Measurement earliest

The earliest molecular beam infrared experiments on Van der Waals complexes used photodissociation spectroscopy a molecular beam is irradiated witli a tunable infrared laser and tire molecular beam intensity is measured as a function of... 

Condensed phase vibrational or vibronic lineshapes (vibronic transitions create vibrational excitations of electronic excited states) rarely provide infonnation about VER (see example C3.5.6.4). Experimental measurements of VER need much more than just the vibrational spectmm. The earliest VER measurements in condensed phases were ultrasonic attenuation studies of liquids [15], which provided an overall relaxation time for slowly (>10 ns) relaxing small molecule liquids. 

In voltammetry a time-dependent potential is applied to an electrochemical cell, and the current flowing through the cell is measured as a function of that potential. A plot of current as a function of applied potential is called a voltammogram and is the electrochemical equivalent of a spectrum in spectroscopy, providing quantitative and qualitative information about the species involved in the oxidation or reduction reaction.The earliest voltammetric technique to be introduced was polarography, which was developed by Jaroslav Heyrovsky... 

The earliest examples of analytical methods based on chemical kinetics, which date from the late nineteenth century, took advantage of the catalytic activity of enzymes. Typically, the enzyme was added to a solution containing a suitable substrate, and the reaction between the two was monitored for a fixed time. The enzyme s activity was determined by measuring the amount of substrate that had reacted. Enzymes also were used in procedures for the quantitative analysis of hydrogen peroxide and carbohydrates. The application of catalytic reactions continued in the first half of the twentieth century, and developments included the use of nonenzymatic catalysts, noncatalytic reactions, and differences in reaction rates when analyzing samples with several analytes. 

To give an idea of the wide rai e of catalytic systems that have been investigated where chemisorption data were essential to interpret the results, some of the author s papers will be discussed. Measurements were reported on the surface areas of a very wide range of metals that catalyze the hydrogenation of ethane. In the earliest paper, on nickel, the specific catalytic activity of a supported metal was accurately measured for the first time it was shown also that the reaction rate was direcdy proportional to the nickel surface area. Studies on the same reaction... 

The earliest observations of carbon nanotubes with very small (nanometer) diameters [151, 158, 159] are shown in Fig. 14. Here we see results of high resolution transmission electron microscopy (TEM) measurements, providing evidence for m-long multi-layer carbon nanotubes, with cross-sections showing several concentric coaxial nanotubes and a hollow core. One nanotube has... 

Table 3.3 summarizes the history of the development of wave-profile measurement devices as they have developed since the early period. The devices are categorized in terms of the kinetic or kinematic parameter actually measured. From the table it should be noted that the earliest devices provided measurements of displacement versus time in either a discrete or continuous mode. The data from such measurements require differentiation to relate them to shock-conservation relations, and, unless constant pressures or particle velocities are involved, considerable accuracy can be lost in data processing. 

Optical devices or optical systems have provided most of the available strong shock data and were the primary tools used in the early shock-compression investigations. They are still the most widely used systems in fundamental studies of high explosives. The earliest systems, the flash gap and mirror systems on samples, provided discrete or continuous measurements of displacement versus time. 

Once such effects had been noted, it became necessary to interpret the observed results and to classify the solvents. The earliest attempts at this were by Stobbe, who reviewed the effects of solvents on keto-enol tautomers [4]. Since then many attempts have been used to explain solvent effects, some based on observations of chemical reactions, others on physical properties of the solvents, and yet others on spectroscopic probes. All of these have their advantages and disadvantages and no one approach can be thought of as exclusively right . This review is organized by type of measurement, and the available information is then summarized at the end. 

Intermediate methods include the earliest procedure based on Stein s equation [33] and one based on Samuels equation [34]. Among the direct methods is an IR spectroscopic method based on the measurement of the dichroic ratio (R), of amorphous absorption bands. In the investigations [35], the amorphous bands 898 cm" and 1368 cm", for which the angles of transition moment are a898 = 39 and aneg = 80 , respectively, were used. Other methods are spectroscopy of polarized fluorescent radiation [35,36], measurement of color di-... 

The choice of alloy for any particular application is determined by the desired physical, mechanical and metallurgical properties. Within these limits, however, a range of materials is usually available. It is essential that at the very earliest stage the choice of materials and the details of design of the installation should be considered from the point of view of corrosion, if the best performance is to be obtained in service. This is particularly true of copper alloys, where protective measures are not normally applied. 

One of the earliest steps in product design is to establish the configuration of the product that will form the basis on which a suitable material is selected to meet performance requirements. During this phase certain design features have to be kept in mind to avoid problems such as reduction of properties. Such features are called detractors or constraints. Most of them are responsible for the unwanted internal stresses that can reduce the available stress level for load bearing purposes. Other features may be classified as precautionary measures that may influence the favorable performance of a product if they are properly incorporated. 

Luminescence measurements on proteins occupy a large part of the biochemical literature. In what surely was one of the earliest scientific reports of protein photoluminescence uncomplicated by concurrent insect or microorganism luminescence, Beccari (64), in 1746, detected a visible blue phosphorescence from chilled hands when they were brought into a dark room after exposure to sunlight. Stokes (10) remarked that the dark (ultraviolet) portion of the solar spectrum was most efficient in generating fluorescent emission and identified fluorescence from animal matter in 1852. In general, intrinsic protein fluorescence predominantly occurs between 300 nm and 400 nm and is very difficult to detect visually. The first... 

Amongst the earliest measurements involving chemical functionality of the probe were those of Nakagawa et al. [69]. They investigated octadecyltrichlorosilane (OTS) chemically modified tips against chemically adsorbed monolayers of different alkyl-trichlorosilanes in ethanol, as shown schematically in Figure 14. When both tip and surface were modified by OTS, a large adhesive force was observed that was not present for the case of an unmodified silicon nitride tip on an OTS-modified surface. Additionally there... 

The earliest attempts to measure the rate of exchange between ferrous and ferric ions in aqueous media utilised the diffusion separation technique. Little agreement was obtained by the different workers Diffusion separation factors, found to be 0.5 , 1.4, 3.5 and 1.2, illustrate the difficulty of the technique. The isotopes used to label the iron were either Fe or Fe, and exchange was found to be complete in hours or many days > in perchlorate media. 

One of the earliest interpretations of latent vectors is that of lines of closest fit [9]. Indeed, if the inertia along v, is maximal, then the inertia from all other directions perpendicular to v, must be minimal. This is similar to the regression criterion in orthogonal least squares regression which minimizes the sum of squared deviations which are perpendicular to the regression line (Section 8.2.11). In ordinary least squares regression one minimizes the sum of squared deviations from the regression line in the direction of the dependent measurement, which assumes that the independent measurement is without error. Similarly, the plane formed by v, and Vj is a plane of closest fit, in the sense that the sum of squared deviations perpendicularly to the plane is minimal. Since latent vectors v, contribute... 

In physical chemistry, entropy has been introduced as a measure of disorder or lack of structure. For instance the entropy of a solid is lower than for a fluid, because the molecules are more ordered in a solid than in a fluid. In terms of probability it means also that in solids the probability distribution of finding a molecule at a given position is narrower than for fluids. This illustrates that entropy has to do with probability distributions and thus with uncertainty. One of the earliest definitions of entropy is the Shannon entropy which is equivalent to the definition of Shannon s uncertainty (see Chapter 18). By way of illustration we... 

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