Early Experimental Work

Two years later came the very important paper On the Caloric Effects of Magneto-Electricity, and on the Mechanical Value of Heat. In this paper he demonstrated that the heat caused by the passage of an electric current is not transferred from another part of the circuit, which is correspondingly cooled. but is actually generated. In his own words, he showed that  

As a result of a number of experiments Joule concluded that the mechanical value of a unit of heat was 838 ft.lbs of work expended to raise one pound of water by one degree (°F). 

These experiments, together with the conclusions drawn, were announced to the Chemical Section of the British Association meeting at Cork in 1843. They were received in silence partly, no doubt, because some of his audience were unable to grasp the full import of what was at stake, partly because others were unwilling to throw overboard the grand principle of the conservation of heat on which the entire science had been erected, and partly because still others felt that too much was being inferred from just one set of experiments. 

But Joule had already, in a postscript to this paper, transferred his attention from the electrical generation of heat to the purely frictional. By forcing water through tiny holes in a perforated cylinder, he had been able to evolve a detectable amount of heat, which compared with the work expended yielded a mechanical value for a unit of heat of 770 ft.lbs. This was in tolerable if not good agreement with the value obtained by means of the electrical experiments.  

Another of his early and little known experiments was to examine the effects of electricity on human beings. His subject was a servant girl who reported her sensations as the voltage was stepped up - he used a larger battery - to the moment when she became unconscious, whereat he felt it advisable to stop the experiment. Unfortunately the young lady s opinions were not recorded. (Cardwell, 1983) 

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Early experimental work in electrorefining at Los Alamos by Mullins et-all ) demonstrated that americium could be partitioned between molten plutonium and a molten NaCl-KCl salt containing Pu+3 ions, and Knighton et-al(8), working at ANL on molten salt separation processes for fuel reprocessing, demonstrated that americium could be extracted from Mg-Zn-Pu-Am alloys with immiscible molten magnesium chloride salts. Work... 

The charge of a number of proteins has been measured by titration. The early experimental work focused on the determination of charge as a function of pH later work focused on comparing the experimental and theoretical results the latter obtained from the extensions of the Tanford-Kirkwood models on the electrostatic behavior of proteins. Ed-sall and Wyman [104] discuss the early work on the electrostatics of polar molecules and ions in solution, considering fundamental coulombic interactions and accounting for the dielectric properties of the media. Tanford [383,384], and Tanford and Kirkwood [387] describe the development of the Tanford-Kirkwood theories of protein electrostatics. For more recent work on protein electrostatics see Lenhoff and coworkers [64,146,334]. 

Douglas et al. [98] have measured protein (serum albumin, ovalbumin, and hemoglobin) mobilities over a range of pH values using a free-flow electrophoresis apparatus and a particle electrophoresis apparatus. They found good agreement between the two measurements however, they also found some differences between their measurements and those reported in the older literature. They attributed the differences to the use of moving-boundary electrophoresis methods in the early experimental work and to differences in... 

A review of the early experimental works can be found in references [56-58]. More recently, Chutjian recorded the electron-impact excitation spectrum of formaldehyde [59,60] and reported transition energies that are taken as reference values in many other works. So are the experimental values compiled by Robin [61]. 

However, although high potassium concentration was thought essential in early experimental work (Acquatella etcd., 1972), Fuller and Pe (1976) reported that potassium concentrations much higher than normal plasma levels led to poor renal function. A number of more recent studies have claimed that solutions containing high concentrations of sodium ions were equally or even more effective than those with high potassium (Moen et al., 1989 Sumimoto etal., 1989 Marshall etal., 1991). 

Most of the early experimental work [250] has been done on molecular materials imbedded in a polymer matrix at concentrations of 10-80%, so a comparison of the intrinsic properties of the materials is not easy. Another obstacle is the dependence of the charge mobilities on the preparation technology (purity, morphology). However, some data are available for true one-component molecular glasses, a selection of which will be presented in the following sections. 

Early experimental work on the oxidation of carbon monoxide was confused by the presence of any hydrogen-containing impurity. The rate of CO oxidation in the presence of species such as water is substantially faster than the bone-dry condition. It is very important to realize that very small quantities of hydrogen, even of the order of 20 ppm, will increase the rate of CO oxidation substantially [8], Generally, the mechanism with hydrogen-containing compounds present is referred to as the wet carbon monoxide condition. 

Much of the early experimental work on allelopathy employed questionable methods and failed to produce unequivocal results. Now there is a substantial body of data obtained by sound techniques, that verifies the role of allelopathy in many plant communities. 

Experimental data are available for large particles at Re greater than that required for wake shedding. Turbulence increases the rate of transfer at all Reynolds numbers. Early experimental work on cylinders (VI) disclosed an effect of turbulence scale with a particular scale being optimal, i.e., for a given turbulence intensity the Nusselt number achieved a maximum value for a certain ratio of scale to diameter. This led to speculation on the existence of a similar effect for spheres. However, more recent work (Rl, R2) has failed to support the existence of an optimal scale for either cylinders or spheres. A weak scale effect has been found for spheres (R2) amounting to less than a 2% increase in Nusselt number as the ratio of sphere diameter to turbulence macroscale increased from zero to five. There has also been some indication (M15, S21) that the spectral distribution of the turbulence affects the transfer rate, but additional data are required to confirm this. The major variable is the intensity of turbulence. Early experimental work has been reviewed by several authors (G3, G4, K3). 

