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  • Articles  (2,704)
  • Wiley-Blackwell  (2,704)
  • 1980-1984
  • 1955-1959  (2,704)
  • 1925-1929
  • 1956  (2,704)
Collection
  • Articles  (2,704)
Years
  • 1980-1984
  • 1955-1959  (2,704)
  • 1925-1929
Year
  • 101
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    Hoboken, NJ : Wiley-Blackwell
    AIChE Journal 2 (1956), S. 429-429 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 102
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    AIChE Journal 2 (1956), S. 431-436 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Chemical equilibrium in this reaction has been determined experimentally by a static or nonflow method at temperatures of 400° and 450°C. and at pressures of 1,000 to 3,500 atm. Equilibrium was approached from both sides and the two reacting gases were always in the stoichiometric ratio. The results are presented both as mole percentage of ammonia in the equilibrium mixture and as the equilibrium constant Kp. The constant, Kp, which is a function of pressure, was calculated from Kp°, its value at p = 0, by five different methods and from them the corresponding mole percentages of ammonia were derived for comparison with the experimental results. All such calculations involve assumptions of varying degrees of validity, and no calculated value can be considered accurate. However two of the calculation methods give values which agree reasonably well with the experimental values.
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  • 103
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    AIChE Journal 2 (1956), S. 468-470 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rates of both the liquid-phase mass transfer and the internal-diffusion steps in ion exchange were studied by means of shallow-bed experiments. The mass transfer coeffcients obtained fitted the general correlations for other packed-bed operations when the Schmidt group was evaluated with experimentally determined ionic counterdiffusivities. An incremental calculation of the diffusion rates within the particles yielded a value of the counterdiffusivity in the resin phase. A general design procedure based on these findings is proposed.
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  • 104
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    AIChE Journal 2 (1956), S. 456-463 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The design and operation of a pilot-scale-moving bed adsorber to separate the various components of a gas mixture using activated carbon as the preferential adsorbent are described. A binary system, methane-acetylene, and a ternary system, methane-carbon dioxide-acetylene, were studied. The performance of the unit was analyzed by means of the transfer-unit-height (H.T.U.) concept based on the observed changes in gas composition during tower operation. For both the binary and ternary systems the transfer-unit height was independent of feed-gas composition but was found to vary linearly with the ratio of feed gas to carbon flow. The over-all transfer-unit-height values based on either the gas or the adsorbed phase were observed to vary from 6.5 in. at 1.39 std. cu. ft./lb. carbon to 36.9 in. at 4.81 std. cu. ft./lb. carbon.
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  • 105
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    AIChE Journal 2 (1956), S. 477-481 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The theoretical-plate concept in chromatography has been treated on the basis of continuous flow of eluent through the plates of the column. A treatment more precise in principle than the previous treatments is presented. General elution and deposition equations have been derived and applied to special cases of practical interest. The derived formulas have the advantage of precision, generality, and simplicity.The theory was found adaptable to the treatment of gradient elution and also to the calculation of the fraction of solute which has been eluted or still-adsorbed on the column during the elution process.A method for the determination of the number of theoretical plates in a chromatographic column is also described.
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  • 106
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    AIChE Journal 2 (1956), S. 545-551 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Liquid-liquid phase separation and mass transfer studies were made in a 4-in.-diam. cyclone of conventional construction. The cyclone was tested with oil-water volume phase ratios ranging from values of 1/3 to 9/1 and for total flows up to 24 gal./min., although most variables were studied at a feed rate of 10 gal./min. Kerosene or a white oil (vis. 9 centipoises at 77°F.) was used as the oil phase. Valve or line premixing was used to disperse the feed. Valve pressure drops were in the range of 0.1 to 1.0 lb./sq.in., and inlet drop sizes, where determined, were about 1 mm. The optimum cyclone geometry (volume, diameter of inlet, overflow and underflow lines) and the optimum split (overflow/underflow) were determined in terms of a phase-separation efficiency Es.At optimum geometry and split a number of mass transfer runs were made in which monobutylamine solute was transferred from the kerosene to the water phase. These runs indicated that Es decreased but mass transfer efficiency increased as the feed rate or pressure drop across the mixing valve was increased.
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  • 107
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 108
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    AIChE Journal 2 (1956), S. 12D-12D 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 109
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    AIChE Journal 2 (1956), S. 12D-12D 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
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  • 110
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    AIChE Journal 2 (1956), S. 578 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 111
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    AIChE Journal 2 (1956), S. 101-106 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The object of this study has been the measurement of concentration profiles of water vapor in a wetted-wall column with fully developed turbulent pipe flow of air for several positions downstream of the inlet. The air Reynolds number was 25,000. The mathematical formulation of this problem involves the Navier-Stokes equations and the mass transfer equation with a boundary condition of constant concentration at the wall. No attempt has been made toward an analytical solution of this problem, as the exact solution of the turbulence problem has not been developed. Instead, values of the mass and momentum transfer correlation, urh, and urux, have been computed as a function of the radius. The eddy diffusivity for momentum and mass and the local mass transfer rates are shown for engineering purposes.
