共查询到20条相似文献，搜索用时 31 毫秒
1.
Chidsey CE 《Science (New York, N.Y.)》1991,251(4996):919-922
The rate constant of the electron-transfer reaction between a gold electrode and an electroactive ferrocene group has been measured at a structurally well-defined metal-electrolyte interface at temperatures from 1 degrees to 47 degrees C and reaction free energies from -1.0 to +0.8 electron volts (eV). The ferrocene group was positioned a fixed distance from the gold surface by the self-assembly of a mixed thiol monolayer of (eta(5)C(5)H(5))Fe(eta(5)C(5)H(4))CO(2)(CH(2))(16)SH and CH(3)(CH(2))(15)SH. Rate constants from 1 per second (s(-1)) to 2 x 10(4) s(-1) in 1 molar HClO(4) are reasonably fit with a reorganization energy of 0.85 eV and a prefactor for electron tunneling of 7 x 10(4) s(-1) eV(-1). Such self-assembled monolayers can be used to systematically probe the dependence of electron-transfer rates on distance, medium, and spacer structure, and to provide an empirical basis for the construction of interfacial devices such as sensors and transducers that utilize macroscopically directional electron-transfer reactions. 相似文献
2.
Berndt T Böge O Stratmann F Heintzenberg J Kulmala M 《Science (New York, N.Y.)》2005,307(5710):698-700
We investigated the formation of new particles in a laboratory study, starting from H2SO4 produced in situ through the reaction of OH radicals with SO2. Newly formed particles were observed for H2SO4 concentrations above 7 x 10(6) per cubic centimeter. At 293 kelvin, a rough estimate yielded a nucleation rate of 0.3 to 0.4 particles per cubic centimeter per second for approximately 10(7) particles per cubic centimeter of H2SO4 (particle size >/= 3 nanometers). These findings are in agreement with observations from the atmosphere. The results demonstrate that under laboratory conditions similar to the atmosphere, particle formation occurs at atmospheric H2SO4 concentration levels. 相似文献
3.
The radiation-induced polymerization of formaldehyde has been studied in the solid state. The time of addition of one new link to a polymer chain increases exponentially in accordance with the Arrhenius law at 140 to 80 K, but approaches a constant value (approximately 10(-2) second) at temperatures below 10 K. Thus, a low-temperature limit to a chemical reaction rate has been observed. It is interpreted as a quantum effect caused by tunneling from the zero vibration level of the initial state, and a semiquantitative theory is given. The phenomenon should be taken into account for understanding tunneling of electrons in biological systems when such tunneling is accompanied by conformational changes. It could also be significant in slow, exothermic chemical reactions at low and ultralow temperatures, which may have had a role in chemical and biological evolution (cold prehistory of life?). 相似文献
4.
Demore WB 《Science (New York, N.Y.)》1973,180(4087):735-737
Chain decomposition of ozone by hydroxyl and hydroperoxyl radicals has been observed. The rate constant at 3000 degrees K for OH + O(3)-->HO(2) + O(2) is 8 x 10(-14) cubic centimeters per second. The rate constant for HO(2) + O(3)--> OH + 2O(2), is 3 x 10(-15) cubic centimeters per second. These results have implications concerning stratospheric ozone. 相似文献
5.
Field measurement of slow metamorphic reaction rates at temperatures of 500 degrees to 600 degrees C
High-temperature metamorphic reaction rates were measured using strontium isotopic ratios of garnet and whole rock from a field site near Simplon Pass, Switzerland. For metamorphic conditions of cooling from 612 degrees +/- 17 degrees C to 505 degrees +/- 15 degrees C at pressures up to 9.1 kilobars, the inferred bulk fluid-rock exchange rate is 1.3(-0.4)(+1.1) x 10(-7) grams of solid reacted per gram of solid per year, several orders of magnitude lower than laboratory-based estimates. The inferred reaction rate suggests that mineral chemistry may lag the evolving conditions in Earth's crust during mountain building. 相似文献
6.
