptake. However, plants in the N2 treatment required a significantly higher level of tissue P to prevent the symptoms of P deficiency occurring in the laminae. Generally, symptoms occurred in laminae of mature leaves containing less than 0.13 per cent P. Increases in concentration of tissue P in response to raising the level of applied P were greatest in the petioles of the mature leaves, and it is suggested that these petioles are the most suitable tissues for the assessment of the P status of tomato plants.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02197780
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  • 7
    Electronic Resource
    Electronic Resource
    Effect of phosphoros nutrition in peat on tomato plant growth and fruit development (1979)
    Springer
    Plant and soil 51 (1979), S. 341-353 
    Details
    ISSN: 1573-5036
    Keywords: Fruit development ; Glasshouse ; Growth ; Nitrogen ; Peat ; Phosphorus ; Protein ; Sand ; Tomato
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The effect of P nutrition on the growth of tomato plants in peat was examined. Initially, plants received an adequate supply of P and then received either nil, 0.78 or 2.34 kg superphosphate per m3 in combination with either 50 μg N/ml (N1) or 300 μg N/ml (N2) as ammonium nitrate in a liquid feed. Vegetative growth was restricted in the lower P treatmentsi.e. inhibited shoot growth, reduced duration of leaf expansion phase, thinner stems and reduced vegetative dry wt. Plants receiving N2 showed a greater restriction in growth compared with N1 plants when the P supply was limiting. P deficiency disrupted protein metabolism in the leaves, in that soluble leaf protein was reduced and trichloroacetic acid-soluble N accumulated. Flower development was accelerated by low P applications but the final numbers of flowers and the fruit-setting efficiency were reduced. Lowering the N supply reduced the fruit yield by 36 per cent while an intermediate P level reduced yields by about 15 per cent. Maximum fruit yields and good vegetative growth occurred when plants contained 0.4 per cent P or above in the mature leaves, and this value was achieved by adding the highest level (2.34 kg/m3) of superphosphate to the peat.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02197781
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  • 8
    Electronic Resource
    Electronic Resource
    Effect of phosphorus on growth and iron nutrition of millet and sorghum (1979)
    Springer
    Plant and soil 51 (1979), S. 551-561 
    Details
    ISSN: 1573-5036
    Keywords: Autoradiography ; Culture solution ; Fe deficiency ; Millet ; P/Fe interaction ; Phosphorus ; Sorghum
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Seedlings of millet (Pennisetum americanum (L) K. Schum var. Tift 23 DA × Tift 18 DB) and guineacorn (Sorghum bicolor (L) Moench var. RS' 702) were employed in growth chamber studies to evaluate the effects of various phosphorus (P) levels on their growth and nutrient composition. The growth medium was Hoagland solution containing 0.0, 0.1, 1.0 and 2.5 mM P and 2.2 mM ferrous sulphate-tartate solution. At the end of twenty-four days, two plants from each treatment were supplied with 0.31 μci/ml of radioactive iron (55Fe) (with the same P levels used to grow them) and then allowed to absorb the55Fe for 3 hours after which they were harvested, separated into roots and shoots. The two components were wet-ashed separately, and assayed for55Fe. The rest of the plants in Hoagland solution were also harvested, separately into roots and shoots. The components parts were also wet-ashed separately and assayed for iron (Fe), manganese (Mn), zinc (Zn), copper (Cu) and phosphorous (P). High P concentration in the growth medium inhibited55Fe absorption and translocation in both millet and sorghum but millet was more tolerant of P-induced Fe deficiency than sorghum. Millet and sorghum grew best at 1.0 and 0.1 mM P, respectively. Fe concentrations in plant declined as P levels increased; while Mn increased in both millet and sorghum with increasing P levels. Millet, however, maintained higher concentrations of Fe and Mn. The distribution patter of55Fe, regardless of P levels could be summarized as follows: Roots〉Vascular tissue〉leaf-sheaths〉leaf blade. Less55Fe was absorbed and translocated to shoots at 2.5 mM P, in millet and sorghum.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02277575
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  • 9
    Electronic Resource
    Electronic Resource
    Water use and phosphorus and potassium status of wheat seedlings colonized byGaeumannomyces graminis orPhialophora radicicola (1979)
    Springer
    Plant and soil 52 (1979), S. 1-8 
    Details
    ISSN: 1573-5036
    Keywords: Gaeumannomyces ; Phialophora ; Phosphorus ; Potassium ; Water use ; Wheat
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary The water consumption and levels of phosphorus, potassium, and total minerals were measured for wheat seedlings colonized byGaeumannomyces graminis var.tritici, Phialophora radicicola var.radicicola, orPhialophora radicicola var.graminicola. Infection byG. graminis resulted in a considerable reduction in water consumption, and reduced level of phosphorus when the supply of phosphorus to the seedlings was plentiful. Colonization byP. radicicola var.radicicola increased levels of phosphorus and potassium, but these increases varied according to the isolate of the fungus and the supply of phosphorus and potassium available to the seedlings. Colonization byP. radicicola var.graminicola resulted in reduced water consumption by the seedlings. The results are discussed in relation to stelar cell wall thickening in wheat roots colonized byP. radicicola, and the effects on nutrient uptake of mycorrhizal root systems.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02197726
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  • 10
    Electronic Resource
    Electronic Resource
    Effect of foliar application of phosphorus on growth and mineral composition in peanut plants (Arachis hypogaea L.) under salt-stress (1979)
    Springer
    Plant and soil 52 (1979), S. 41-48 
    Details
    ISSN: 1573-5036
    Keywords: Foliar fertilization ; Growth ; Leaf area ; Mineral composition ; Peanut ; Phosphorus ; Sand culture ; Stomatal frequency ; Yield
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Peanut (Arachis hypogaea L., Var. TMV-2) plants were raised in sand cultures under natural photoperiod. Salt treatment (0.4% NaCl on dry weight basis) was given 10 days after sowing. Nutrient solution was supplied 15 days after sowing to control and salinized plants. Phosphate (0.1% NaH2PO4 with 0.01% Tween-80) was sprayed to the plants to the drip point once daily from 20th to 25th day and from 30th to 35th day. The plants were harvested at 30th and 40th day for analysis. The plants grown under saline conditions showed a market reduction in growth. When phosphorus was supplied to saline plants by foliar application, there was an increase in dry weight, leaf area, stomatal frequency, and yield and the increase was more marked when the plants received phosphate for two periods. Phosphorus content decreased due to salinity which was restored by foliar spray of phosphate. With salinity, sodium accumulated while potassium and calcium were lowered. Phosphate spray decreased sodium and increased potassium and calcium in general.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02197730
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  • 11
    Electronic Resource
    Electronic Resource
    Effect of algal growth on the availability of phosphorus, iron and manganese in rice soils (1979)
    Springer
    Plant and soil 52 (1979), S. 139-149 
    Details
    ISSN: 1573-5036
    Keywords: Algal growth ; Iron ; Manganese ; Phosphorus ; Rice soils
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary Laboratory experiments were conducted to study the effect of algal growth on the change of (I) pH, (II) available phosphorus and (III) solubility of iron and manganese content in five waterlogged alluvial rice soils of West Bengal, India. The results showed that the algal growth initially caused an increase in the soil pH, which later declined to the original value in some of the soils. The available phosphorus content decreased upto 90 days of their growth and began to increase towards the later period of incubation. The drastic fall of water soluble plus exchaneable manganese content of the soils due to algal growth was accompanied by similar increase in reducible manganese content. No appreciable change in water soluble plus exchangeable ferrous iron content was encountered but theN-NH4OAC(pH 3) extractable iron due to algal growth progressively decreased with the progress of the incubation period.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02184556
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  • 12
    Electronic Resource
    Electronic Resource
    Influence of soil moisture regimes and organic matter application on the extractable Zn and Cu content in rice soils (1979)
    Springer
    Plant and soil 53 (1979), S. 203-213 
    Details
    ISSN: 1573-5036
    Keywords: Alluvial soil ; Alternate waterlogged and saturated ; Copper ; Immobilization ; Interaction ; Iron ; Manganese ; Organic matter ; Phosphorus ; Reduction ; Rice ; Saturated ; Waterlogged ; Zinc
    Source: Springer Online Journal Archives 1860-2000
    Topics: Agriculture, Forestry, Horticulture, Fishery, Domestic Science, Nutrition
    Notes: Summary A laboratory incubation experiment was conducted to study the influence of three moisture regimes,viz (i) waterlogged (W1), (ii) alternate waterlogged and saturated (W2) and (iii) continuous saturated (W3) and two levels of organic matter application,viz (i) 0 (T1) and (ii) 0.5% of the soil (T2) in their all possible combinations on the extractable (N NH4OAC, pH 7.0) zinc and copper in three lowland alluvial rice-growing soils of West Bengal (India). The results showed that the extractable zinc and copper content in soils recorded marked decrease on incubation under all the moisture regimes, but the same was most prominent under the continuous saturated moisture regime (W3), followed by waterlogged (W1) and alternate waterlogged and saturated (W2) moisture regimes. Application of organic matter brought about further decrease in the content of these elements. Organic matter application combined with saturated moisture regime brought about the greatest decrease both in zinc and copper content. The microbiological immobilisation and the antagonistic effect of increased concentration of extractable iron, manganese and phosphorus have been suggested as the possible reasons for the observed decrease of the content of extractable zinc and copper.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF02181891
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  • 13
    Electronic Resource
    Electronic Resource
    Phosphorus in a model pond study: I sediment selection and preparation (1979)
    Springer
    Hydrobiologia 63 (1979), S. 11-15 
    Details
    ISSN: 1573-5117
    Keywords: Fertilizer ; Nutrients ; Soluble Phosphate ; Equilibrium Phosphate Concentration ; Phosphorus ; Pond ; Sediment ; Erosion
    Source: Springer Online Journal Archives 1860-2000
    Topics: Biology
    Notes: Abstract We chose two surface soils with contrasting textures as model sediments for a model pond study. One soil, a calcareous clay, had a relatively high natural phosphate content and a large phosphate adsorption capacity. The second soil, a non calcareous loam, had a relatively low natural phosphate content and a small phosphate adsorption capacity. Chemical characteristics of both soils were roughly proportional to mineral surface area. Pasture sites of each soil were tilled to a depth of 15 cm and two plots at each site were fertilized by hand with triple superphosphate. A third plot at each site was left unfertilized. After fertilization the plots were mechanically mixed and left fallow for 2 to 3 months. Then the plots were resampled and equilibration phosphate concentrations were determined again. Results showed significant phosphate fixation by the clay soil but no fixation by the loam soil.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1007/BF00021012
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  • 14
    Electronic Resource
    Electronic Resource
    Erratum (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 103-104 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110106
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  • 15
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110201
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  • 16
    Electronic Resource
    Electronic Resource
    Neighboring group participation of polar β substituents in the gas-phase pyrolysis of 2-substituted ethyl chlorides (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 109-115 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of 2-dimethylaminoethyl chloride in the temperature range of 360-400°C and the pressure range of 60-271 mmHg is a homogeneous, unimolecular, first-order reaction giving dimethylvinyl amine and hydrogen chloride. 2-Methoxyethyl chloride pyrolysis in the temperature range of 450-490°C and the pressure range of 53-110 mmHg by a similar unimolecular, first-order reaction yields methylvinyl ether and hydrogen chloride. These reactions were carried out in a seasoned reaction vessel and in the presence of a propene inhibitor. The methylvinyl ether decomposes slowly into other products at the temperature of pyrolysis. The rate constants are given by the Arrhenius equations(a) 2-dimethylaminoethyl chloride: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (13.22 \pm 0.17) - (203.7 \pm 2.1)kJ/mol/2.303RT $$\end{document}(b) 2-methoxyethyl chloride: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = (14.06 \pm 0.53) - (244.7 \pm 7.1)kJ/mol/2.303RT $$\end{document}The effects of polar β substituents in the 2 position of ethyl chloride are discussed in terms of anchimeric assistance and electron-withdrawing deactivation in these elimination reactions. The present results are consistent with the heterolytic nature of the four-centered cyclic transition state for the gas-phase pyrolysis of alkyl halides.