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  • 112
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    AIChE Journal 2 (1956), S. 94-100 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An apparatus for the determination of relative permeability under simulated reservoir conditions has been designed, constructed, and operated successfully. Complete water-oil relative-permeability data, with kerosene and simulated reservoir brine have been taken on four natural-sandstone cores at fluid pressures to 5,000 1b./sq. in. and overburden pressures to 10,000 1b./sq. in. One run was made at low pressure at a temperature of 160°F. for comparison with the results at low temperature. The apparatus is now being expanded so that gas-oil relative-permeability data may be taken, and crude oil containing gas in solution may be employed as the oil phase.The results indicate that essentially the same water-oil relative-permeability data are obtained at fluid pressures of 5,000 1b./sq. in. as at 30 1b./sq. in. gauge. The application of overburden pressure causes a reduction in both water and oil effective permeability in about the same proportion as it affects the single-phase permeability. Consequently the calculated relative permeabilities are affected to only a moderate extent. The results of the one run at 160°F. were in good agreement with the values obtained at room temperature.
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  • 113
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    AIChE Journal 2 (1956), S. 148-152 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An investigation using the hexone-water system was made of flooding in a 1-in.-diam. ten-plate pulse column. An analysis of column operation led to the derivation of an equation for predicting conditions of inadequate pulsation and for establishing the amount of liquid recycled under any operating conditions.
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  • 114
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    AIChE Journal 2 (1956), S. 157-162 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A natural-circulation loop with water as the circulating fluid was studied for a range of operation covering two-phase flow. The work reported in this paper is concerned with the periodic oscillations of the flow rate and fluid temperature. The oscillations occurred even with constant heat input and constant cooling-water properties for the heat exchanger. The analytical approach includes a theoretical analysis of an open-ended system and numerical solutions obtained with an analogue computer for a simplified loop system. Also presented are the equations of motion, continuity, and energy, which were developed for a transient two-phase flow model for adaptation to more detailed numerical evaluations.
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  • 115
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    AIChE Journal 2 (1956), S. 163-168 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The liquid-metal-fuel reactor under development at the Brookhaven National Laboratory uses a fuel which is a solution of U233, Mg, and Zr in liquid bismuth. For a power breeder thermal reactor, high neutron economy is essential, and this calls for low concentrations of those fission products in the fuel which are high neutron capturers. Roughly 45% by weight of the fission products can be continuously removed from the fuel by salt extraction with alkali and alkaline-earth fused-salt mixtures. These fission products contain the highly “poisonous” rare earths. This paper will present a discussion of processdesign considerations and proposed flow sheets.
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  • 116
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    AIChE Journal 2 (1956), S. 177-183 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Knowledge of local heating rates is needed for estimation of operating temperatures, thermal stresses, and cooling requirements in nuclear reactor components. Heat is liberated by the dissipation of the energy of fission fragments, beta particles, fast neutrons, and gamma photons. Heating rates are formulated in terms of either neutron or gamma flux densities, the corresponding collision probabilities, and appropriate energy transfer coefficients, the forms of which are given. Special methods of estimating the flux densities are discussed. The data on the magnitudes of the various energy sources are reviewed.
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  • 117
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the proposed system for counting variables in separation processes the processes are resolved into their simpler component classes, e.g., theoretical plates, heat exchangers, reboilers, distillation columns, etc., and a distinction is made between those variables which are inherent in the systems and those which may be specified for design. Results are presented for the most commonly occurring component classes, and all possible process relations existing among these classes are expressed by a set of generalized equations [(16) to (19)]. The procedure of counting variables is therefore reduced to compositon from variables for the component classes by use of the generalized equations.
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  • 118
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    AIChE Journal 2 (1956), S. 249-250 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Natual and forced convection have always been correlated on different bases although the two phenomena have much in common. Accordingly, a method for correlating both types of convection on the same basis, at least for heat transfer outside horizontal cylinders, would be of interest.A tentative method of accomplishing this for transverse convection is presented, involving certain simplifying assumptions relating to drag and buoyancy, from which an “effective velocity” for natural convection is calculated (by means of the well-known drag correlation) and incorporated in a Reynolds number. The Nusselt number for natural convection is then correlated in terms of the Prandtl number and this Reynolds number in much the same manner as that for McAdams's well-known correlation for forced convection. For 150 different combinations of independent variables covering seven different fluids and wide ranges of diameter, surface temperature, and bulk fluid temperature, the transformed natural-convection data agree with Douglas and Churchill's recent refinement of McAdams's relationship for forced convection with an average deviation of about ±10%.