The early experimental work showed that the alkylation reactions could be carried out thermally and by using hydrofluoric acid or aluminum chloride as catalysts. Successful processes were developed with the hydrofluoric acid catalyst, and the first commercial HF unit started up on Christmas Day 1942, having a capacity of 1950 BPD (3). Other commercial HF alkylation units followed quickly. The thermal and aluminum chloride-catalyzed alkylation processes had limited commercial acceptance. 

In the most successful designs, the mercury is mechanically pushed out of the capillary. This type of electrode was constructed and used in the early experimental work of Randles and White [22]. Mercury was pushed from the... 

Seawater is the most abundant aqueous solution on Earth, and, as a consequence, has been the subject of countless studies (Millero 2001). The occurrence of marine evaporites has spurred much of the work on seawater solidification, which can occur by either evaporation or freezing. Early experimental work on the evaporation of seawater was done by Usiglio (1849). Whereas most evaporites on Earth probably involved mainly or only evaporation (particularly under hot, arid climatic conditions, 25-50 °C), cold-climate evaporation and freezing without evaporation are also common means by which... 

A number of examples in the gas phase are known, some of which are summarized in Refs. 1, 52, and 53. In solution, there is much early experimental work on VET for the CH stretch fundamental in assorted molecules, which invoked involvement of a Fermi resonance between the CH stretch and the overtone of the CH bend (54) reviews of this work can be found in Refs. 1, 55, and 56. 

Early experimental work on the conformational preferences in solution for a variety of 2-substituted heterocycles 194 is summarized in Table 36. Most of these conclusions were deduced either from dipole moment measurements in benzene or by the use of lanthanide-induced shifts for chloroform solutions. 

In early experimental work, the interior and exterior cell concentrations of K+, Na+, and Cl ions were measured and compared against those obtained from the Nernst potentials, given by... 

This type of experiment was extensively used in very early experimental works on craze growth. Doll and coworkers used it with optical interferometry to evaluate... 

As shown above, there are two important plots the craze length S or thickness Tmax versus log (VJ and the log (V ) versus log (%) plots. Both will give the relative activation volumes of the craze fibrils growth and breakage. It has been shown by early experimental work that for PMMA and other materials the craze length or thickness remains almost constant over severeal decades of velocity as well... 

Due to the changes in the dynamics, a general relationship for stochastic dynamics is not available like it is for deterministic dynamics. However, for mesoscopic systems, a mesoscopic FR is useful. Therefore, there has been much work on developing stochastic models with different conditions. Andrieux and Gaspard developed a stochastic fluctuation relation for nonequilibrium systems whose dynamics can be described by Schnakenberg s network theory (e.g. mesoscopic electron transport, biophysical models of ion transport and some chemical reactions). Due to early experimental work on protein unfolding and related molecular motors, and their ready treatment by stochastic dynamics, a number of papers have appeared that model these systems and test the or JE for these. FR... 

It is important to understand the experimental measurement of blend time. The early experimental work was done by using the... 

Cardiac effects were reported from early experimental work using very high doses of ebastine, but they are not believed to be clinically relevant in normal use. In one study serial electrocardiograms showed no changes with doses up to the maximum used (30 mg). Ebastine in doses up to five times the recommended therapeutic dose did not cause clinically relevant changes in QTc interval in healthy subjects (2). Co-administration of ebastine with ketoconazole or erythromycin did not lead to significant changes in the QTc interval (3,4). 

Walter Hleber (1895-1976) was a student of Rudolf Weinland, who performed early experimental work on Alfred Werner s theory of coordination compounds (Hauptvalenzen, Nebenvalenzen). Hieber received his Ph. D. in 1919 from Tubingen University on a topic concerning ferric complexes of hypophosphorous acid. He then developed metal carbonyl chemistry, mainly at Technische Hochschule Miinchen (1935-1964) he is now considered the pioneering researcher in this area of study. His name is associated with compounds like HCo(CO)4 and H2pe(CO)4 that are relevant to catalytic hydrogen-transfer reactions (hydroformylation Section 2.1.1). Nucleophilic addition to metal carbonyls, e. g., Fe(CO)5 -i-OH —> [(C0)4FeC(=0)0H] , is known as the Hieber base reaction (cf. [76]). 

We have evaluated both DHDECMP and DBDECMP as actinide extractants from the ICPP wastes. Both reagents were purchased from Wateree Chemical Company, Inc., Lugoff, S.C. on a "custom-synthesis" basis. Due to the ease of purifying the "as-received" DBDECMP, much of our early experimental work was with this compound C7,8). When aqueous solubility measurements indicated DBDECMP to be appreciably soluble (60 g/L) in 0.1M HN03 our attention was directed to the use of DHDECMP which exhibits an aqueous solubility similar to TBP (0.4 to 0.5 g/L) (7 99). 

Although a general mathematical treatment of system peaks was published very early by Helfferich and Klein [8], most early experimental work ignored these theoretical explanations. The first experimental observation of system peaks was probably reported by Fornstedt and Porath [9], while Solms et al. [10] made the... 

Early experimental work on /(N-C) has been summarized by Randall, (86) Lichter, (87) and Axenrod. (88) In the discussion that follows, empirical trends, observed for /(N-C) in different classes of nitrogen compounds, are presented. 

The early experimental work that determined the mechanism by which purines are synthesized was carried out on a variety of laboratory animals and microorganisms. None of the data so obtained indicates a difference in the reactions utilized by the various species, nor is there evidence to indicate that man is unique in this regard. 

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