    Additional Material: 4 Tab.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110202
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  • 17
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism for the iodination of methylmalonic acid (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 131-145 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction\documentclass{article}\pagestyle{empty}\begin{document}$ CH\left({CH_3 } \right)\left({COOH} \right)_2 + I_2 \rightleftharpoons CI(CH_3)\left({COOH} \right)_2 + H^ + + I^ - $\end{document} was followed spectrophotometrically at 353 nm and 470 nm at 25°C under various conditions of pH and methylmalonic acid concentration. The equilibrium constant for the reaction is 0.11 ± 0.02. An iterative technique was used to integrate postulated rate equations. Agreement between experimental and calculated absorbance versus time curves was generally better than 0.005 A (approximately 5% of maximum) at both wavelengths for a mechanism where the rate-determining step is formation of an enolate (k = 1.63 Θ 10-4 ± 0.03 Θ 10-4 sec-1). The enolate may be rapidly transformed to the enol or enol carboxylate anion depending on the pH. All three forms are rapidly iodinated. The mechanism of general base catalysis is supported by rate increases proportional to base concentration in buffer solutions. The bases, acetate ion, chloracetate ion, sulfate ion, dichloracetate ion, and water, follow a Brønsted relationship with β = 0.7.
    Additional Material: 2 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110205
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  • 18
    Electronic Resource
    Electronic Resource
    Kinetics of oxidation of some amino acids by KMNO4 in a moderately concentrated H2SO4 medium in the presence and absence of Ag+ (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 165-173 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of glycine, alanine, phenylalanine, serine threonine, aspartic, and glutamic acid by acid permanganate were investigated to elucidate the mechanism of the reactions. The rate law was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - d[Mn\left({VII} \right)]}}{{dt}} = k_0 [a\min oacid][Mn\left({VII} \right)] $$\end{document} The reactions were found to be acid catalyzed, and the kinetic data indicate the participation of the water molecules in the rate-determining step as a proton-abstracting agent from the substrate, as per Bunnett's hypothesis. As Ag+ was found to catalyze these reactions, the oxidation of glycine and glutamic acid was studied, and the rate law was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ \frac{{ - d\ln [Mn\left({VII} \right)]}}{{dt}} = \frac{{Kk_c^{''} [a\min oacid][Ag^ +]}}{{1 + K[a\min oacid] = K[Ag^ +]}}$$\end{document} A probable mechanism consistent with the observed results is discussed.
    Additional Material: 1 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110208
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  • 19
    Electronic Resource
    Electronic Resource
    Competitive chlorination-dehydrochlorination of 1,1,1,2-C2H2Cl4 (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 117-124 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The competitive photochlorination and chlorine photosensitized dehydrochlorination of 1,1,1,2-C2H2Cl4 have been studied over the temperature range of 349.4-404.5 K after less than 1% conversion. The results are discussed and a value of \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_{4A} (\sec ^{ - 1}) = (11.6\pm 0.6) - (16,400\pm 1000)/4.58T $$\end{document} is proposed for the reaction \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm CCl}_{\rm 3} {\rm CHCl}\mathop \to \limits^{(4{\rm A)}} {\rm CCl}_{\rm 2} {\rm CHCl + Cl} $$\end{document} This result, combined with existing thermochemical data, indicates that there is no evidence of an activation energy for the addition of a Cl atom on the most chlorinated carbon in trichloroethylene: in that case the selectivity of the addition of Cl on the less chlorinated carbon should not depend on temperature.
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    URL: http://dx.doi.org/10.1002/kin.550110203
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    Electronic Resource
    Pressure saturation of SO2(3B1 0,0,0) lifetimes (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 125-130 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Lifetime data have been obtained for the decay of SO2(3B1 0,0,0) at 25°C over the pressure range of 1-762 torr. The 3B1 state was populated by direct absorption to eliminate any possible complications in interpretation due to the participation of excited-singlet manifolds. At pressures greater than about 10 torr, the measured lifetimes are longer than predicted from low-pressure Stern-Volmer parameters. This deviation can be interpreted in terms of Freed's theory on collisionally induced intersystem crossing and provides unequivocal evidence to support earlier speculations that the lengthening of the lifetimes at high pressures is due to saturation in depopulation of the 3B1 state.
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  • 21
    Electronic Resource
    Electronic Resource
    Mechanistic details of the Belousov-Zhabotinsky oscillations. II. The organic reaction subset (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 155-164 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Our previous mechanistic model for the Belousov-Zhabotinsky reaction has been revised to include a more realistic set of reactions for the oxidation pathways of the organic intermediates. A few other rate constants have also been modified to include new information. The revised mechanism reproduces the essential experimental observations, although the periods of oscillation are somewhat too long and oscillations cease at malonic acid concentrations about ten times greater than the observed lower limit. However, the essential features of the mechanism are clearly understood.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110207
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  • 22
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110301
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  • 23
    Electronic Resource
    Electronic Resource
    The kinetics and mechanism of n-butyraldehyde photolysis in the vapor phase at 313 nm (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 219-237 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The photolysis was investigated at 313 nm wavelength, 253-529 K temperatures, and 4 × 10-11-2 × 10-9 mol·photon/cm2·sec light intensities by determining the quantum yields of 20 reaction products. Primary quantum yields for the seven primary processes and rate constant ratios, rate constants, and Arrhenius parameters for secondary processes were derived on the basis of the suggested reaction scheme. The dependence of the quantum yields of the four major primary processes on experimental conditions was established.
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    URL: http://dx.doi.org/10.1002/kin.550110302
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  • 24
    Electronic Resource
    Electronic Resource
    Kinetics and mechanism of oxidation of dimethyl sulfoxide by chloramine-T in aqueous solution (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 261-273 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of dimethyl sulfoxide (DMSO) by chloramine-T (CAT) is studied in HClO4 and NaOH media with OsO4 as a catalyst in the latter medium. In acid medium, the rate law is -d [CAT]/dt = k [CAT][DMSO][H+]. Alkali retards the reaction and the rate law takes the form -d [CAT]/dt = k [CAT][DMSO][OsO4]/[NaOH], but is reduced to -d [CAT]/dt = k [CAT][DMSO] at higher alkali concentrations. The reaction is subjected to changes in (a) ionic strength, (b) concentrations of added neutral salts, (c) concentrations of added reaction product, (d) dielectric constant, and (e) solvent isotope effect, and the subsequent effects on the reaction rate are studied.The reaction mechanism in acid medium assumes an electrophilic attack by the free acid RNHCl (CAT′) at the sulfur site in DMSO, forming a reaction intermediate which subsequently decomposes to dimethyl sulfone on hydrolysis. Formation of a cyclic complex between RNHCl and OsO4 which interacts with the substrate in a slow step explains the observed results in alkaline medium. The simplification of the rate equation at higher alkali concentrations is attributed to a direct reaction between chloramine-T and the substrate.
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  • 25
    Electronic Resource
    Electronic Resource
    Rate constants for the combination of trichloromethyl radicals and the electron-transfer reaction between hydroxymethyl radicals and carbon tetrachloride in solution (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 495-509 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the bimolecular combination of trichloromethyl radicals in methanol is determined as a function of temperature by steady-state kinetics and electron-spin resonance with modulated radical initiation. The rate constant is in accord with the Smoluchowski equation and indicates a diffusion-controlled radical termination. The temperature dependence of the rate constant for the electron-transfer reaction between hydroxymethyl radicals and carbon tetrachloride in methanol is determined, and is found to disagree with predictions of the Marcus theory. This disagreement is tentatively ascribed to the structure of the transition state.
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    URL: http://dx.doi.org/10.1002/kin.550110504
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  • 26
    Electronic Resource
    Electronic Resource
    A model for explosions during carbon monoxide oxidationPaper 32 in the Series Oscillations in Chemical Systems. For Paper 31 see [1]. (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 821-841 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: During the oxidation of carbon monoxide containing a trace of water, ten well-known atomic and molecular species can be identified as of potential significance. All conceivable reactions of these species in their ground electronic states were considered, and rate constants for all those that are of potential importance are either known or can be estimated with considerable confidence. For compositions and temperatures of experimental interest an isothermal system goes to a single steady state that is stable to perturbation and will neither explode nor oscillate. These steady-state computations also predict that as the temperature is raised above about 1000 K most of the water is converted to H, OH, and HO2 radicals. Under such conditions, exothermic reactions would be so rapid that strong thermal gradients would develop in any real system of plausible dimensions. A simple model based on these calculations predicts explosion limits consistent with those observed experimentally. Simultaneous behavior in time and in space must be calculated in detail before it is clear whether or not this model based on ground electronic states can model the oscillations that are sometimes observed in this system.
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  • 27
    Electronic Resource
    Electronic Resource
    Estimating the positions of transition states from experimental data (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 853-865 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A procedure is suggested to estimate the positions of a transition state (TS) along the reaction coordinate in reaction series involving several radical reactions. It is based on the dependence between experimental activation energies U± and heat effects Q. Taking into account the shift of a TS position, the following relation between these quantities is obtained: U± -; U0± = A (Q - Q0)2 + B(Q - Q0). The subscript 0 indicates the standard reference reaction. For three series, namely, the hydrogen abstraction from hydrocarbon substrates by radicals CH3·, CF·3, and Br·, the bond lengths characterizing the TS reaction center are evaluated. The TS positions appear to vary significantly in the reaction series, which accounts for significant changes in the experimentally observed activation volumes. The derivation of the Hammond rule and the range of its validity for the series with polar and steric substituent effects are discussed.
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  • 28
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    Abstraction of chlorine atoms from chloroalkanes. V. The liquid-phase reaction between Et3SiH radicals and CH2Cl2, CHCl3, CCl4, and CCl3CN (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 899-906 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of chlorine transfer from CH2Cl2, CHCl3, CCl4, and CCl3CN to the triethylsilyl radical was studied in the liquid phase by a competitive method. Br abstraction from 1-bromopentane was used as a reference. The following Arrhenius parameters were determined:where the error limits are two standard deviations (2σ). Based on these results, the observed reactivity trends in the chlorine transfer reactions of Et3Si radicals appear to primarily reflect the variation in entropy of activation rather than in activation energies.