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  • 119
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    AIChE Journal 2 (1956), S. 259-264 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 120
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    AIChE Journal 2 (1956), S. 251-258 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Interest in the course of chemical reactions in turbulent flow has made desirable detailed knowledge of the temperature distribution in flowing streams. One method of predicting the temperature distribution under a variety of conditions is reviewed here, the approach being limited to conditions of local uniform transport of momentum. A discussion of some of the aspects of eddy conductivity is included along with a brief review of the velocity distribution in uniform flow.The results serve to illustrate the relation of microscopic conditions of flow to the temperature distribution in a turbulently flowing stream. The importance of the molecular Prandtl number upon the transfer process is stressed.
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  • 121
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    AIChE Journal 2 (1956), S. 271-272 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method, based upon the pertinent flat-plate heat transfer equation, is presented for computing the local heat transfer coefficients for a boundary layer subjected to streamwise velocity and pressure gradients. No extensive mathematical background is required as the complexity of a rigorous solution for this type of problem is avoided. The validity of the method for gases is demonstrated by comparison of the predicted coeffcients with the experimental data for two widely different problems.
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  • 122
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    AIChE Journal 2 (1956), S. 264-270 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect of chemical reaction on plate efficiency has been given little attention in the determination of bubble-plate efficiencies, although it is of importance in many operations. A typical example is the absorption of carbon dioxide in monoetnanolamine solutions.The over-all Murphree gas-phase plate efficiency can be shown to be a function of Kg(A/V) where A/V is the interfacial surface area formed per tray per unit volume of gas. In order to evaluate variations in tray efficiency due to factors influencing Kg, data available in the literature for the absorption of carbon dioxide in monoethanolamine were considered. These showed that the liquid film was controlling and that for a packed column at constant liquid rate the absorption coefficient could be satisfactorily expressed by an equation that resembles somewhat equations which have been developed for the effect of rapid secondorder reactions on kL. However, the observed effect of carbon dioxide partial pressure in the gas is not so great as the theoretical equations would predict.By use of the equation mentioned above to predict Kg, satisfactory correlation of observed plate efficiencies is obtained for a commercial column over a considerable range of conditions. It appears that the correlation can be extended to other pressures, flow rates, and column designs by an evaluation of the effect of these variables on A/V and Kg.
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  • 123
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    AIChE Journal 2 (1956), S. 273-276 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Because little information is available concerning the behavior of hydrocabons under conditions far from equilibrium, it appears desirable to obtain data for the diffusion coefficients of the lighter hydrocarbons in the gas phase.The Maxwell diffusion coefficients of n-heptane in the gas phase of the ethane-n-heptane and propane-n-heptane systems were measured at temperatures from 100° to 220° F. and for pressures up to 60 lb./sq. in. The fick diffusion coefficient was calculated as a function of state from these measurements.The experimental results indicate that the interfacial resistance between the liquid and the gas phases into which the transport was taking place is small. It was found that pressure exerted a significant influence upon the Maxwell diffusion coefficient for both of the binary systems investigated. There is a marked decrease in the Maxwell diffusion coefficient with an increase in molecular weight of the stagnant component.
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  • 124
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    AIChE Journal 2 (1956), S. 280 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 125
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    AIChE Journal 2 (1956), S. 16J 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 126
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    AIChE Journal 2 (1956), S. 18J 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 127
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    AIChE Journal 2 (1956), S. 372-380 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Measuring the spreading of a tracer dye from a point source yields information on diffusion in glass-sphere beds fluidized in water. Particulately fluidized beds, which are here formed, are well described by the statistical turbulence equations of Taylor. Mixing parameters - eddy diffusivity, scale, and intensity of turbulence - are established. Transition of these variables is traced from fixed beds through fluidized beds in different degrees of bed expansion.Mixing characteristics of these “ideal” types of fluidization may provide a frame of reference for consideration of more complex systems.
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  • 128
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    AIChE Journal 2 (1956), S. 384-388 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The purpose of this investigation was to study the process of heat transfer to a liquid drop rising through another liquid. In experimental runs various-sized drops of S.A.E.-10 lubricating oil, kerosene, and xylene were heated with water; also, water drops were heated with various organic liquids. Theoretical calculations of temperature change were made, various mechanisms of heat transfer being assumed. The temperature change predicted with each mechanism was compared with the experimental results and the controlling mechanism thus determined for each system studied.
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  • 129
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    AIChE Journal 2 (1956), S. 381-384 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The removal of a trivalent ion (Fe+++) from acidic nitrate solutions by a fixed bed of Dowex-50 cation-exchange resin was studied at entering iron concentrations from 14 to 4 meq./liter, flow rates of 0.073 to 1.20 liters/(hr.)(sq. cm.), and bed sizes from 3.7 to 5.4 g. of dry resin/sq. cm. Acid strengths were below 0.45 N. The results were correlated is a relatively simple break-through equation based on the assumptions of an equilibrium extremely favorable to iron adsorption and liquid-film diffusion being the rate-controlling factor. The capacity of the resin for iron was dependent upon the acid concentration of the sulation.The results provide a design equation requiring a minimum of experimental work.
