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31.
The basic principle of comparing the sample
mass with the mass of a reference body in equilibrium gives the equal-armed
beam balance a unique accuracy. Main parameters characterising the suitability
of the instrument are measuring range, resolution and relative sensitivity
(resolution/maximum load). The historical development of the values of these
parameters achieved depended strongly on the practical need in those times.
Technically unfavourable scales of the oldest Egyptian dynasties (~3000
BC) could resolve mass differences of 1 g and had a relative sensitivity of
at least 10–3. More sophisticated instruments
from the 18th Dynasty (~1567–1320 BC) achieved
a relative sensitivity of 10–4 independent
of the size of the instrument. In 350 BC Aristotle clarified the theory of
the lever and at about 250 BC Archimedes used the balance for density determinations
of solids. The masterpiece of a hydrological balance was Al Chazini’s
'Balance of Wisdom’ built about 1120. Its relative sensitivity
was 2⋅10–5.
Real progress took
place when scientists like Lavoisier (1743–1794) founded modern chemistry.
At the end of the 19th century metrological balances
reached a relative sensitivity of 10–9 with
a maximum load of several kilogrammes. That seems to be the high end of sensitivity
of the classical mechanical beam balance with knife edges. Improvements took
place by electrodynamic compensation (Emich, Gast).
In 1909 Ehrenhaft
and Millikan could weigh particles of 10–15
g by means of electrostatic suspension. In 1957 Sauerbrey invented the oscillating
quartz crystal balance. By observing the frequency shift of oscillating carbon
nanotubes or of silica nanorods, masses or mass changes in the attogram or
zeptogram have been observed recently. 相似文献
32.
33.
Christo I. Ivanov Nikolai Tyutyulkov Gottfried Olbrich H. Barentzen Oscar E. Polansky 《Theoretical chemistry accounts》1988,73(1):27-42
Utilizing an extended Hubbard-type Hamiltonian which incorporates both nearest-neighbour Coulomb repulsion and exchange interactions, we have studied the energy dispersion of the lowest elementary excitation from the ferromagnetically aligned state of quasi one-dimensional alternant hydrocarbon networks. It was found that the main effect of the long range Coulomb interaction may be thought of as a renormalization (screening) of the on-site Hubbard integral. This implies an enhancement of the kinetic exchange term and impairs the stability of the ferromagnetic state towards single spin inversions. However, for physically relevant values of the parameters entering the model Hamiltonian, the collective spin excitation represents a magnon, whose energy band lies above the reference value pertaining to the magnetically saturated configuration.Dedicated to Prof. Dr. Adolf Neckel on the occasion of his 60th birthday 相似文献
34.
In weakly acidic buffer medium, the interaction of amikacin with calf thymus DNA, yeast RNA and denatured DNA has been investigated by using resonance Rayleigh scattering (RRS) technique. The result shows that calf thymus DNA is capable of enhancing the RRS intensity of the amikacin, while yeast RNA and denatured DNA have very little enhancement effect. Based on the characteristics, a sensitive assay for detecting double-stranded DNA in the presence of denatured DNA and yeast RNA has been developed. The enhancement of the RRS signal is directly proportional to the concentration of double-stranded DNA in the range 0.02-12.0 μg ml−1 for calf thymus DNA and its detection limit (3σ) is 2.5 ng ml−1. The method shows a wide linear range and high sensitivity, and almost no interference can be observed from RNA, denatured DNA, amino acid and most of the metal ions. The trace amounts of nucleic acid in synthetic samples and practical samples are determined with satisfactory results. Therefore, the proposed method is promising for as an effect means for recognition in vivo and determination in situ of double-stranded DNA. 相似文献
35.
We developed a novel measurement method of the Donnan potential difference at a charged membrane/salt solution interface. The method can measure the potential under the condition that the membrane charge density is much lower than the KCl concentration of the salt bridge. This method is very useful for obtaining the effective charge density of each layer of a bipolar membrane. The present experiments in a system of a negatively charged poly(vinyl alcohol) membrane and a single salt solution of KCl, NaCl, LiCl, CaCl2 and LaC3 revealed that the membrane effective charged density has the same value for all the ions. The experiments in mixed KCl and CaCl2 solution revealed that the potential in the system is governed mainly by the concentration of the counterion having the highest valence in the system. 相似文献
36.
New spin-state-selective (S3) NMR pulse sequences exclusively applying cross-polarization schemes to achieve optimum homonuclear and heteronuclear 1H-X coherence transfer are reported for the simple and accurate measurement of the magnitude and sign of heteronuclear coupling constants for samples at natural abundance. The proposed spin-edited HCP-TOCSY experiments are based on clean heteronuclear S3 excitation, generated by simultaneous co-addition of two independent in-phase and anti-phase components created during the mixing heteronuclear J-cross-polarization (HCP) step, which is finally transferred to other protons by a conventional homonuclear TOCSY mechanism. Selective 1D and non-selective 2D approaches for the easy determination of long-range proton-carbon and proton-nitrogen coupling constants on any protonated and non-protonated heteronuclei are presented and discussed for several organic molecules. 相似文献
37.