Activities of beryllium-10 and aluminum-26 dissolved in 200-year-old Greenland ice were found to be 18.4 (+ 8.4, - 4.8) x 10(-6) and 3.2 +/- 0.9 x 10(-7) disintegration per minute per liter, respectively. From these values and the precipitation rate (30 milliliters of water per square centimeter per year), the production rates of these isotopes are calculated to be 3.6 (+ 1.6, - 0.9) x 10(-2) and 1.7 +/- 0.5 x 10(-4) atom per second * square centimeter. These rates agree with the rates calculated for the production of these isotopes by cosmic rays in the atmosphere. Probably all the Al(26) in the ice is accounted for by such atmospheric production; however, an upper limit for the influx of cosmic dust bearing aluminum-26 is calculated at 3.2 x 10(5) tons per year for Earth. Only upper limits could be found for Al(26) and Be(10) in the undissolved particulate matter in the ice; their addition to the activities in the dissolved material leaves our conclusions unchanged. 相似文献
7.
We measured the Newtonian constant of gravity, G, using a gravity gradiometer based on atom interferometry. The gradiometer measures the differential acceleration of two samples of laser-cooled Cs atoms. The change in gravitational field along one dimension is measured when a well-characterized Pb mass is displaced. Here, we report a value of G = 6.693 x 10(-11) cubic meters per kilogram second squared, with a standard error of the mean of +/-0.027 x 10(-11) and a systematic error of +/-0.021 x 10(-11) cubic meters per kilogram second squared. The possibility that unknown systematic errors still exist in traditional measurements makes it important to measure G with independent methods. 相似文献
8.
Beryllium-10 (10Be) in excess of that expected from in situ cosmic ray spallation reactions is present in lunar surface soil 78481; its presence was revealed with a sequential leaching technique. This excess 10Be, representing only 0.7 to 1.1% of the total 10Be inventory, is associated with surface layers (<1 micrometer) of the mineral grains composing 78481. This excess 10Be and its association with surficial layers corresponds to (1.9 +/- 0.8) x 10(8) atoms per square centimeter, requiring a 10Be implantation rate of (2.9 +/- 1.2) x 10(-6) atoms per square centimeter per second on the surface of the Moon. The most likely site for the production of this excess (10)Be is the Sun's atmosphere. The 10Be is entrained into the solar wind and transported to the lunar surface. 相似文献
9.
Direct catalytic hydration of terminal alkenes to primary alcohols would be an inexpensive route to industrially useful alcohols and a convenient synthetic route for the synthesis of terminal alcohols in general. The reaction between trans- PtHCl(PMe(3))(2) (where Me = CH(3)) and sodium hydroxide in a one-to-one mixture of water and 1-hexene yields a species that, at 60 degrees C and in the presence of the phasetransfer catalyst benzyltriethylammonium chloride, catalyzes selective hydration of 1-hexene to n-hexanol at a rate of 6.9 +/- 0.2 turnovers per hour. Hydration of 1-dodecene to n-dodecanol occurs at a rate of 8.3 +/- 0.4 turnovers per hour at 100 degrees C. Deuterium labeling experiments with trans-PtDCl(PMe(3))(2) show that hydration involves reductive elimination of a C-H bond. At low hydroxide concentrations (<8 equivalents), hydration of the water-soluble olefin 3-butene-1-ol to 1,4-butanediol exhibited a first-order dependence on hydroxide concentration for loss of catalytic activity. This suggests that hydroxide attacks the coordinated alkene slowly. At high hydroxide concentrations, the rate of catalysis was hydroxide-independent and first order in alkene. Substitution of coordinated water (k(1) = 9.3 +/- 0.5 x 10(-3) liters per mol per second) appears to be limitng under these conditions. 相似文献
10.
Redfield AC 《Science (New York, N.Y.)》1967,157(3789):687-692
Radioactive carbon determinations of the age of peat indicate that at Bermuda, southern Florida, North Carolina, and Louisiana the relative sea level has risen at approximately the same rate, 2.5 x 10(-3) foot per year (0.76 x 10(-3) meter per year), during the past 4000 years. It is proposed tentatively that this is the rate of eustatic change in sea level. The rise in sea level along the northeastern coast of the United States has been at a rate much greater than this, indicating local subsidence of the land. Between Cape Cod and northern Virginia, coastal subsidence of 13 feet appears to have occurred between 4000 and 2000 years ago and has continued at a rate of about 1 x 10(-3) foot per year since then. On the northeastern coast of Massachusetts, subsidence of 6 feet occurred between 4000 and 3000 years ago; since then sea level has risen at about the eustatic rate. Between 12,000 and 4000 years ago, sea level rose at an average of about 11 x 10(-3) foot per year. The part played by local subsidence or temporary departures from the average rate during this period is uncertain. 相似文献
11.