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  • 130
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    AIChE Journal 2 (1956), S. 393-403 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 131
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    AIChE Journal 2 (1956), S. 11S 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 132
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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  • 133
    ISSN: 0001-1541
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  • 134
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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  • 135
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    AIChE Journal 2 (1956), S. 444-447 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Measurements of the terminal velocity of liquid drops immersed in an insoluble liquid were made for eleven liquid systems, covering a wide range of physical properties: continuous-phase density 0.960 to 1.145 g./cc., viscosity 0.93 to 1.56 centiposes; dispersed-phase density 0.807 to 1.674 g./cc., viscosity 0.59 to 72.1 centipoises; interfacial tension 0.3 to 42.4 dynes/cm. A correlation of the data was developed for each of the two velocity-drop-diameter regions which permits easy computation of the drop velocities. The correlations are shown to reproduce the present data and much of the published data very satisfactorily. Photographs permitted measurement of the drop eccentricities, which are shown to be a function of the drop diameter, density difference, and interfacial tension.
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  • 136
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    AIChE Journal 2 (1956), S. 471-476 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The photographic method was used to measure bubble sizes and frequencies for methanol boiling at atmospheric pressure outside a 3/8-in. O.D., steam-heated, horizontal copper tube. The average temperature of the tube was measured by use of the tube as a resistance thermometer. For nucleate boiling at heat fluxes up to 80% of the maximum, the product of bubble diameter and frequency was constant at 4 in./sec. In this region both the Rohsenow equation and the Forster-Zuber equation gave good predictions of the heat transfer. At higher fluxes the product f × D increased and the equations were much less suitable. The critical temperature difference for copper to methanol was not a single value but was a region extending from 52° to 62°F. The heat flux was nearly constant throughout this range at a maximum of 115,000 B.t.u./(hr.)(sq. ft.). For film boiling, f × D was nearly constant at 11 sec.-1 Bromley's equation was unsuitable for ΔT values less than 180°F., but it became applicable at this ΔT. The use of Nusselt's equation for steam condensing inside the tube was found to be satisfactory, proof that the slight slope of the tube was sufficient to permit adequate condensate drainage.
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    AIChE Journal 2 (1956), S. 482-488 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A fluidized-bed heat transfer mechanism is proposed that assumes that the chief resistance to heat exchange between a confining wall and a fluidized bed is in the laminar film at the vessel boundary. Heat flow through the film is by conduction. As the solids-particle velocity along the wall will modify film thickness, correlation of film coefficients in terms of particle velocities or the equivalent suggests itself. That heat transport from the boundary of the heating element to the fluidized core proceeds by way of turbulent solids mixing seems indicated by the considerable effect that the solids heat capacity appears to exert on over-all coefficients.The resulting correlation is examined critically in relation to pertinent literature data. The effect of fluidized-bed parameters on heat transfer coefficients is considered, and applicability and limits of the correlation are ascertained.
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    AIChE Journal 2 (1956), S. 489-497 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The effect on point and integral average conversion of chemical reaction, coupled with radial diffusion and radial distribution of reaction times in viscous-flow tubular reactors, is reported. Solutions are given for first-order reaction over an extensive range of dimensionless rate and time variables. An expression is given for a criterion of the conditions when the contribution of diffusion is so small that it may safely be disregarded as a variable. Another criterion also is given for the situation when diffusivity is so large, in comparison with other system constants, that the simple plug flow solution may be used without incurring more than a specified error.The hydrolysis of acetic anhydride was studied in 1/4- and 1/2-in.-diam. reactors in 10- and 15-ft. lengths. Reynolds numbers were between 40 and 400 and temperatures between 25° and 35 °C. It was found that the derived equations form a proper description of experiments in the smaller tube. Deviations from theory in the larger tube are explained in terms of free convection arising from nonisothermal conditions and from concentration gradients in the tube. Grashof criteria for initiation of convection in the system are discussed.
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    AIChE Journal 2 (1956), S. 518-524 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper reports a direct experimental comparison of the cracking of cumene in a fluidized bed of silica-alumina catalyst with the same reaction in a fixed bed. The effects of fluidization on the kinetics of this reaction are interpreted in terms of an empirical approach using effectiveness factors and by a simplified mathematical model.
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    AIChE Journal 2 (1956), S. 508-513 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Group-contribution values are presented and, together with those already developed for the aliphatic hydrocarbons (10, 11), make possible the evaluation of both van der Waals' constants for the naphthenic hydrocarbons. These constants can be used to produce the critical temperatures, pressures, and volumes of these compounds entirely from a knowledge of their chemical structure.Critical constants have been calculated for several naphthenes, and from a comparison of them with the constants resulting from the methods of Riedel (5, 6) and Lydersen (3) it was found that the critical constants calculated by these three methods were in fair agreement for naphthenes having short alkyl side chains and progressively deviated from each other as the chains were permitted to lengthen. An appraisal has been made on five naphthenes along the lines proposed by Sondak and Thodos (9) in order to see whether these calculated critical constants properly represent the vapor-pressure function resulting from vapor-pressure data found in the literature for these hydrocarbons.Critical constants have been produced for more than fifty naphthenes, for which vapor-pressure data are available in the literature, and will be used in a separate, comprehensive vapor-pressure study for hydrocarbons of this type.