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    URL: http://dx.doi.org/10.1002/kin.550110808
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  • 29
    Electronic Resource
    Electronic Resource
    Mutual combination of ClO radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 649-664 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The mutual combination reaction is proposed as the rate-limiting step in the removal of ClO radicals at moderate pressures. The third--order rate constants measured at room temperature were k1(Ar) = 3.51 ± 0.14 × 109 l2/mol2·ec; k1(He) ≈ 2.8 × 109 l2/mol2·sec, and k1(O2) ≈ 7.9 × 109 l2/mol2·sec. There is also an independent second-order reaction for which k3 ≈ 8 × 106 l/mol·sec. A new absorption spectrum has been observed in the ultraviolet and attributed to Cl2O2. The extinction coefficient for Cl2O2 has been measured at six wavelengths, and, between 292 and 232 nm, it increases from 0.4 × 103 to 2.9 × 103 l/mol·cm. In the presence of the chlorine atom scavengers OClO or Cl2O, Cl2O2 exists in equilibrium with ClO. The equilibrium constant Ke1 = 3.1 ± 0.1 × 106 l/mol at 298 K, and, with ΔS10 estimated to be -133 ± 11 J/K·mol, ΔH10 = -69 ± 3 kJ/mol and ΔHf0(Cl2O2) = 136 ± 3 kJ/mol.
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    URL: http://dx.doi.org/10.1002/kin.550110611
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  • 30
    Electronic Resource
    Electronic Resource
    Quantum effects and isotope effects in chemical kinetics (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 665-683 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The relations of quantum and kinetic isotope effects are investigated using the exact quantum corrections to the collision and activated complex theories. The latter are computed for the collinear three-atomic reaction H2 + H → H + H2 and the related isotopic reactions using realistic potential energy surfaces. Taking into account the bent configurations of the collision complex H-H-H gives a very good agreement between the quantum collision theory and the experimental data for the absolute values and the isotopic ratios of rate constants. Classical trajectory calculations yield considerably lower results.
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    URL: http://dx.doi.org/10.1002/kin.550110612
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  • 31
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110501
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  • 32
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    Study of the reactions of oxygen atoms with carbonothioicdichloride, carbonothioicdifluoride, and tetrafluoro-1,3-dithietane (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 453-460 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of ground-state oxygen atoms with carbonothioicdichloride, carbonothioicdifluoride, and tetrafluoro-1,3-dithietane have been studied in a crossed molecular jet reactor in order to determine the initial reaction products and in a fast-flow reactor in order to determine their overall rate constants at temperatures between 250 and 500 K. These rate constants arek(O + C2CS) =(3.09 ± 0.54) × 10-11 exp(+115 ± 106 cal/mol/RT),k(O + F2CS) = (1.22 ± 0.19) × 10-11 exp(-747 ± 95 cal/mol/RT), andk(O + F4C2S2) = (2.36 ± 0.52) × 10-11 exp(-1700 ± 128 cal/mol/RT) cm3/molec·sec. The detected reaction products and their rate constants indicate that the primary reaction mechanism is the electrophilic addition of the oxygen atom to the sulfur atom contained in the reactant molecule to form an energy-rich adduct which then decomposes by C-S bond cleavage.
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  • 33
    Electronic Resource
    Electronic Resource
    The reactions of methyl radicals with chloromethanes (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 511-527 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction of methyl radicals with CCl4 and CCl3Br have been reinvestigated in the gas phase over a wide range of temperatures and pressures using both the photolysis of acetone and the pyrolysis of di-tertiary butyl peroxide (dtBP) as the methyl radical sources. The results are in essential agreement with previous work; however, these new studies provide evidence that at higher pressures the major source of HCl in the reactions is due to methyl radical attack on CH3CCl3, formed via the combination of methyl and trichloromethyl radicals.From these investigations Arrhenius parameters for the reactions have been determined: \documentclass{article}\pagestyle{empty}\begin{document}$$ k_2 = 10^{8.8 \pm 0.3} {\rm exp - }\left({\frac{{{\rm 10}{\rm .1} \pm {\rm 0}{\rm .5}\,{\rm kcal}}}{{RT}}} \right)1/{\rm mol} \cdot {\rm sec} $$\end{document} \documentclass{article}\pagestyle{empty}\begin{document}$$ k_{15} { } = { 10}^{8.1 \pm {0}{.3}} { exp - }\left({\frac{{{3}{.5 } \pm { 0}{.5 kcal}}}{{RT}}} \right){ 1/mol} \cdot {sec} $$\end{document}Pyrolysis of dtBP in the presence of relatively high-pressure mixtures of CCl4 and CCl3Br resulted in no enhanced methane formation, since, under these conditions, the only termination product is C2Cl6, and the HCl precursor CH3CCl3 is not formed. A competitive technique has been used in which dtBP was pyrolysed in the gas phase in the presence of high-pressure mixtures of CCl3Br and a chloromethane. Arrhenius parameters were obtained for the reactions and the results were used to provide information on the importance of polar effects for hydrogen abstraction from halogenated methanes.
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    URL: http://dx.doi.org/10.1002/kin.550110505
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  • 34
    Electronic Resource
    Electronic Resource
    Chlorine atom and ClO wall reaction products (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 543-557 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The products of the heterogeneous reactions of chlorine atoms and chlorine oxide radicals with acid coated Pyrex walls have been directly determined for the first time. Contrary to the usual assumption that chlorine atoms recombine to form Cl2, we find that the major product is HCl, with small amounts of perchlorate also formed. Similarly, ClO radicals form HCl rather than Cl2. The source of hydrogen for these reactions is probably the water always found in this type of vacuum system. These results may change the interpretation of flow tube experiments with chlorine atoms. Application to the H + HCl reaction is discussed as an example.
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  • 35
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    Electronic Resource
    Effect of substituents in the gas-phase elimination kinetics of β-substituted ethyl acetates (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 561-567 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of gas-phase elimination of 3-methyl-1-butyl acetate and 3,3-dimethyl-1-butyl acetate into acetic acid and the corresponding substituted butenes have been measured over the temperature range of 360-420°C and the pressure range of 63-250 Torr. The reactions are homogeneous in both clean and seasoned vessels, obey first-order law, and are unimolecular. The temperature dependence of the rate constants is given by the Arrhenius equation3-methyl-1-butyl acetate: \documentclass{article}\pagestyle{empty}\begin{document}$$ {log k(sec}^{{ - 1}} {) = (12}{.73 } \pm { 0}{.29) - (202}{.5 } \pm { 3}{.8) kJ/mol/2}{.303}RT $$\end{document}3,3-dimethyl-1-butyl acetate: \documentclass{article}\pagestyle{empty}\begin{document}$$ {log k(sec}^{{ - 1}} {) = (12}{.34 } \pm { 0}{.35) - (194}{.1 } \pm { 4}{.2) kJ/mol/2}{.303}RT $$\end{document} The points in a plot of log (k/k0) of β-alkyl and several β-substituted ethyl acetates against Es values appear aligned in an approximate linear relationship. These results may be interpreted as a consequence of steric effects, namely, steric accelerations.
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    Electronic Resource
    Photosensitized decomposition of hydrocarbons by infrared-laser-induced energy transfers (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 595-604 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using the technique of CO2 laser photosensitized decomposition, ethane and propane decomposition was investigated in relation to energy transfer from an SF6 photosensitizer to the hydrocarbon. The end products appearing in the course of irradiation are similar to those formed during classical thermal pyrolysis. The energy transfer from SF6 to the hydrocarbon is closely related to hydrocarbon decomposition. A similar overall kinetic behavior for the two alcanes allows the use of a general diffusional kinetic treatment, provided pressure, intensity, and duration of irradiation are well defined.
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    URL: http://dx.doi.org/10.1002/kin.550110606
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    Kinetics of the reaction HO2 + NO2(+M) = HO2NO2 using molecular modulation spectrometry (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 635-648 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants for the reaction HO2 + NO2(+ M) = HO2NO2(+ M) have been obtained from direct observations of the HO2 radical using the technique of molecular modulation ultraviolet spectrometry. HO2 was generated by periodic photolysis of Cl2 in the presence of excess H2 and O2, and k1 was determined from the measured concentrations and lifetime of HO2 with NO2 present. k1 increased with pressure in the range of 40-600 Torr, and a simple energy transfer model gave the following limiting second- and third-order rate constants at 283 K: k1∞ = 1.5 ± 0.5 × 10-12 cm3/molec·sec and k1III = 2.5 ± 0.5 × 10-31 cm6/molec·sec. The ultraviolet absorption spectrum of peroxynitric acid was also recorded in the range of 195-265 nm; it showed a broad feature with a maximum at 200 nm, σmax = 4.4 × 10-18 cm2.
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  • 38
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    The kinetics and the mechanism of the thermal decomposition of bis-pentafluorosulfurtrioxide (SF5OOOSF5) (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 613-619 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of SF5O3SF5 has been investigated between 5 and 25°C. In the presence of sufficient high pressures of O2 the only products formed are SF5O2SF5 and O2: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm SF}_5 {\rm O}_3 {\rm SF}_5 { } \to { SF}_{5} {O}_{2} {SF}_{5} { + (}{\raise0.5ex\hbox{$\scriptstyle {1}$} \kern-0.1em/\kern-0.15em\lower0.25ex\hbox{$\scriptstyle {2}$}}{) O}_{2} {, }\Delta n{ = }{\raise0.5ex\hbox{$\scriptstyle {1}$} \kern-0.1em/\kern-0.15em \lower0.25ex\hbox{$\scriptstyle 2$}} $$\end{document} The reaction is homogeneous. Its rate is strictly first order with respect to the trioxide pressure and independent of the total pressure of the reaction products and of oxygen above a certain limiting pressure: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{{\rm d}[{\rm SF}_5 {\rm O}_3 {\rm SF}_5 ]}}{{{\rm dt}}}{ = + }\frac{{{\rm d}[{\rm SF}_5 {\rm O}_2 {\rm SF}_5 ]}}{{{\rm dt}}}{ = 2}\frac{{{dp}}}{{{\rm dt}}}{ = k[SF}_{5} {O}_{3} {SF}_{5} {]} $$\end{document} The experimental results can be explained with the following mechanism: In the presence of O2 〉 100 Torr the concentration of SF5 is insignificantly small. Therefore reactions (5) and (6) do not have to be considered any more, and steps (2) and (2′) will be of no importance. From reactions (1)-(4) it follows: \documentclass{article}\pagestyle{empty}\begin{document}$$ - \frac{{d[{\rm SF}_{\rm 5} {\rm O}_{\rm 3} {\rm SF}_{\rm 5} ]}}{{dt}} = + \frac{{d[{\rm SF}_{\rm 5} {\rm O}_{\rm 2} {\rm SF}_{\rm 5} ]}}{{dt}} = k_1 \frac{{[{\rm SF}_{\rm 5} {\rm O}_{\rm 3} {\rm SF}_{\rm 5} ]}}{{1 + k'_1 (1/2k_3 k_4 )^{1/2} }}k({\rm sec}^{{\rm - 1}}) = k_1 /\left[ {1 + k'_1 \left({\frac{1}{{2k_3 k_4 }}} \right)^{1/2} } \right] = 10^{16.06 \pm 0.37} {\rm exp( - 26,000} \pm {\rm 500}\,{\rm cal)/1}{\rm .987 }T $$\end{document}The numerical value of the factor [1 + (k′12/2k3k4)1/2] is small. It can be estimated that E3 ≃ 2 ± 1 kcal; therefore, E - E1 ≤ 1 kcal, and D (SF5O—O2SF5) = (26 - 1) ± 1.0 kcal.
