22 resultados para Rate constant
Resumo:
The total phenols, apigenin 7-glucoside, turbidity and colour of extracts from dried chamomile flowers were studied with a view to develop chamomile extracts with potential anti-inflammatory properties for incorporation into beverages. The extraction of all constituents followed pseudo first-order kinetics. In general, the rate constant (k) increased as the temperature increased from 57 to 100 °C. The turbidity only increased significantly between 90 and 100 °C. Therefore, aqueous chamomile extracts had maximum total phenol concentration and minimum turbidity when extracted at 90 °C for 20 min. The effect of drying conditions on chamomile extracted using these conditions was determined. A significant reduction in phenol concentration, from 19.7 ± 0.5 mg/g GAE in fresh chamomile to 13 ± 1 mg/g GAE, was found only in the plant material oven-dried at 80 °C (p ⩽ 0.05). The biggest colour change was between fresh chamomile and that oven-dried at 80 °C, followed by samples air-dried. There was no significant difference in colour of material freeze-dried and oven-dried at 40 °C.
Resumo:
The relative rate method has been used to measure the room-temperature rate constants for the gasphase reactions of ozone and NO3 with selected monoterpenes and cyclo-alkenes with structural similarities to monoterpenes. Measurements were carried out at 298 ! 2 K and 760 ! 10 Torr. The following rate constants (in units of 10"18 cm3 molecule"1 s"1) were obtained for the reaction with ozone: methyl cyclohexene (132 ! 17), terpinolene (1290 ! 360), ethylidene cyclohexane (223 ! 57), norbornene (860 ! 240), t-butyl isopropylidene cyclohexane (1500 ! 460), cyclopentene (543 ! 94), cyclohexene (81 ! 18), cyclooctene (451 ! 66), dicyclopentadiene (1460 ! 170) and a-pinene (107 ! 13). For the reaction with NO3 the rate constants obtained (in units of 10"12 cm3 molecule"1 s"1) were: methyl cyclohexene (7.92 ! 0.95), terpinolene (47.9 ! 4.0), ethylidene cyclohexane (4.30 ! 0.24), norbornene (0.266 ! 0.029), cyclohexene (0.540 ! 0.017), cyclooctene (0.513 ! 0.029), dicyclopentadiene (1.20 ! 0.10) and a-pinene (5.17 ! 0.62). Errors are quoted as the root mean square of the statistical error (95% con!dence) and the quoted error in the rate constant for the reference compound. Combining these results with previous studies, new recommendations for the rate constants are presented. Molecular orbital energies were calculated for each alkene and the kinetic data are discussed in terms of the deviation from the structureeactivity relationship obtained from the rate constants for a series of simple alkenes. Lifetimes with respect to key initiators of atmospheric oxidation have been calculated suggesting that the studied reactions play dominant roles in the night-time removal of these compounds from the atmosphere.
Resumo:
Time-resolved kinetic studies of silylene, SiH2, generated by laser flash photolysis of 1-silacyclopent-3-ene and phenylsilane, have been carried out to obtain rate constants for its bimolecular reactions with methanol, ethanol, 1-propanol, 1-butanol and 2-methyl-1-butanol. The reactions were studied in the gas phase over the pressure range 1-100 Torr in SF6 bath gas, at room temperature. In the study with methanol several buffer gases were used. All five reactions showed pressure dependences characteristic of third body assisted association reactions. The rate constant pressure dependences were modelled using RRKM theory, based on Eo values of the association complexes obtained by ab initio calculation (G3 level). Transition state models were adjusted to fit experimental fall-off curves and extrapolated to obtain k∞ values in the range 1.9 to 4.5 × 10-10 cm3 molecule-1 s-1. These numbers, corresponding to the true bimolecular rate constants, indicate efficiencies of between 16 and 67% of the collision rates for these reactions. In the reaction of SiH2 + MeOH there is a small kinetic component to the rate which is second order in MeOH (at low total pressures). This suggests an additional catalysed reaction pathway, which is supported by the ab initio calculations. These calculations have been used to define specific MeOH-for-H2O substitution effects on this catalytic pathway. Where possible our experimental and theoretical results are compared with those of previous studies.
Resumo:
1. Data for modern egg-type hybrids reared on constant daylengths show that, as expected, they mature more quickly than earlier genotypes. However, the constant photoperiod which gives earliest sexual maturity has not changed as a result of selection and is 10 h for both early and modern genotypes. 2. Further analysis showed that the rate of delay in sexual maturity for constant photoperiods above 10 h is similar for modern and for early hybrids ( +0.29 d for each incremental one hour of photoperiod), the response of modern hybrids below 10 h ( +4.22 d for each one-hour reduction in photoperiod) is more than double that of early hybrids ( +1.71 d/h).
Resumo:
Despite long-standing interest in the forms and mechanisms of density dependence, these are still imperfectly understood. However, in a constant environment an increase in density must reduce per capita resource availability, which in turn leads to reduced survival, fecundity and somatic growth rate. Here we report two population experiments examining the density dependent responses under controlled conditions of an important indicator species, Chironomus riparius. The first experiment was run for 35 weeks and was started at low density with replicate populations being fed three different rations. Increased ration reduced generation time and increased population growth rate (pgr) but had no effect on survival, fecundity and female body weight in the first generation. In the second generation there was a six-fold increase in generation time, presumably due to the greatly reduced per capita resource availability as the estimated initial densities of the second generation were 300 times greater than the first. Juvenile survival to emergence, fecundity, adult body weight and pgr declined by 90%, 75%, 35% and 99%, respectively. These large between-generation effects may have obscured the effects of the threefold variation in ration, as only survival to emergence significantly increased with ration in the second generation. These results suggest that some chironomid larvae survive a reduction in resource availability by growing more slowly. In the ephemeral habitats sometimes occupied by C. riparius, the effects of population density may depend crucially on the longevity of the environment. A second experiment was therefore performed to measure pgr from six different starting densities over an eight-week period. The relationship between pgr and density was concave, viewed from above. At densities above 16 larvae per cm(2), less than 1% of the population emerged and no offspring were produced. Under the conditions of experiment 2 - an 8-week habitat lifespan carrying capacity was estimated as 8 larvae per cm(2).
Resumo:
A series of three-point bend tests using single edge notched testpieces of pure polycrystalline ice have been performed at three different temperatures (–20°C, –30°C and –40°C). The displacement rate was varied from 1 mm/min to 100 mm/min, producing the crack tip strain rates from about 10–3 to 10–1 s–1. The results show that (a) the fracture toughness of pure polycrystalline ice given by the critical stress intensity factor (K IC) is much lower than that measured from the J—integral under identical conditions; (b) from the determination of K IC, the fracture toughness of pure polycrystalline ice decreases with increasing strain rate and there is good power law relationship between them; (c) from the measurement of the J—integral, a different tendency was appeared: when the crack tip strain rate exceeds a critical value of 6 × 10–3 s–1, the fracture toughness is almost constant but when the crack tip strain rate is less than this value, the fracture toughness increases with decreasing crack tip strain rate. Re-examination of the mechanisms of rate-dependent fracture toughness of pure polycrystalline ice shows that the effect of strain rate is related not only to the blunting of crack tips due to plasticity, creep and stress relaxation but also to the nucleation and growth of microcracks in the specimen.