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    AIChE Journal 2 (1956), S. 498-507 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Direct enthalpy measurements were carried out for the methanol-benzene system as a function of composition, temperature (250° to 500°F.), and pressure (30 to 1,400 lb./sq. in. abs.). From these data pressure-enthalpy diagrams were prepared to show the enthalpy and entropy above a reference state of saturated liquid at 77°F. Similar results were obtained for a single binary system of methanol and n-hexane and a single ternary mixture.The conventional generalized correlations were not satisfactory for predicting vapor-phase enthalpies for mixtures involving methanol. A new method requiring a knowledge of the heat of dimerization, the equilibrium constant for the reaction, and the interaction constant, is proposed for such polar-nonpolar systems based upon association of the polar component.The most striking feature of the data for mixtures was the large heat of mixing in the vapor phase for the systems containing methanol. The same type of equation found suitable for the heat of mixing in the vapor phase was applicable to the liquid data.From the enthalpy data across the two-phase region, it was possible to predict a limited amount of information on the compositions of the liquid and vapor phases in equilibrium. An azeotrope exists in the methanol-benzene system, which at 325°F. contains 75 mole % methanol.
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    AIChE Journal 2 (1956), S. 525-528 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: An empirical method is suggested which permits the prediction of vapor-liquid equilibrium data for binary hydrocarbon mixtures at various total pressures on the basis of equilibrium data at one constant pressure. This method has been tested with the vapor-liquid equilibrium data of six nonideal systems measured at twenty-one different experimental conditions. The total pressure range varies from 50 mm. of mercury to 4 atm. In all cases the predicted results are in good agreement with the experimental data.
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    AIChE Journal 2 (1956), S. 529-535 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This investigation was undertaken to show how the efficiency of solute transfer between two immiscible liquids is influenced by the type, size, and submergence and rotational speed of the impeller and the degree of baffling, residence time, and phase ratio. The system water-kerosene-n-butylamine solute was agitated in a continuous-flow 14 3/4-in. -diam. vessel using propellers, spiral turbines, and flat-blade turbines from 4 to 10 in. in diameter. The feed streams were introduced at the wall at the bottom of the vessel and left at the top of the vessel.On the basis of the power required for a given level of stage efficiency, the best agitator design is any impeller that has a diameter about 40% of the vessel diameter and is centered in the unbaffled vessel. Without baffles the impeller type and depth of submergence have little effect on performance. The power increase required by the addition of baffles is small at the highest stage efficiencies, especially with the larger radial-flow impellers, but may be severalfold at efficiency levels of 70 to 90%. This presumably results from the lowered mass transfer driving force caused by the increase in end-to-end mixing due to wall baffles. Whether baffles have such a large adverse effect if the feed is introduced into the impeller rather than at the vessel wall is not fully established, but there is some evidence that baffling is also undesirable in this case. For baffled operation, impeller type and submergence do affect performance.A correlation of stage efficiency is presented in terms of Reynolds number and power number. In addition, energy input per volume of total flow is correlated in terms of residence time and stage efficiency for one size of baffled propeller.Spot samples taken from the vessel showed large, random-concentration fluctuations out to 20 residence times and perhaps indefinitely. Reproducible results were obtained by taking time-averaged samples.
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    AIChE Journal 2 (1956), S. 42-45 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Because of the large scale of the motion responsible for mixing in turbulent fields, turbulent transport processes differ from molecular transport processes in that the mixing depends on the previous history of the diffusing material and turbulent fields are generally nonhomogeneous.The effect of the time dependency of the diffusion process is examined for the case of heat transfer from a hot wall to a cold wall through a turbulently flowing fluid. The fluid is assumed to have a uniform velocity and the turbulence is assumed to be homogeneous and isotropic. The calculations are carried out by assuming a distribution of heat sources along the hot wall and of heat sinks along the cold wall. G. I. Taylor's theory of turbulent diffusion for a homogeneous isotropic field is used to describe the properties of these sources and sinks. These calculations are compared with temperature profiles obtained as a solution to Fick's Law using a constant diffusion coefficient. A marked difference between the two sets of curves is obtained in the vicinity of the wall and in the beginning of the heat exchange section.A calculated profile on the basis of an idealized model of heat transfer in channel flow is compared with actual measurements made by Page, Corcoran, Schlinger, and Sage (7) at a distance far enough downstream so that the temperature profile had reached a steady condition.