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  • 39
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    Pyrolytic production of Se (3P) from carbon diselenide. II. Rate of CSe2 decay (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1109-1130 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Pyrolytic decay of carbon diselenide was monitored by ultraviolet absorption spectroscopy in reflected shock waves in the temperature range of 1600-2600°K. The temperature dependence of the absorption coefficient of CSe2 at 2308 Å was determined and was used to provide kinetic information along with a deconvolution procedure which accounted for and removed systematic distortions of the fast time-resolved absorbance profile. For temperatures of 1600-2600°K and argon densities of 1.5-7.0 × 10-5 mol/cm3 dilute (1.0-9.0 × 10-9 mol/cm3) CSe2 pyrolyzed with measured first-order decay rates in the range of log10 k1 (sec-1) = 3.0-5.7; at midrange (2100°K and 4.3 × 10-5 mol/cm3 in Ar) k1 ≈ 3 × 104 sec-1. The decay probably occurs via a unimolecular low-pressure process, first order in both CSe2 and Ar, for which k2 ± 109 cm3/mol·sec at 2100°K. The deconvoluted data yield Arrhenius activation energies of 53.2 kcal/mol under second-order treatment, but the activation energy is less reliable than the general magnitude of the rate constant. A comparison of CSe2 with other molecules which are isoelectronic in their valence shells (CO2, CS2, OCS, and N2O) is made.
    Additional Material: 13 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550111009
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    Electronic Resource
    Electronic Resource
    Sensitivity and uncertainty of reaction mechanisms for photochemical air pollution (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1137-1162 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A sensitivity/uncertainty analysis is performed on a mechanism describing the chemistry of the polluted troposphere. General features of the photochemical reaction system are outlined together with an assessment of the uncertainties associated with the formulations of mechanistic details and rate data. The combined effects of sensitivity and uncertainty are determined using the Fourier amplitude sensitivity test (FAST) method. The results of this analysis identify the key parameters influencing the chemistry of NO2, O3, and PAN. Based on these findings, a series of recommendations are made for future experimental kinetic studies.
    Additional Material: 8 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550111102
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  • 41
    Electronic Resource
    Electronic Resource
    Redox kinetics of metal complexes in nonaqueous solutions. V. Kinetics and mechanism of the iron (II) reduction of the acetylacetonates of manganese (III) and cobalt (III) in acetonitrile (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 741-756 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The electron transfer step of the reduction of Mn(acac)3 and Co(acac)3 by Fe(II) in acetonitrile is preceded by the one-ended dissociation of an acac ligand and the formation of a binuclear bridged complex. After the electron transfer has taken place through the bridging ligand, the complex dissociates into the products M(acac)2 (M = Mn, Co) and Fe(acac)2+. These primary reaction products could not be identified, since the transfer of acac from M(acac)2 to Fe(acac)2+ is too rapid, producing ultimately Fe(acac)3 and M2+. The M(III)-oxygen cleavage is accelerated by M(acac)2. Furthermore, the dissociation of the binuclear intermediate is catalyzed by the M(acac)3 reactant. Mn(acac)3 is reduced more than a thousand times faster than Co(acac)3.
    Additional Material: 9 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110707
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  • 42
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550111201
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  • 43
    Electronic Resource
    Electronic Resource
    Addition of trichloromethyl radicals to tetrachloroethylene (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1263-1269 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The gamma-radiation-induced free-radical chain reactions in liquid CCl4—C2Cl4—c—C6H12 mixtures were studied in the temperature range of 363-448°K. The main products in this system are chloroform, hexachloropropene and chlorocyclohexane. These products are formed via reactions (1)-(5): with G values (molec/100 eV) of the order of magnitude of 102 and 103 at the lowest and highest temperatures, respectively. Values of k2/k1 were determined from the product distribution. In turn, these values gave the following Arrhenius expression for k2/k1 (θ = 2.303RT, in kcal/mol): \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 /k_1 = ( - 1.21 + 0.10) + (1.59 \pm 0.27)/\theta $$\end{document} From this result and the previously determined Arrhenius parameters of reaction (1), k2 is found to be given by \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }\,k_2 (1/{\rm mol} \cdot {\rm sec) = 7}{\rm .58 - 9}{\rm .49/}\theta $$\end{document}.
    Additional Material: 1 Ill.
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  • 44
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    Electronic Resource
    Comments on the paper “reaction between nitrous acid and hydrogen peroxide in perchloric acid medium” (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 339-341 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: No Absract.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110310
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  • 45
    Electronic Resource
    Electronic Resource
    Bimolecular self-reactions of phenyl-substituted phenoxyl radicals studied by flash photolysis (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 357-374 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate, equilibrium, and thermodynamic data for reaction (1) of 2,6-diphenyl-4R-phenoxyl radicals, where R==OCH3 (I), Ph (II), OC2H5 (III), O-n-C18H37 (IV), and 2,6-dicyclohexyl-4-phenylphenoxyl radical (V), in various solvents are obtained. The k1 values of radicals I to V are within (5.5 ± 1.0) × 107-(1.4 ± 0.3) × 109M-1·sec-1 in propanol. The solvent effect on k1 for radicals I and II was studied. The dimerization of radical I is diffusion-controlled in all solvent studies. The dimerization of radical II is viscosity-dependent but not diffusion-controlled. Plots of k1 against ET have a V shape. Specific solvent-solute interactions are seeming to be responsible for numerical k1 values of radicals I and II. The solvent effect is more pronounced for “slow” dimerization of radicals II than for “fast” dimerization of radicals I. The minimum k1 values correspond to pyridine and chloroform. The reaction (1) rate strongly depends upon the composition of a chloroform (S)-cosolvent binary mixture. Besides reaction (1) the following reactions proceed in binary mixture: \documentclass{article}\pagestyle{empty}\begin{document}$$ K_{14} = 0.18 \pm 0.05M^{ - 1},k_{15} = (2.0 \pm 1.0) \times 10^8 M^{ - 1} \cdot \sec ^{ - 1} $$\end{document} (radical I, S-CCL4 mixture) \documentclass{article}\pagestyle{empty}\begin{document}$$ K_{14} = 0.9 \pm 0.2M^{ - 1},k_{15} = (1.2 \pm 0.5) \times 10^7 M^{ - 1} \cdot \sec ^{ - 1} $$\end{document}(radical II, S-C6H14 mixture) \documentclass{article}\pagestyle{empty}\begin{document}$$ K_{14} = 0.45 \pm 0.10M^{ - 1},k_{15} = (9.0 \pm 2.0) \times 10^6 M^{ - 1} \cdot \sec ^{ - 1} $$\end{document}(radical II, S-CCL4 mixture)In all cases k16 ≪ k15. Factors influencing dimerization rates in strongly nonideal mixtures CH3OH-CCL4 and CH3OH-CHCl3 are discussed.
    Additional Material: 10 Ill.
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  • 46
    Electronic Resource
    Electronic Resource
    Kinetics of cerium (IV) oxidation of mandelic acid. Ionic strength and specific cation effects (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 415-425 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the redox reaction between mandelic acid (MA) and ceric sulfate have been studied in aqueous sulfuric acid solutions and in H2SO4—MClO4 (M+ = H+, Li+, Na+) and H2SO4—MHSO4 (M+ = Li+, Na+, K+) mixtures under various experimental conditions of total electrolyte concentration (that is, ionic strength) and temperature. The oxidation reaction has been found to occur via two paths according to the following rate law: rate = k[MA] [Ce(IV)], where k = k1 + k2/(1 + a)2[HSO4-]2 = k1 + k2/(1 + 1/a)2[SO42-]2, a being a constant. The cations considered exhibit negative specific effects upon the overall oxidation rate following the order H+ ≤ Li+ 〈 Na+ 〈 K+. The observed negative cation effects on the rate constant k1 are in the order Na+ 〈 Li+ 〈 H+, whereas the order is in reverse for k2, namely, H+ ≤ Li+ 〈 Na+. Lithium and hydrogen ions exhibit similar medium effects only when relatively small amounts of electrolytes are replaced. The type of the cation used does not affect significantly the activation parameters.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110407
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  • 47
    Electronic Resource
    Electronic Resource
    Evidence for production of the hydroxycarbonyl radical in the decomposition of formic acid on platinum (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 445-449 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Formic acid molecules highly diluted in argon were passed through a clean platinum screen at 420-730 K and condensed onto an 8-K CsI window. The well-known decomposition products, CO2, CO, and H2O, were observed in the infrared spectra of the resulting matrices. In addition, new absorptions which are attributed to the OCOH free radical were also observed. Experiments with partially deuterated formic acids confirmed that the carbon-hydrogen bond of the formic acid was lost in the formation of the new intermediate species. The activation energy for CO2 production, Ea = 3.5 ± 0.2 kcal/mol, was determined by monitoring its appearance rate at several different catalyst temperatures.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110409
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  • 48
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110401
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  • 49
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    Disproportionation-to-combination ratios for cyclohexyl-h11 and -d11 radicals in the gas phase as determined by the radiolysis of water vapor-cyclohexane mixtures (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 345-355 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: In the radiolysis of water vapor containing small concentrations of cyclohexane, the principal products which account for about 98% of all end products are found to be hydrogen, cyclohexene, and bicyclohexyl. Cyclohexene and bicyclohexyl yields were determined over a range of temperatures (70-200°C), total pressures (50-2400 torr), and total doses (0.15-2.0 Mrad). The disproportionation-combination ratio kdH/kcH for c-C6H11 radicals could be determined as 0.56 ± 0.01 from the ratio of cyclohexene to bicyclohexyl yield. By using c-C6D12, the ratio kdD/kcD for c-C6D11 radicals is found to be 0.38 ± 0.01. Comparison of the reactivity pattern of C6H11 and C6D11 radicals leads to (kdH)/(kcH)/(kdD/kcD) = 1.47 ± 0.02. The corresponding values for the reactions of c-C6H11 with c-C6D11 were also determined.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110402
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  • 50
    Electronic Resource
    Electronic Resource
    A simple preparation of stable, nonreactive surfaces for gas kinetic studies of reactions of hydrogen atoms (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 411-413 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A quartz surface has been prepared for which γ, the mean collisional efficiency for removal of hydrogen atoms, is given by \documentclass{article}\pagestyle{empty}\begin{document}$$ 10^4 \gamma = 0.78 \pm 0.30 $$\end{document} over the temperature range from 315 to 818 K. The preparation “cleans” the surface by contact with 10M aqueous NaOH for ˜ 15 hr and then deactivates it by contact with 10M aqueous HNO3 for ˜15 hr. The surface is stable and long-lived even after prolonged contact with air. Preliminary results show that a similar result can be obtained using Pyrex glass surfaces.