Sundström G Mowat JR Danared H Datz S Broström L Filevich A Källberg A Mannervik S Rensfelt KG Sigray P Ugglas MA Larsson M 《Science (New York, N.Y.)》1994,263(5148):785-787
Knowledge of the abundance of H(3)(+) is needed in interstellar and planetary atmospheric chemistry. An important destruction mechanism of H(3)(+) is low-energy electron impact followed by dissociation, but estimates of the reaction rate span several orders of magnitude. As an attempt to resolve this uncertainty, the cross section for dissociative recombination of vibrationally cold H(3)(+) has been measured with an ion storage ring down to collision energies below 1 millielectron volt. A rate coefficient of 1.15 x 10(-7) cubic centimeters per second at 300 kelvin was deduced. The cross section scaled with collision energy according to E(-1.15), giving thee rate a temperature dependence of T(-0.65). 相似文献
12.
The region of W-44 was mapped at 8350 megacycles per second. The degree of linear polarization of the most intense portion of W-44 integrated over the 10.8-minute-of-arc beam was 11+/-2 percent at position angle 45 degrees +/-5 degrees . This high degree of polarization is further evidence that W-44 is a supernova remnant. The integrated flux density of (95+/-25) x 10(-26) watt per square meter per cycle per second for this source is consistent with measurements at lower frequencies extrapolated with the use of a spectral index of-0.44, obtained by other observers. In addition, the compact source 3 minutes of right ascension west of W-44 was unpolarized, within the error of measurement. The flux density of (23+/-6)x 10(-26) watt per square meter per cycle per second determined for it along with the results of other observers indicate that this source has a thermal spectrum. 相似文献
13.
Platinum black efficiently catalyzes the oxidation of methane by iron(III) to generate carbon dioxide and eight equivalents of iron(II) in solutions of sulfuric acid in water. The rate of oxidation increases over 4 hours to reach approximately 4.83 x 10(-2) moles of iron(II) per gram atom of surface platinum per second. A redox fuel cell was assembled that used this reaction in a liquid reformer to generate soluble reducing equivalents of iron(II) from methane, which was electrochemically oxidized to iron(III) in the cell. A vanadium(V)-(IV)-nitric acid-O(2) redox system catalyzed the electrochemical reduction of O(2). The open-circuit voltage of the cell was 0.48 volt, and the maximum power output of the cell was 8.1 milliwatts per cubic centimeter of graphite felt electrode. 相似文献
14.
Talukdar R Mellouki A Gierczak T Burkholder JB McKeen SA Ravishankara AR 《Science (New York, N.Y.)》1991,252(5006):693-695
The rate coefficients, k(1), for the reaction of OH with CHF(2)Br have been measured using pulsed photolysis and discharge flow techniques at temperatures (T) between 233 and 432 K to be k(1), = (7.4 +/- 1.6) x 10(-13) exp[-(1300 +/- 100)/T] cubic centimeters per molecule per second. The ultraviolet absorption cross sections, sigma, of this molecule between 190 and 280 nanometers were measured at 296 K. The k(1), and sigma values were used in a one-dimensional model to obtain an atmospheric lifetime of approximately 7 years for CHF(2)Br. This lifetime is shorter by approximately factors of 10 and 2 than those for CF(3)Br and CF(2)ClBr, respectively. The ozone depletion potentials of the three compounds will reflect these lifetimes. 相似文献
15.
A method for the fast measurement of the diffusion coefficients of both small and large molecules in thin capillaries is reported. The method relies on Taylor-Aris dispersion theory and uses standard instrumentation for capillary zone electrophoresis. With this equipment, which consists of thin capillaries (50 to 100 micrometers in inner diameter), an injection system, detector ports, and computer data acquisition, a sample plug is pumped through the capillary at known velocity and the peak dispersion coefficient (D(*)) is measured. With the experimentally measured values of D(*) and flow velocity, and knowledge of the inner diameter of the capillary, the molecular diffusion coefficient (D) can be rapidly derived. For example, for ovalbumin a D value of 0.759 x 10(-6) square centimeter per second is found versus a tabulated value of 0.776 x 10(-6) square centimeter per second (error, 2 percent). For hemoglobin a D value of 0.676 x 10(-6) square centimeter per second is obtained versus a literature value of 0.690 x 10(-6) square centimeter per second (error, 1.5 percent). 相似文献
16.