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    AIChE Journal 2 (1956), S. 46-54 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The hydrogenation of carbon monoxide and carbon dioxide on various steel catalysts was studied in the temperature range of 800° to 1,300°F. and at pressures from 5 to 30 atm. The feed gases (3.75 to 20 SCFH) were passed over a catalyst bed of 1/8-in. steel balls supported in a brass-lined reactor 0.81 in. in diam. The percentage of carbon oxides in the feed was 30% in the runs using a H2—CO2 feed and varied from 15 to 38% in the runs with a H2—CO feed. The effects of temperature, pressure, feed composition, space velocity, and mass velocity were studied. Carbon deposition did not affect the activity of the catalyst and could be removed readily.
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    AIChE Journal 2 (1956), S. 34-37 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: In the usual method of calculating the solvent extraction of complex mixtures it is assumed that the complex mixture behaves like a binary mixture. However, the hypothetical binary composition of the mixture is never explicitly used; rather, an additive property of the mixture is used as an indication of its composition. The calculation must be done graphically on a triangular diagram or its equivalent.On the assumption that the complex mixture consists of only two hypothetical components, empirical equations have been arrived at relating the distribution coefficients of these two components and of the solvent to the phase compositions. These equations contain three arbitrary constants. By use of the data from a minimum of three simple laboratory batch extractions of a given complex mixture, the three constants, plus the hypothetical binary composition of the original complex mixture, can be determined.With the equations for the distribution coefficients, the equilibrium curve and tie lines for the system can be calculated. Properties of the raffinates and extracts can be measured and related to the hypothetical binary compositions of these mixtures.The use of the method is demonstrated by comparing calculated results with laboratory yields and properties. The calculated results show good agreement with the experimental results. Calculations can be carried out not only on the triangular diagram, but by any of the other graphical methods that have been developed for the solvent extraction of binary mixtures. Equally important, calculations can be done analytically, and therefore the use of automatic computers is feasible.
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    AIChE Journal 2 (1956), S. 55-58 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The physical processes are discussed by which a fluid is displaced from a porous medium during steady state viscous flow by another fluid of the same density and viscosity under conditions of complete miscibility of the two fluids. The displacement occurs on a microscopic scale as a result of combined convective and diffusional mixing. The length of the zone of mixing which comprises the displacement front is predicted to be dependent upon the rate of flow, the diffusion coefficient for the two-fluid system, the characteristics of the pore geometry, and the distance the front has traversed at the time of its observation.Experimental data are presented for the displacement of benzene by ethyl n-butyrate at several rates of flow from packed sand columns. These data show that the length of the frontal mixing zone after a prescribed distance of flow is greater at the higher rates of flow. The postulated dependence of the length of the front upon the diffusion coefficient and the pore geometry has not yet been investigated.
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    AIChE Journal 2 (1956), S. 59-62 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The chemical engineer frequently has to correlate kinetic data for heterogeneous reactions simply and accurately in order to make useful predictions of reaction rates over a range of conditions. The Langmuir-Hinshelwood approach, which is frequently used for this purpose, does not have the theoretical validity commonly attributed to it, and its use leads to unnecessary mathematical complexity. A simpler method of analysis is suggested which is based on power dependencies of the rate on concetrations, the powers being restricted to integral of half-integral values. The data for several reactions are shown to be adquately correlated by the suggested procedure, which is simple and convenient.
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    AIChE Journal 2 (1956), S. 62-64 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The wide applicability of the Langmuir-Hinshelwood classical kinetics to surfaces which are known to depart strongly from ideal Langmuir behavior is a well-known paradox of surface catalysis. The applicability and limitations of the classical method are illustrated by means of a simple reaction. The generality of the method is demonstrated by its applicability to ammonia synthesis with and without water vapor. The limitations are often more than compensated for by the added insight into reaction mechanism which it can provide without unded complexity. A three-step approach to surface kinetics is suggested and discussed.
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    AIChE Journal 2 (1956), S. 107-112 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Although vacuum crystallizers are used widely, crystal-size-control methods have not been adequately analyzed. This paper supplies in part the deficiency of technical information on this problem. Industrial crystallizers may have inherent nucleation rates in excess of or below the seed-crystal requirement for the desired product-crystal size. This paper deals specifically with means of crystal-size control by removal of excess nuclei from mixed circulating suspensions as encountered in vacuum crystallizers. It is shown that under certain conditions the cumulative size distribution in the suspension varies as the fourth power of the size. Therefore, it may also be shown that the key to effective size-control procedures is the segregation time of nuclei in the fines-removal system. Procedures based mainly on crystal-size classification by hydraulic elutriation can hardly be effective unless they are also designed to meet the segregation-time requirements.
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    AIChE Journal 2 (1956), S. 127-138 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 2 (1956), S. 113-117 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: Extension of the understanding of properties of films of metals produced on glass surfaces by vacuum evaporation has permitted the fabrication of film-resistance thermometers that with simple instrumentation accurately measure surface or average surface temperatures without altering the geography of that surface. Formerly unknown and unstabled related properties of such films have been classified and may be anticipated or eliminated by recommended experimental procedures. Films of several of the most chemically inert and refractory metals 300 to 3,000 Å. thick have been shown to attain accuracies as high as 0.01°C. for practical periods of time. Their use, which is described, is developing satisfactorily, and the technique and equipment for their preparation are relatively simple.