Atomic chemisorption of hydrogen and oxygen on the Ni(100) surface has been studied using an Effective Core Potential (ECP) approach described in a previous paper. Clusters of up to 50 nickel atoms have been used to model the surface. The computed chemisorption energies are 62 kcal/mol (exp. 63 kcal/mol) for hydrogen and 106 kcal/mol (exp. 115–130 kcal/mol) for oxygen. Correlating the adsorbate and the cluster-adsorbate bonds is extremely important for obtaining accceptable results, particularly for oxygen. Reasonable convergence of chemisorption energies is obtained with 40–50 cluster atoms for both hydrogen and oxygen. For hydrogen the addition of a third cluster layer stabilizes the results considerably. Both hydrogen and oxygen are adsorbed at (or close to) the four-fold hollow site. The calculated barriers for surface migration are also in good agreement with the experimental estimates. The calculated equilibrium heights above the surface are on the other hand too high compared with experiments. This disagreement is believed to be due to core-valence correlation effects, which are not incorporated in the present ECP. The cluster convergence for the height above the surface is much slower than for the chemisorption energy. 相似文献
38.
Summary Time-dependent perturbation theory has been applied to calculate the doubly excited triplet statesNsns:3Se,Npnp:3De andNdnd:3Ge (N=2, 3, 4,n=N+1, ... ,5) for He, Li+, Be2+ and B3+. A time-dependent harmonic perturbation causes simulataneous excitation of both the electrons with a change of spin state. The doubly excited energy levels have been identified as the poles of an appropriately constructed linearized variational functional with respect to the driving frequency. In addition to the transition energies, effective quantum numbers of these doubly excited states have been calculated and analytic representations of their wave functions are obtained. These are utilized to estimate the Coulomb repulsion term for these states which checks the consistency of the wave functions. These wave functions may also be used for calculating other physical properties of the systems. 相似文献
39.
《Electroanalysis》2004,16(8):650-655
An analytical solution is developed for heterogeneous ECE processes occurring at channel electrode surface for both laminar and turbulent flow. The solution explicitly links the behavior of ECE processes and the parameters. A simple expression of the effective number of electrons transferred, covering all the reaction rate constants and different diffusion coefficients of the reactant A and the intermediate product B, is obtained. Excellent agreement with previous numerical and analytical results is shown . Parametric studies illustrate the effects of diffusion coefficients, hydrodynamic factors and reaction rate constants on the effective number of electrons transferred and the currents. 相似文献
40.
Band structure calculations at the level of LMTO-ASA provide insight into the electronic structure of BaV10O15 and the origin of the structural phase transition. A crystal orbital Hamiltonian population/integrated crystal orbital Hamiltonian population analysis provides evidence that the crystallographic phase transition is driven by V-V bond formation. As well, the energy bands near the Fermi level are very narrow, <1 eV, consistent with the fact that the observed insulating behavior can be due to electron localization via either Mott-Hubbard correlation and/or Anderson disorder. The partial solid solution, BaV10−xTixO15, was examined to study the effect of Ti-doping at the V sites on the structure and electronic transport properties. In spite of the non-existence of “BaTi10O15”, the limiting x=8, as indicated by a monotonic increase in the cell volume and systematic changes in properties. This limit may be due to the difficulty of stabilizing Ti2+ in this structure. For x=0.5 both the first order structural phase transition and the magnetic transition at 40 K are quenched. The samples obey the Curie-Weiss law to x=3 with nearly spin only effective moments along with θ values which range from −1090 K (x=0.5) to −1629 K (x=3). For x>3 a very large, ∼2×10−3 emu/mol, temperature independent (TIP) contribution dominates. Conductivity measurements on sintered, polycrystalline samples show semiconducting behavior for all compositions. Activation energies for Mott hopping derived from high temperature data range from ∼0.1 eV for x=0-1 and fall to a plateau of 0.06 eV for x=3-7. Low temperature data for x=3, 5 and 7 show evidence for Mott variable range hoping (VRH) with a T1/4 law and in one case between 5 and 17 K, a Efros-Shklovskii correlated hopping, T1/2 law, was seen, in sharp contrast to BaV10O15 where only the E-S law was observed up to 75 K. Seebeck coefficients are small (<35 μV/K), positive, roughly TIP and increase with increasing x up to x=5. This may point to a Heikes hopping of holes but a simple single carrier model is impossible. The compositions for x>3 are remarkable in that local moment behavior is lost, yet a metallic state is not reached. The failure of this system to be driven metallic even at such high doping levels is not fully understood but it seems clear that disorder induced carrier localization plays a major role. 相似文献