    Additional Material: 1 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550110406
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  • 51
    Electronic Resource
    Electronic Resource
    Automatic sensitivity analysis of kinetic mechanisms (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 427-444 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: An algorithm for the automatic sensitivity analysis of kinetic mechanisms based on the Fourier amplitude sensitivity test (FAST) method of Shuler and co-workers is reported. The algorithm computes a measure of the relative sensitivity of each concentration to each parameter of interest, such as rate constants, Arrhenius parameters, stoichiometric coefficients, and initial concentrations. Arbitrary variations in the magnitude of the parameters are allowable. The algorithm is illustrated for the simple example of computing the sensitivity of the concentration of species A to variation of the two Arrhenius parameters for the hypothetical reaction A + A →.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110408
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  • 52
    Electronic Resource
    Electronic Resource
    The interpretation of pressure-dependent very-low-pressure pyrolysis experiments (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 317-331 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Unimolecular rate data from systems such as very-low-pressure pyrolysis (steady-state flow) and static experiments where gas-gas collisions compete with gas-wall collisions must be interpreted in terms of reactant inhomogeneity arising from finite diffusion rates, rather than using the usual assumption of a well-stirred reactor. An integrodifferential equation describing this process is derived, and a numerical variational solution applicable to weak gas-gas collisions is presented. This gives a powerful method for obtaining collisional energy transfer probabilities from such experiments. Previously reported data (on cyclobutane and cycloheptatriene reactions) are reinterpreted to give conventional values for average energy transfer, replacing the anomalously low collisional efficiencies proposed previously.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110308
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  • 53
    Electronic Resource
    Electronic Resource
    A new mechanism for the reaction of ozone with olefins (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 399-410 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mechanism for ozone-olefin reactions is developed that is consistent with the recent findings of several investigations. These findings suggest a reaction sequence leading to the production of fewer free radical species than has been assumed in the past. Computer simulations using the new mechanism reproduce experimental results obtained from the ozonolysis of propylene in air.
    Additional Material: 5 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110405
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  • 54
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    Electronic Resource
    Anionic σ-complexes from sulfite ion attack on n-methyl-N-β-hydroxyethyl picramide and its spiro complex. Search for geometric isomerism in 1:2 complexes. An instructive example of complex kineticsThis is part 20 in the series “Intermediates in Nucleophilic Aromatic Substitution.” Part 19: C. F. Bernasconi and J. R. Gandler, J. Am. Chem. Soc., 100, 8117 (1978). (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 375-397 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: N-Methyl-N-β-hydroxyethyl picramide (PH) forms a 1:1 (PHS2-) and a 1:2 (PHS24-) anionic σ-complex with sulfite ion. In alkaline solution PH is present mainly in the form of its spiro Meisenheimer complex (M-) which also adds sulfite ion to form a complex MS3-. Rate and equilibrium constants for the various reactions which interrelate the five species PH, PHS2-, PHS24-, M-, and MS3- (scheme I) were determined. PHS24- and MS3- can, in principle, exist in the form of two geometric isomers. Despite a careful search by nuclear magnetic resonance and kinetic techniques, no experimental manifestation of this isomerism could be found. Various limiting situations are discussed under which the absence of experimental evidence does or does not exclude the presence of two isomers. Our preferred but unproven interpretation is that in the case of PHS24- one isomer (trans?) is thermodynamically strongly favored over the other, whereas in the case of MS3- both isomers are of similar thermodynamic stability and have also similar rates. This latter feature would make the isomerism kinetically undetectable. Several other features of scheme I make it an instructive example in complex chemical kinetics.
    Additional Material: 6 Ill.
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  • 55
    Electronic Resource
    Electronic Resource
    Rate constants for the termination of benzyl radicals in solution (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 705-713 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the bimolecular combination of benzyl radicals in cyclohexane and toluene is determined as a function of temperature. Further, it is studied in cyclohexane-toluene mixtures of different compositions. In the entire range covered, 9.8 × 108 ≤ 2kt ≤ 9.0 × 109M-1·sec-1, the data are very well described by the Smoluchowski equation for a diffusion-controlled reaction to ground-state products using a spin statistical factor of 1/4, a temperature- and solvent-independent reaction distance, and the known diffusion coefficient of toluene.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110704
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  • 56
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    The thermal reactions of ethylene at 500°C in the presence and absence of small quantities of oxygen (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 757-774 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Initial rates of formation of primary products have been measured in the pyrolysis of ethylene at 500°C, and a mechanism for the reaction is proposed based on the isomerization of the n-hexyl radical. Additions of oxygen in amounts less than 0.1% markedly increased the rate of formation of all products, but oxygen was not completely consumed in the reaction. It is shown that secondary initiation processes are important at very low conversions, and butene-1 is the most reactive product. Bimolecular reactions between olefins and with oxygen are important steps in the mechanism.
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    URL: http://dx.doi.org/10.1002/kin.550110708
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  • 57
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110801
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    Kinetics and mechanism of palladium (II) chloride catalyzed oxidation of allyl alcohol by potassium hexacyanoferrate (III) (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 813-819 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A kinetic study of the oxidation of allyl alcohol by potassium hexacyanoferrate (III) in the presence of palladium (II) chloride is reported. The reaction was observed by measuring the disappearance of the potassium hexacyanoferrate (III) spectrophotometrically. The reaction is first order with respect to allyl alcohol and palladium (II) chloride, inverse second order with respect to [Cl-], and zero order with respect to potassium hexacyanoferrate (III). The rate is found to increase linearly with hydroxyl ion concentration.
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    URL: http://dx.doi.org/10.1002/kin.550110802
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  • 59
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    The reaction of CH3O2 with SO2 (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 907-914 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mixtures of Cl2, CH4, and O2 were flash photolyzed at room temperature and pressures of ∽60-760 Torr to produce CH3O2. The CH3O2 radicals decay by the second-order process with k6 = (3.7 ± 0.3) × 10-13 cm3/sec in good agreement with other studies. This value ignores any removal by secondary radicals produced as a result of reaction (6), and therefore the true value might be as much as 30% lower. The value is independent of total pressure or the presence of H2O vapor. With SO2 also present, the CH3O2 decay becomes pseudo first order at sufficiently high SO2 pressure which indicates the reaction The value of (8.2 ± 0.5) × 10-15 cm3/sec at about 1 atm total pressure (mostly CH4) was found for CH3O2 removal by SO2, in good agreement with another recent measurement. This value can be equated with k1, unless the products rapidly remove another CH3O2 radical, in which case k1 would be a factor of 2 smaller.
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    URL: http://dx.doi.org/10.1002/kin.550110809
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  • 60
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    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110901
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  • 61
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    A quantitative study of alkyl radical reactions by kinetic spectroscopy III. Absorption spectrum and rate constants of mutual interaction for the ethyl radical (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 995-1005 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Intrinsic spectral and kinetic parameters have been measured for the ethyl radical, which was formed in the gas phase by the flash photolysis of azoethane. Absolute values of the extinction coefficient ε(λ) were derived from complementary measurements of the yield of nitrogen and the absorbance of an equivalent concentration of the ethyl radical. The absorption spectrum is broad, structureless, and comparatively weak; ε(247) = 4.8 × 102 l/mol·cm at the maximum, and the oscillator strength is (9.1 ± 0.5) × 10-3. This is in good qualitative agreement with a spectrum obtained independently using the technique of molecular modulation spectrometry.The biomolecular reactions of mutual interaction were the only significant reactions of the ethyl radical in this system; kinetic analysis of the second-order decline of the absorbance during the dark period yielded a value of k/ε(λ) for each experiment. The rate constant for mutual interaction was evaluated from the product of corresponding measurements of k/ε(λ) and ε(λ) individual values are independent of the wavelength of measurement, and the mean value is k = (1.40 ± 0.27) × 1010 l/mol·sec. The rate constant for mutual combination was derived with the aid of product analysis as k2 = (1.24 ± 0.23) × 1010 l/mol·sec; it stands in close agreement with the set of “high” values obtained by direct measurement using a variety of methods.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110906
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    Combination and disproportionation reactions of allylic radicals with ethyl, propyl, and t-Butyl Radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1055-1069 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1-Methylallyl, 1,1-dimethylallyl, 1,2-dimethylallyl, 1,3-dimethylallyl, 1,1,2-trimethylallyl, and 1-ethylallyl radicals have been generated in the gas phase at 20 ± 1°C by addition of H atoms, formed by Hg(63P1) photosensitization of H2, to appropriate dienes. Their combination reactions with ethyl radicals have been studied and the relative reactivities of the reaction centers in each allylic radical determined. Similar measurements have been made for some combination reactions of n-propyl, i-propyl, and t-butyl with 1-methylallyl and 1,1,2-trimethylallyl radicals. The more substituted reaction centers are found to be the less reactive. In addition the self-combination and disproportionation of 1-methylallyl radicals has been investigated, as has cross disproportionation of each allylic radical with ethyl. The results establish a general pattern of reactivity for these radicals, which is interpreted primarily in terms of the effects of steric interaction during reaction.
    Additional Material: 4 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550111004
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    Reaction of methoxy radicals with oxygen. I. Using dimethyl peroxide as a thermal source of methoxy radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1045-1053 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Using dimethyl peroxide as a thermal source of methoxy radicals overthe temperature range of 110-160°C, and the combination of methoxy radicals and nitrogen dioxide as a reference reaction: a value was determined of the rate constant for the reaction of methoxy radicals with oxygen: is independent of nitrogen dioxide or oxygen concentration and added inert gas (carbon tetrafluoride). No heterogeneous effects were detected. The value of k4 is given by the expression \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm log }k_4 {\rm = 9}{\rm .0} \pm {\rm 0}{\rm .6 - 4}{\rm .8 } \pm {\rm 1}{\rm .1/}\theta {\rm (M}^{{\rm - 1}} \cdot \sec ^{ - 1}) $$\end{document} In terms of atmospheric chemistry, this corresponds to a value of 105.6 M-1·sec-1 at 298 K. Extrapolation to temperatures where the combustion of organic compounds has been studied (813 K) produces a value of 107.7 M-1·sec-1 for k4. Under these conditions, reaction (4) competes with hydrogen abstraction or disproportionation reactions of the methoxy radical and its decomposition (3): In particular k3 is in the falloff region under these conditions. It is concluded that reaction (4) takes place as the result of a bimolecular collision process rather than via the formation of a cyclic complex.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550111003
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    A Program package using stiff, sparse integration methods for the automatic solution of mass action kinetics equations (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1097-1108 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A portable program package, MACKSIM, for mass action chemical kinetics simulation, is discussed. As these kinetics are readily expressed in explicit mathematical terms, such a package contains two major and distinct modules, the numerical analysis and the user interface. For the first, MACKSIM uses the latest proven developments incorporating sparse matrix techniques in the backward difference predictor corrector methods originated by Gear for the integration of stiff ordinary differential equations, and thus requires minimal computing time to solve large systems of equations. For the second, the program provides a flexible interface which permits simple specification and variation of reactions, requires no special character input, and has no limit on the number of reactions or species involved other than that imposed by the size of the computer. The technology of these components is discussed briefly, the use of the package for standard reactions is illustrated, and current applications are mentioned.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550111008
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    The detailed mechanism of the Dushman reaction explored by computer (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 693-703 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Since 1926 investigations of the Dushman reaction have relied mainly upon “constant-rate” measurements, usually by instrumental methods. Since about that time, the confusion surrounding this venerable reaction has been growing. In part, the confusion arises because the reaction involves reactive intermediate species that have not been studied directly - and may never be. Alternative detailed mechanisms have been assumed with little restraint. One of these, which is built around H2I2O3, has been explored by computer with promising results. The mechanism seems capable of reducing the confusion now attending the Dushman reaction and others related to it.