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    AIChE Journal 2 (1956), S. 139-139 
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    Keywords: Chemistry ; Chemical Engineering
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    AIChE Journal 2 (1956), S. 184-189 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The rate of mass transfer was measured for solid metal shapes dissolving into mercury at room temperature. Sherwood numbers for horizontal tin, cadmium, zinc, and lead cylinders dissolving by natural convection agreed with Nusselt numbers for heat transfer in nonmetallic liquids at the same Rayleigh (Grashof × Prandtl) numbers. Dissolving of zinc tubes by mercury flowing turbulently within them agreed with heat transfer to nonmetals in tubes. Dissolving of random beds of lead spheres by mercury flowing through the bed agreed with similar nonmetal systems. It is concluded that mass transfer processes in liquid metals follow substantially the correlations for other fluids in heat or mass transfer, which with moderate safey factors may thus be used for at least preliminary design purposes.
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    AIChE Journal 2 (1956), S. 17J 
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    AIChE Journal 2 (1956), S. 428 
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    AIChE Journal 2 (1956), S. 10S 
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    AIChE Journal 2 (1956), S. 437-443 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The film theory of liquid-side resistance to gas absorption, embodying the assumption of a thin stagnant liquid film adjacent to the interface in which steady state diffusion occurs, has long been open to question, particularly in packed columns. Higbie's penetration theory, believed to be more reasonable, pictures the liquid as flowing over a piece of packing for a very short period of time before being mixed as it flows to the next piece of packing. In the penetration model absorption occurs during a series of brief contacts, and unsteady state mass transfer conditions prevail in the liquid.Several short glass-wetted-wall columns 1.9 to 4.3 cm. long were constructed to simulate the assumptions of the penetration theory. Because of the short length ripples were absent except when the gas rate was higher than ReG = 2,200. The desorption of carbon dioxide from water and of chlorine from dilute hydrochloric acid (0.16 to 0.18 N) was studied. The desorption rate of carbon dioxide was unaffected by gas velocity up to ReG of 2,200 and increased 1.1%/°C. over the temperature range of 22° to 31°C.
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    AIChE Journal 2 (1956), S. 448-450 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
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    AIChE Journal 2 (1956), S. 451-455 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A study was made of the effect of physical properties and of geometrical and dynamical characteristics of several liquid-liquid extraction systems on the mass transfer coefficients. The two-component systems studied consisted of the following solvents with water: cyclohexanol, methyl ethyl ketone, furfural, normal butanol, and nitromethane. The transfer studies were made in a horizontal glass pipe with the phases flowing counter-currently at velocities from 1,000 to 15,000 lb./(hr.)(sq. ft.). The transfer of solvents into the water phase and of the water into the solvent phase was measured. The film coefficients of mass transfer for a solvent through the water film and for water through the solvent film were correlated by new dimensionless equations which include interfacial tension and diffusivity.
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    AIChE Journal 2 (1956), S. 463-467 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: A method for estimating adsorption equilibria based on a modification of the Polanyi adsorption-potential theory was developed for use in the investigation described in Part I of this article. In addition, the recently published correlation method of Lewis, Gilliland, Chertow, and Cadogan, suitably modified for the present application, was successfully employed in the correlation and extrapolation of the ternary equilibrium data.
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    AIChE Journal 2 (1956), S. 552-554 
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    Keywords: Chemistry ; Chemical Engineering
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    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: By use of Cp values from the literature and experimentally determined vapor-pressure-temperature and pressure-volume-temperature relationships, a thermodynamic network has been established for tertiary butyl alcohol in the range of 78° to 500°F. and 14.7 to 700 lb./sq. in. abs. The results include tabulated values of p, v, T, H, S, f, and Z, as well as the vapor-pressure-temperature curve, the critical properties, and constants for the Beattie-Bridgeman equation.The original pressure data were accurate to within 0.14% in the high range and to within 4% in the low range. The limits on the experimental volume data were 0.07% for large vapor volumes and 2% for liquid volumes. The temperature was determined to within 0.1 °F., or less than 0.02% of the absolute temperature.Experimentally determined vapor pressures were found to be lower than those reported in the literature in the range above 1 atm. Values previously reported were obtained by extrapolation of a vapor-pressure-temperature relation developed for use at subatmospheric pressures. For pressures below 1 atm. the experimental values agreed with the reported values.