The mass of extraterrestrial material accreted by the Earth as submillimeter particles has not previously been measured with a single direct and precise technique that samples the particle sizes representing most of that mass. The flux of meteoroids in the mass range 10(-9) to 10(-4) grams has now been determined from an examination of hypervelocity impact craters on the space-facing end of the Long Duration Exposure Facility satellite. The meteoroid mass distribution peaks near 1.5 x 10(-5) grams (200 micrometers in diameter), and the small particle mass accretion rate is (40 +/- 20) x 106 kilograms per year, higher than previous estimates but in good agreement with total terrestrial mass accretion rates found by geochemical methods. This mass input is comparable with or greater than the average contribution from extraterrestrial bodies in the 1-centimeter to 10-kilometer size range. 相似文献
17.
Gaseous, neutral H(2)O was detected in the coma of comet Halley on 22.1 and 24.1 December 1985 Universal Time. Nine spectral lines of thev(3) band (2.65 micrometers) were found by means of a Fourier transform spectrometer (lambda/triangle uplambda approximately 10(5)) on the NASA-Kuiper Airborne Observatory. The water production rate was approximately 6 x 10(28) molecules per second on 22.1 December and 1.7 x 10(29) molecules per second on 24.1 December UT. The numbers of spectral lines and their intensities are in accord with nonthermal-equilibrium cometary models. Rotational populations are derived from the observed spectral line intensities and excitation conditions are discussed. The ortho-para ratio was found to be 2.66+/-0.13, corresponding to a nuclear-spin temperature of 32 K (+5 K, -2 K), possibly indicating that the observed water vapor originated from a low-temperature ice. 相似文献
18.
A glass filter from Surveyor 3 has a surface density of approximately 1 x 10(6) tracks per square centimeter from heavy solar flare particles. The variation with depth is best fitted with a solar particle spectrum dN/dE = 2.42 x 10(6) E(-2) [in particles per square centimeter per year per steradian per (million electron volts per nucleon)], where E is the energy and N is the number of particles, from 2 million electron volts per nucleon to approximately 7 million electron volts per nucleon and dN/dE = 1.17 x 10(7) E(-3) at higher energies. Not much difference is observed between 0.5 and 5 micrometers, an indication that there is a lack of track-registering particles below 0.5 million electron volts per nucleon. The Surveyor data are compatible with track results in lunar rocks, provided an erosion rate of approximately 10(-7) centimeter per year is assumed for the latter. The results also suggest a small-scale erosion process in lunar rocks. 相似文献
19.
Schreiner PR Reisenauer HP Ley D Gerbig D Wu CH Allen WD 《Science (New York, N.Y.)》2011,332(6035):1300-1303
Chemical reactivity is conventionally understood in broad terms of kinetic versus thermodynamic control, wherein the decisive factor is the lowest activation barrier among the various reaction paths or the lowest free energy of the final products, respectively. We demonstrate that quantum-mechanical tunneling can supersede traditional kinetic control and direct a reaction exclusively to a product whose reaction path has a higher barrier. Specifically, we prepared methylhydroxycarbene (H(3)C-C-OH) via vacuum pyrolysis of pyruvic acid at about 1200 kelvin (K), followed by argon matrix trapping at 11 K. The previously elusive carbene, characterized by ultraviolet and infrared spectroscopy as well as exacting quantum-mechanical computations, undergoes a facile [1,2]hydrogen shift to acetaldehyde via tunneling under a barrier of 28.0 kilocalories per mole (kcal mol(-1)), with a half-life of around 1 hour. The analogous isomerization to vinyl alcohol has a substantially lower barrier of 22.6 kcal mol(-1) but is precluded at low temperature by the greater width of the potential energy profile for tunneling. 相似文献
20.
A new method for calculating the stress field in bounded ice shelves is used to compare strain rate and deviatoric stress on the Ross Ice Shelf, Antarctica. The analysis shows that strain rate (per second) increases as the third power of deviatoric stress (in newtons per square meter), with a constant of proportionality equal to 2.3 x 10(-25). 相似文献