    Additional Material: 3 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550110703
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    Homogeneous decomposition of vinyl ethers. The heat of formation of ethanal-2-yl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 715-730 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal unimolecular decomposition of three vinylethers has been studied in a VLPP apparatus. The high-pressure rate constant for the retro-ene reaction of ethylvinylether was fit by log k (sec-1) = (11.47 + 0.25) - (43.4 ± 1.0)/2.303 RT at 〈T〉 = 900 K and that of t - butylvinylether by log k (sec-1) = (12.00 ± 0.27) - (38.4 ± 1.0)/2.303 RT at 〈T〉 = 800 K. No evidence for the competition of the higher energy homolytic bond-fission process could be obtained from the experimental data. The rate constant compatible with the C—O bond scission reaction in the case of benzylvinylether was log k (sec-1) = (16.63 ± 0.30) - (53.74 ± 1.0)/2.303 RT at 〈T〉 = 750 K. Together with ΔHf,3000(benzyl·) = 47.0 kcal/mol, the activation energy for this reaction results in ΔHf,3000(CH2CHO) = +3.0 ± 2.0 kcal/mol and a corresponding resonance stabilization energy of 3.2 ± 2.0 kcal/mol for 2-ethanalyl radical.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110705
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    Predicting gas phase organic molecule reaction rates using linear free-energy correlations. I. O(3P) and OH addition and abstraction reactions (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1197-1209 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Linear free-energy (LFE) correlations for gas phase O(3P) and OH addition and abstraction reactions with a number of organic compounds have been established using existing room-temperature rate constants evaluated from the literature. Addition reaction rate constant correlations with ionization potential and abstraction reaction rate constant correlations with bond dissociation energies are examined and compared to the LFE approach. Using multiple regression analysis, empirical linear equations are derived and used to predict rate constants for reactions of O(3P) and OH with a number of organic molecules. The use of LFE room-temperature rate predictions permits chemical modeling efforts to be extended to compounds where experimental determinations of rate coefficients are lacking and also serves as a useful tool in evaluation of experimental rate measurements.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550111106
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    Wall effects in the pyrolysis of diethylether. A case of hetero-homogeneous pyrolysis at 500°C (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 789-798 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The pyrolysis of diethylether has been studied at 500°C and 50 Torr initial pressure in packed vessels (surface-to-volume ratio 11 cm-1). In untreated vessels the reaction appears to be essentially homogeneous as reported before. On the contrary, it is very sensitive to the walls of PbO-coated or NaOH-treated vessels. Thus most of the initial rates of product formation are increased in the PbO-coated vessel and decreased in the NaOH-treated vessel. The efficiency of the walls has been monitored for several weeks and was shown to decrease slowly with the vessel aging time. These phenomena are interpreted in terms of a free-radical chain mechanism in which a part of the initiation or termination steps occurs at the walls, the propagating steps being homogeneous. The present work clearly proves the existence of hetero-homogeneous chain reactions at 500°C. This new class of reaction could be of practical interest in the design of industrial reactors.
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    Reaction of NO with hypochlorous acid (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 843-851 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between NO(g) at concentrations between 0.1 and 1.0 Torr in 1-atm N2 and aqueous solutions of NaClO has been studied over the pH range of 6-12 and hypochlorite concentrations between 0.01 and 1.0M. A very rapid and efficient reaction occurs leading to the production of about 30%-40% of the NO as NO2 and with conversions of NO up to 98% at about 1-sec contact time. It is shown that a fast chain reaction initiated by the endothermic step can account for the data. The very exothermic reaction NO + ClO- → NO2 + Cl- is shown to be at least 30-fold slower than i. The overall reaction seems very promising as a method of reducing NO and NO2 emissions from the exhausts of industrial plants.
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    URL: http://dx.doi.org/10.1002/kin.550110804
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    Thermal decomposition of hexamethylethane in a flow system (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 867-882 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Hexamethylethane has been decomposed in a flow system in the temperature range of 700-900 K. The mechanism involves carbon-carbon bond cleavage at the most highly substituted position and rapid formation of isobutene from the t-butyl radical. The rate expression is \documentclass{article}\pagestyle{empty}\begin{document}$$ \begin{array}{*{20}c}{k({\rm (tC}_{\rm 4} {\rm H}_{\rm 9})_2 \to 2t{\rm C}_{\rm 4} {\rm H}_{\rm 9}.) = 10^{17.4} {\rm exp(} - 36,000/{\rm T)}} & {{\rm sec}^{ - 1}}\\\end{array} $$\end{document} and is completely consistent with deductions from radical buffer, shock-tube, and direct recombination studies. Of special importance is experimental evidence for large decreases of the A factor with increasing temperature and a high heat of formation for the t-butyl radical, ΔHf(tC4H9·)300 = 52.7 ± 6 kJ.
    Additional Material: 7 Ill.
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    Kinetic flash spectroscopic study of the CH3O2—CH3O2 and CH3O2—SO2 reactions (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 921-933 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Methylperoxy radicals were generated by the flash photolysis of azomethane-oxygen mixtures. The observed broadband spectrum of the CH3O2 radical is similar, but not identical to those reported previously. The CH3O2 decay followed second-order kinetics at high CH3O2 concentrations with k4' = (2.5 ± 0.3) × 108 liter/mol·sec (23 ± 2°C); 2CH3O2 → products (4). Because of the potential loss of CH3O2 through the reactions with HO2 and CH3O radicals subsequently formed in this system, simulations suggest that the true k4 is in the range: 2.5 × 108 ≥ k4 ≥ 2.3 × 108 liter/mol·sec. Deviations from linearity of the plot of the reciprocal of the CH3O2 absorbance versus time were seen at long times and were attributed to the reaction (5) with an apparent rate constant k5' ⋍ (1.6 ± 0.4) × 105 liter/mol·sec; CH3O2 + Me2N2 → product (5). The CH3O2-SO2 reaction, CH3O2 + SO2 → products (16), was studied by observing CH3O2 decay in flashed mixtures of Me2N2, O2, and SO2. The results gave the apparent second-order rate constant k16' ⋍ (6.4 ± 1.4) × 106 liter/mol·sec. It appears likely that each occurrence of reaction (5) and (16) is followed by the loss of an additional CH3O2 radical and that k5 ⋍ k5'/2 and k16 ⋍ k16'/2. Our findings suggest that a significant fraction of the SO2 oxidation in a sunlight-irradiated NOx-RH-polluted atmosphere, may occur by reaction with CH3O2 as well as from the HO and HO2 reactions.
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    URL: http://dx.doi.org/10.1002/kin.550110811
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    The absolute rate constant for the metathesis t-C4H9• + DI → C4H9D + I• and the heat of formation of the t-butyl radical (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 969-976 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The Arrhenius parameters for the title reaction have been measured in a very-low-pressure pyrolysis apparatus in the temperature range 644-722 K and are given by log k2 (M-1 · sec-1) = 9.68 - 2.12/θ, where θ = 2.303RT in kcal/mol. Together with the published Arrhenius parameters for the reverse reaction from iodination studies, they result in a standard heat of formation of the t-butyl radical of 8.4 kcal/mol, accepting S0(C4H9·) = 72.2 e.u. at 300 K from other kinetic data, and thus confirm the accepted value for ΔHf0(t-C4H9·), at variance with recent investigations which yielded significantly higher values. This value for ΔHf0(t-C4H9·) results in a bond-dissociation energy (BDE) for isobutane of 92.7 kcal/mol.
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    Neighboring olefinic double-bond participation in gas phase pyrolysis of some alkenyl chlorides (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1279-1286 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 4-Chloro-1-butene, 5-chloro-1-pentene, and 6-chloro-1-hexene have been shown to decompose, in a static system, mainly to hydrogen chloride and the corresponding alkadienes. In packed and unpacked clean Pyrex vessels the reactions were significantly heterogeneous. However, in a vessel seasoned with allyl bromide these reactions were homogeneous, unimolecular, and follow a first-order law. The working temperature range was 389.6-480.0°C and with a pressure range of 53-221 Torr. The rate constants for the homogeneous reactions were expressed by the following Arrhenius equations: 4-chloro-1-butene: logk(sec-1) = (13.79 ± 0.17) - (223.8 ± 2.1)kJ/mole/2.303RT; 5-chloro-1-pentene: logk(sec-1) = (14.25 ± 1.20) - (238.4 ± 12.7)kJ/mole/2.303RT; and 6-chloro-1-hexene: logk(sec-1) = (12.38 ± 0.22) - (209.6 ± 2.9)kJ/mole/2.303RT. The olefinic double bond has been found to participate in the rate of dehydrohalogenation of 4-chloro-1-butene. The insulation of the CH2=CH in chlorobutene by one or two methylene chains to the reaction center does not indicate neighboring group participation. The three-membered conformation is the most favored structure for anchimeric assistance of the double bond in gas phase pyrolysis of alkenyl chlorides. The heterolytic nature of these eliminations is also supported by the present work.
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    A kinetics study of the temperature dependence of the reactions of OH(2Π) with CF3CHCl2, CF3CHClF, and CF2ClCH2Cl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 187-197 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The flash photolysis resonance fluorescence technique has been utilized to determine the rate constants for three reactions involving the hydroxyl radical [OH(2≅)] and three halogenated C2 alkanes. The nominal temperature range covered was 250-375 K. The compounds studied and the resulting Arrhenius expressions in units of cm3/molec·sec are The error limits in these expressions are such that they include any possible systematic errors due to the presence of impurities in the halocarbon samples. Tropospheric lifetimes have been calculated for the above species by combining the above rate constant data with global seasonally and diurnally averaged hydroxyl radical concentrations.
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    URL: http://dx.doi.org/10.1002/kin.550110210
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    The photolysis of n-butyraldehyde in isooctane at 313 nm (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 239-260 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The effects of aldehyde concentration, incident light intensity, and temperature on the quantum yields of reaction products were studied. Mechanisms for primary and secondary photochemical processes were suggested, and primary quantum yields as well as rate constant ratios were derived. Reversibility of intramolecular γ-hydrogen transfer and disproportionation of the radical pair formed in the reaction of an excited triplet and ground state molecule were shown to provide important pathways for radiationless decay of the triplet state.
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    URL: http://dx.doi.org/10.1002/kin.550110303
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    Evaluation of boundary-layer effects in shock-tube studies of chemical kinetics (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 285-304 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Particle times of flight in incident shock flow were determined experimentally by marking several positions of the test gas (mainly Ar) in the shock tube with an infrared emitting gas (NO or CO2). From the local particle velocity, derived from the particle flight times, temperature and pressure changes behind the shock front were evaluated. Several experimental data were found to be correctly described by Mirels's formulations when used properly. The limitations of the formulations are discussed. It is found to be advisable to evaluate boundary-layer effects on shock-tube flow by experiments, rather than theory, in carrying out chemical kinetics studies.
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    URL: http://dx.doi.org/10.1002/kin.550110306
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  • 77
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    The 5-hexenyl cyclization (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 333-338 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The cyclization of the 5-hexenyl radical to form the cyclopentylmethyl radical has been reexamined by kinetic EPR spectroscopy at temperatures between 183 and 232°K in cyclopropane solvent. The rate constant, kc for this important radical rearrangement can be represented by \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k_c (\sec ^{ - 1}) = (9.5 \pm 1.1) - (6.1 \pm 1.1)/\theta $$\end{document} where Θ = 2.3RT kcal/mol.
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    Competitive unimolecular reactions at low pressures. The pyrolysis of cyclobutyl chloride (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 11-21 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of cyclobutyl chloride has been investigated over the temperature range of 892-1150 K using the technique of very low-pressure pyrolysis (VLPP). The reaction proceeds via two competitive unimolecular channels, one to yield ethylene and vinyl chloride and the other to yield 1,3-butadiene and hydrogen chloride, with the latter being the major reaction under the experimental conditions. With the usual assumption that gas-wall collisions are «strong,» RRKM calculations, generalized to take into account two competing pathways, show that the experimental unimolecular rate constants are consistent with the high-pressure Arrhenius parameters given by log k1(sec-1) = (14.8 ± 0.3) - (61.1 ± 1.0)/Θ for vinyl chloride formation and log k2(sec-1) = (13.6 ± 0.3) - (55.7 ± 1.0)/Θ for 1,3-butadiene formation, where Θ = 2.303 RT kcal/mol. The A factors were assigned from previous high-pressure low-temperature data of other workers assuming a four-center transition state for 1,2-HCl elimination and a chlorine-bridged biradical transition state for vinyl chloride formation. The activation energies are in good agreement with the high-pressure results which were obtained with a conventional static system. The difference in critical energies is 4.6 kcal/mol.
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    URL: http://dx.doi.org/10.1002/kin.550110103
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    Thermal decomposition of ethane (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 23-44 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of C2H6 in Ar was studied by laser-absorption and laser-schlieren measurements of the reaction rate behind incident shock waves with 1300 〈 T 〈 2500°K and 1.1 〈 ρ 〈 4.4 × 10-6 mol/cm3. The experimental profiles were parameterized by suitable measures of reaction progress. Computer simulations using a 14-reaction mechanism were used to compare assumptions about rate constant expressions with the experimental parameters and to investigate the sensitivity of computed parameters to these assumptions. A rate constant expression k(cm3/mol·sec) = 2 × 10111 T-25.26 exp(-80 320/T) was found for the primary dissociation step C2H6 + M = CH3 + CH3 + M under the conditions studied; no difference in rate was discernable between M = Ar and M = C2H6. Rate constant expressions found to be suitable for the remaining reactions of the mechanism, to some of which the computed parameters were sensitive, were in accord with previous proposals. Our results and results from earlier investigations of the primary decomposition reaction, in both forward and reverse directions, were extrapolated, using RRK methods, to obtain low-pressure limiting rate constants and found to be concordant.
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  • 80
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    Computer modeling of smog chamber data: Progress in validation of a detailed mechanism for the photooxidation of propene and n-butane in photochemical smog (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 45-101 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A detailed mechanism is presented for reactions occurring during irradiation of part-per-million concentrations of propene and/or n-butane and oxides of nitrogen in air. Data from an extensive series of well-characterized smog chamber experiments carried out in our 5800-liter evacuable chamber-solar simulator facility designed for providing data suitable for quantitative model validation were used to elucidate several unknown or uncertain kinetic parameters and details of the reaction mechanism.The mechanism was then tested against the data base from the smog chamber runs. In general, most calculated concentration-time profiles agreed with experiments to within the experimental uncertainties. Fits were usually attained to within ∼±20% or better for ozone, NO, propene, and n-butane, to within ∼±30% or better for NO2, PAN, methyl ethyl ketone, 2-butyl nitrate, butyraldehyde, and (in runs not containing propene) methyl nitrate, to within ⋐±50% or better for the minor products 1-butyl nitrate and propene oxide, and to within a factor of 2 for methyl nitrate in propene-containing runs. Propionaldehyde was consistently underpredicted in all runs; it is probably a chamber contaminant. For formaldehyde and acetaldehyde, the major products in both systems, fits to within ⋐±20% were often obtained, yet for a number of experiments, significantly greater discrepancies were observed, probably as a result of experimental and/or analytical problems.The good fits to experimental data were attained only after adjusting several rate constants or rate constant ratios related to uncertainties concerning chamber effects or the chemical mechanism. The largest uncertainty concerns the necessity to include in the mechanism a significant rate of radical input from unknown sources in the smog chamber. Other areas where fundamental kinetic and mechanistic data are most needed before a predictive, detailed propene + n-butane-NOx-air smog model can be completely validated concern other chamber effects, the O3 + propene mechanism, decomposition rates of substituted alkoxy radicals, primary quantum yields for radical production as a function of wavelength for aldehyde and ketone photolyses, and the mechanisms and rates of reactions of peroxy radicals with NO and NO2.
    Additional Material: 12 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110105
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    The very-low-pressure study of the kinetics and equilibrium: Cl + CH4 ⇄ CH3 + HCl at 298 K. The heat of formation of the CH3 radical (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 147-154 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The bimolecular rate constant for the direct reaction of chlorine atoms with methane was measured at 25°C by using the very-low-pressure-pyrolysis technique. The rate constant was found to be \documentclass{article}\pagestyle{empty}\begin{document}$$ k_1^{298} = (0.93 \pm 0.05) \times 10^{ - 13} cm^3 /mole \cdot \sec $$\end{document} In addition, the ratio k1/k-1 was observed with about 25% accuracy: K1(298) = 1.3 ± 0.3. This gives a heat of formation of the methyl radical ΔH° f 298(CH3) = 35.1 ± 0.15 kcal/mol. A bond dissociation energy BDE (CH3 — H) = 105.1 ± 0.15 kcal/mol in good agreement with literature values was obtained.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110206
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  • 82
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    Electronic Resource
    Collisional deactivation of O2(1Σg+) (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 175-185 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Relaxation rates for O2(1Σg+) by nonradiative pathways have been determined using the fast-flow technique. O2(1Σg+) is formed from O2(1Δg) by an energy pooling process. O2(1Δg) is generated by passing purified oxygen through a microwave discharge. Oxygen atoms are removed by distilling mercury vapor through the discharge zone. It has been observed that the wall loss rate for O2(1Σg+) decreases with increasing pressure of oxygen and thus appears to be diffusion controlled. Quenching rate constants for O2, N2, and He have been determined and found to be (1.5 ± 0.1) × 104, (1.0 ± 0.05) × 106 and (1.2 ± 0.1) × 105 l./mol·sec, respectively.
    Additional Material: 6 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110209
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  • 83
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    Radical equilibrium studies. II. The thermodynamic parameters of s-butyl (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 199-215 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The thermal decomposition of azomethane in the presence of propene has been investigated in the range of 568-638°K at reactant partial pressures of up to about 7 torr in the presence of at least 170 torr of argon. The elementary reactions taking place in such conditions are discussed in detail. It is shown that a situation approaching equilibrium is attained between the processes Values are obtained for the equilibrium constant K2, which can be described by the equation \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm logK}_{\rm 2} \left({{\rm atm}} \right){\rm = 7}{\rm .66 - 26}{\rm .1kcal/mol/(2}{\rm .3RT)} $$\end{document} Using the best available thermodynamic parameters for methyl and propene, it is concluded that those for s-butyl are in need of adjustment. We recommend the values ΔHf0 (300°K) = 13.8 ± 1.0 kcal/mol and S3000 (1 atm standard state) = 75.6 ± 3.0 cal/mol°K together with group additivity values of the heat capacity. A comparison of measured values of K2 with values calculated from independent measurements of k2 and k-2 shows a discrepancy of about a factor of 3.5.
    Additional Material: 8 Tab.
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    URL: http://dx.doi.org/10.1002/kin.550110211
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  • 84
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    Quenching of *UF6 (A state) by alkanes (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 275-283 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The removal of *UF6 (A state) molecules by selected alkanes has been investigated at 25°C. The following rate constants (units of 1011 l/mol·sec) were evaluated: iso-C4F10, 0.0432 ± 0.0115; n-C4F10, 0.0764 ± 0.020; C2F6, 0.0192 ± 0.0052; CH4, 0.0612 ± 0.0061; C2H6, 3.78 ± 0.60; C3H8, 5.08 ± 0.60; n-C4H10, 5.05 ± 0.78; iso-C4H10, 4.17 ± 1.15; neo-C5H12, 6.59 ± 0.93; CF3—CH3, 0.0385 ± 0.0056; CF2H—CF2H, 0.0729 ± 0.0074; and CF2H—CFH2, 0.149 ± 0.015. The perfluoro-alkane quenching of *UF6 proceeds via a physical mechanism. The other alkane quenching reactions are consistent with a chemical mechanism also contributing in varying degrees which may involve removal of two hydrogens from the alkane.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110305
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  • 85
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    Electronic Resource
    Shock-tube study of thermal decomposition of nitric oxide between 2700 and 3500 K (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 305-315 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of nitric oxide at temperatures ranging from 2700 to 3500 K was studied by means of the shock tube. The experimental data were reduced by the method described in a preceding paper and explained consistently by a set of the elementary reactions. The rate constant of the initiation reaction 2NO → N2O + O, which was not well known in this temperature range, was deduced precisely. k1 was one order of magnitude lower than that reported previously in similar shock-tube experiments, and was consistent with results obtained below 2000 K and from the reverse reaction.
    Additional Material: 7 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110307
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  • 86
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    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110101
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  • 87
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    Kinetics and mechanism of acetylacetonate transfer from acetylacetonatomanganese(III) to iron(III) in acetonitrile catalysis and inhibition effects (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 1-9 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reaction between tris(acetylacetonato)magnanese(III) and hexa(N,N-dimethylformamide)iron(III) perchlorate in acetonitrile proceeds in two stages. The first stage corresponds to the reaction of pentacoordinated Fe(DMF)53+ with Mn(acac)3, and the rate-determining step of the second stage consists mainly in the elimination of a DMF ligand from Fe(DMF)63+ to yield Fe(DMF)53+ which reacts rapidly with the manganese complex. The formation of Fe(DMF)53+ is catalyzed by Mn(acac)3, this catalytic effect being decreased by manganese products. The rate-determining step for the formation of Fe(acac)3 is the transfer of the first acetylacetonate to yield Fe(acac)2+. The final products of iron depend on the ratio of reactant concentrations. With Mn or Fe in excess, Fe(acac)3 or Fe(acac)2+ are mainly produced.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110102
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  • 88
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    Classical kinetic theory of fluids, by R. Resibois and M. de Leener, John Wiley, New York, 1977. 400 pp (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 105-106 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110107
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  • 89
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    Mechanism of catalytic ascorbic acid oxidation system Cu2+-ascorbic acid-O2 (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 461-494 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Analysis is made of reported results on the kinetics and mechanism of ascorbic acid oxidation with oxygen in the presence of cupric ions. The diversities due to methodological reasons are cleared up. A kinetic study of the mechanism of Cu2+ anaerobic reaction with ascorbic acid (DH2) is carried out. The true kinetic regularities of catalytic ascorbic acid oxidation with oxygen are established at 2.7 ≤ pH 〈 4, 5 × 10-4 ≤ [DH2] ≤ 10-2M, 10-4 ≤ [Cu2+] ≤ 10-3M, and 10-4 ≤ [O2] ≤ 10-3M: \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_0 = {}_{K1}[{\rm Cu}^{{\rm 2} +}][{\rm DH}_2][{\rm O}_2]{}^{0.5}/[{\rm H}^ +] $$\end{document} wherek1 (25°C) = 0.13 ± 0.01 M-0.5·sec-1. The activation energy for this reaction is E1 = 22 ± 1 kcal/mol. It is found by means of adding Cu+ acceptors (acetonitrile and allyl alcohol) that the catalytic process is of a chain nature. The Cu+ ion generation at the interaction of the Cu2+ ion with ascorbic acid is the initiation step. The rate of the chain initiation at [Cu2+] ± 10-4M, [DH2] ± 10-2M, 2.5 〈 pH 〈 4, is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_{\rm i} = {}_{K{\rm i,1}}[{\rm Cu}^{{\rm 2} +}]^2 [{\rm DH}_2]/[{\rm H}^ +] $$\end{document} whereki,1 (25°C) = (1.8 ± 0.3)M-1·sec-1, Ei,1 = 31 ± 2 kcal/mol. The reaction of the Cu+ ion with O2 is involved in a chain propagation, so that the rate of catalytic ascorbic acid oxidation for the system Cu2+—DH2—O2 is \documentclass{article}\pagestyle{empty}\begin{document}$$ {\rm W}_{\rm 0} = {}_{k{\rm 1}}[{\rm Cu}^ +][{\rm O}_2] $$\end{document} wherek1 (25°C) = (5 ± 0.5) × 104 M-1·sec-1. The Cu+ ion and a species interacting with ascorbate are involved to quadratic chain termination. By means of photochemical and flow electron spin resonance methods we obtained data characteristic of the reactivities of ascorbic acid radicals and ruled out their importance for the catalytic chain process. A new type of chain mechanism of catalytic ascorbic acid oxidation with oxygen is proposed: .
    Additional Material: 16 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110503
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  • 90
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110601
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  • 91
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    The kinetics of dimerization of chlorotrifluoroethene (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 585-593 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Rate constants determined for the thermal dimerization of chlorotrifluoroethene to dichlorohexafluorocyclobutane at 404-672 K have been correlated with previously published results. For the temperature range of 404-800 K, \documentclass{article}\pagestyle{empty}\begin{document}$$ k{ = 1}{.08} \times { 10}^{{ - 9}} { T }^{{4}{.02}} { exp ( - 86,700/RT) m}^{3} {/mol} \cdot \sec $$\end{document} The dependence of the preexponential factor on temperature corresponds to a value of 17 J/K·mol for the difference in heat capacity (ΔCp±) between the activation complex and the reactant.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110605
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  • 92
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    Bimolecular self-reactions of 2-arylindandione- 1,3-yl radicals studied by flash photolysis (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 621-633 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Kinetic and thermodynamic data for reaction (1) of certain C-centered aromatic radicals (referred to in this paper by the numbers I to X) in chlorobenzene: have been obtained. The k1 values of radicals varied between (1.1 ± 0.2) × 106M-1·sec-1 (radical VIII) and (3.6 ± 0.7) × 109M-1 sec-1 (radical VI) at 20°C. An investigation of the relationship between the recombination rates of radicals I-VIII and X and the solvent viscosity (mixture of toluene and dibutylphthalate, 0.6 〈 η 〈 18.4 cP) has shown that the recombination reactions involving radicals I-IV are limited by diffusion in solvents having a viscosity η〉 10 cP and are activation reactions in solvents having a viscosity η 〈 10 cP. The recombination of radicals VIII and IX is an activation reaction, while that of radicals V-VII is diffusion-controlled in the entire viscosity range. The recombination of radical X is limited, in the viscosity range of 18.4 to 2 cP, by intrusion into the first coordination sphere of the partner, the effect of viscosity on the radical X recombination rate in the specified range being the same as its effect on diffusion-controlled reactions. The possible reasons of the discrepancies between the experimental fast recombination rate constants and the theoretical values calculated by the Debye-Smoluchowski theory are discussed. The equilibrium constant depends strongly on the nature of the substituent in the phenyl fragment: the substituents which increase unpaired electron delocalization in the radical intensify the dissociation of the respective dimer. Long-wave absorption bands have been recorded for radicals I-X and their extinction coefficients obtained. Dimers I-V are thermo- and photochromic compounds.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110609
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  • 93
    Electronic Resource
    Electronic Resource
    Masthead (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979) 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110701
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  • 94
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    Electronic Resource
    The question of the applicable time regime for the steady-state approximation in the simulation of complex mechanisms (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 687-691 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: A mechanism proposed by Pilling and Noyes for ignition in carbon monoxide containing traces of water has been modeled using a complete numerical integration, and results have been compared with the steady state treatment (QSSA) of the previous authors. The numerical results were found to be in close agreement. However, the complete solution also yields the time required for the steady state to be reached, and it is shown that this is too large for the results of the QSSA to be considered applicable to this problem. This is substantiated by a further calculation in which temperature is introduced as an additional variable, and it is shown that thermal runaway is reached without any of the intermediate radicals which propagate the reaction chain ever going into a steady state.This study provides an example of the failure of QSSA to provide an adequate solution to a chemical kinetic problem for reasons which have not been previously discussed in the literature. For problems of more than a very few variables there is no practical way short of numerical integration to estimate the time regime during which the steady state applies. Practitioners of QSSA are thus advised of yet another precaution in assesing the credibility of their results.
    Additional Material: 1 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110702
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  • 95
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    Kinetics and mechanism of oxidation of sugars by quinquevalent vanadium in binary mixture solvents of DMSO-water and acetic acid-water in H2SO4 medium (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 731-740 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of oxidation of aldosugars and ketosugar by quinquevalent vanadium in binary mixtures of DMSO-water and acetic acid-water in sulfuric acid medium have been studied. The reaction is first order in both oxidant and substrate. The effect of acidity on the reaction kinetics has been determined. The effect of acidity shows a clear difference. The ketose has a unit dependence, whereas aldoses have a 0.5 dependence in H0. The role of solvent in these reactions has also been studied, and the effect of temperature on these reactions has been determined. A suitable mechanism has been postulated taking all the observed facts into consideration.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110706
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  • 96
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    Rate of decomposition of hexafluoroazomethane and the absolute rate of recombination of trifluoromethyl radical at higher temperatures (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 775-788 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The unimolecular homogeneous decomposition of hexafluoroazomethane was studied in a VLPP apparatus in the temperature range 720-1050 K and is consistent with the following Arrhenius parameters: \documentclass{article}\pagestyle{empty}\begin{document}$$ \log k(\sec ^{ - 1}) = 16.2 - 55.2/\theta $$\end{document} at 900 K, where the A factor was assumed to be the same as for 2,2′-azoisobutane. The homogeneous rate of recombination of ·CF3 radicals at temperatures around 1000 K was also studied under VLPP conditions and was found to be in the fall-off region, corresponding to k/k∞ = 8.5 × 10-3 when a rotational transition-state model was used. This model predicts an essentially constant value of kr∞ of 109.7 over the temperature range 300-1000 K.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110709
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  • 97
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    Absolute rate constants for the reaction of bromine atoms with ozone from 234 to 360 K (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 799-809 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The rate constant for the reaction of Br + O3 → BrO + O2 has been measured at four temperatures from 234 to 360 K by the technique of discharge flow coupled with resonance-fluorescence detection of bromine atoms. The measured rate constants obey the Arrhenius expression k = (9.45 ± 2.48) × 10-12 exp(-659 ± 64/T) cm3/molec·sec (one standard deviation). The results are compared with two previous studies, one of which utilized the flash-photolysis-resonance-fluorescence technique and the other utilized the discharge-flow-mass-spectrometric technique. The result is also discussed from a theoretical point of view.
    Additional Material: 6 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110711
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  • 98
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    Very-low-pressure pyrolysis (VLPP) of group IV (A) tetramethyls: Neopentane and tetramethyltin (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 529-542 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The decomposition of neopentane was studied using the very-low-pressure pyrolysis (VLPP) technique at temperatures from 1000 to 1260 K. The derived Arrhenius parameters \documentclass{article}\pagestyle{empty}\begin{document}$$ {log k(sec}^{{ - 1}} {) = 17}{.3 - 80}{.8/}\theta { at 1000 K } $$\end{document} are consistent with δHf0(t-butyl) = 8.4 kcal/mol. Using the above A factor, data on the decomposition of tetramethyltin yield DH0(Sn(CH3)3 - CH3) = 69 ± 2 kcal/mol.
    Additional Material: 3 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110506
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  • 99
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    Kinetic study of some elementary reactions of sulfur compounds including reactions of S and SO with OH radicals (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 569-577 
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    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The reactions of S + OH → SO + H (1) and SO + OH → SO2 + H (2) were studied in a discharge flow reactor coupled to an EPR spectrometer. The rate constants obtained under the pseudo-first-order conditions with an excess of S or SO were found to be k1 = (6.6 ± 1.4) × 10-11 and k2 = (8.4 ± 1.5) × 10-11 at room temperature. Units are cm3/molec·sec. Besides no reactivity was observed between S and CO2 at 298 K and between CIO and SO2 up to 711 K.
    Additional Material: 2 Ill.
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    URL: http://dx.doi.org/10.1002/kin.550110603
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  • 100
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    Kinetics of iodination of hydrogen sulfide by iodine and the heat of formation of the SH radical (1979)
    New York, NY : Wiley-Blackwell
    International Journal of Chemical Kinetics 11 (1979), S. 579-583 
    Details
    ISSN: 0538-8066
    Keywords: Chemistry ; Physical Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: The kinetics of the gas-phase thermal iodination of hydrogen sulfide by I2 to yield HSI and HI has been investigated in the temperature range 555-595 K. The reaction was found to proceed through an I atom and radical chain mechanism. Analysis of the kinetic data yields log k (l/mol·sec) = (11.1 ± 0.18) - (20.5 ± 0.44)/θ, where θ = 2.303 RT, in kcal/mol. Combining this result with the assumption E-1 = 1 ± 1 kcal/mol and known values for the heat of formation of H2S, I2, and HI, ΔHf,2980(SH) = 33.6 ± 1.1 kcal/mol is obtained. Then one can calculate the dissociation energy of the HS—H bond as 90.5 ± 1.1 kcal/mol with the well-known values for ΔHf,2980 of H and H2S.
    Additional Material: 3 Ill.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1002/kin.550110604
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