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    AIChE Journal 2 (1956), S. 555-560 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: This paper describes an investigation of the factors affecting the change in composition with vaporization of a binary-component spray in heated air at atmospheric pressure. The behavior of the system orthodichlorobenzene-tetrachloroethylene was studied in air ranging from 400° to 1,000°F. Initial drop diameters in the sprays were in the 20- to 400-µ range. The experimental data obtained indicated that the rate of change of spray composition during vaporization was affected only by the chamber-air temperature, the initial feed composition, and the nozzle characteristics.Equations are presented which mathematically describe the vaporization process, liquid diffusion being assumed within the drop controls. These equations have been solved by a stepwise procedure for three initial drop sizes. Results of these calculations have been added statistically according to the initial-drop-size distribution in order to predict the vaporization behavior of the spray. Details of this process of statistical combination have been summarized by Culverwell (1).The calculations agreed with the experimental data previously obtained during the first 5 in. of nozzle-to-tray travel. After 5 in. the deviation was great. Future experimental work to determine more precise values of drop-size distribution, initial drop velocity, and liquid diffusion coefficient may result in more complete agreement.
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    AIChE Journal 2 (1956), S. 560-567 
    ISSN: 0001-1541
    Keywords: Chemistry ; Chemical Engineering
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology , Process Engineering, Biotechnology, Nutrition Technology
    Notes: The production of oil and gas by pressure depletion involves both the formation of bubbles and the diffusion of gas from the liquid phase into these bubbles. Studies were undertaken to outline in detail the process of bubble formation when the driving force is small. This work shows that the formation of bubbles is a random process which can, however, be described by a simple probability distribution function. Also, calculations have been made to determine how fast gas will diffuse into uniformly distributed gas bubbles.These results make it possible to describe the manner in which a gas phase is established during the pressure depletion process. In this process the rate of pressure decline is the most important factor influencing the total number of bubbles produced. Laboratory tests have substantiated the finding that in certain types of porous media the amount of oil recovered is sensitive to the number of bubbles formed.
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    Zeitschrift für anorganische Chemie 283 (1956), S. 277-286 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das früher auf Grund thermischer Analyse aufgestellte Zustandsdiagramm des Systems KF—MgF2 wird auf röntgenometrischem Wege bestätigt. Außer der ein ausgeprägtes Schmelzpunktsmaximum aufweisenden Verbindung KMgF3 mit Perowskitstruktur tritt darin eine inkongruent schmelzende Verbindung K2MgF4 auf, die tetragonal kristallisiert. Sie unterscheidet sich von den aus Schmelzen mit 50 bis 78,5 Mol-% KF primär sich abscheidenden Mischkristallen dadurch, daß sie aus regelmäßig miteinander abwechselnden KF- und KMgF3-Schichten aufgebaut ist, während in den Mischkristallen die gleichen Schichten in völlig regelloser Folge vorliegen. Aus den Mischkristallen bildet sich die Verbindung durch zwei bei verschiedenen Temperaturen (861° und 840°) im festen Zustande verlaufende Vorgänge: Zerfall der Mischkristalle unter Ausstoßung der überschüssigen KF-Schichten und Wiedereinbau der KF-Schichten unter Bildung des für K2MgF4 typischen Kristallgitters.
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die katalytische Umwandlung des Parawasserstoffs wird an kompakten Kupfer-Nickel- und Kupfer-Palladium-Legierungen untersucht. Nickel und Palladium sind in bezug auf die Aktivität und auf die Aktivierungsenergie wesentlich wirksamer als Kupfer, die Wirksamkeit nimmt mit steigendem Kupfergehalt nicht stetig, sondern sprunghaft ab. Das Verhalten der gleichen Legierungskatalysatoren gegenüber der Parawasserstoff-Umwandlung und der Äthylenhydrierung ist sehr ähnlich, was auf einen beiden Reaktionen gemeinsamem Primärvorgang (H2-Aktivierung) schließen läßt.An Cu—Pd-Legierugen mit geordneter Atomverteilung („Überstruktur“) verläuft die p-H2-Umwandlung mit niedrigerer Aktivierungsenergie als an den Mischkristallen mit ungeordneter Atomverteilung.Die Ergebnisse werden gemeinsam mit früheren Ergebnissen im Zusammenhang mit den Elektronenbindungsverhältnissen in den Legierungen auf der Grundlage der Anschauungen DOWDENS diskutiert.
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    Zeitschrift für anorganische Chemie 283 (1956), S. 299-303 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Graphit nimmt aus einer mit Jodmonochlorid gesättigten Atmosphäre 2,5 g JCl/1 g C auf. Die Aufweitung des Graphitgitters durch die Einlagerung von JCl beträgt 3,21.Während Graphit mit gasförmigem Chromylchlorid nur in sehr geringem Umfang reagiert, quillt er in flüssigem CrO2Cl2 stark. Aus pyknometrischen Messungen wird die aufgenommene Menge zu 1,05 CrO2Cl2/1 g C bestimmt. Die Identitätsperiode Ic beträgt 14,6 kX, die Aufweitung des Gitters 2,18.
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Mitführungsmessungen im Chlorstrom mit den Dichloriden MnCl2, CoCl2 und NiCl2 als Bodenkörper ergaben beim Kobalt eine sehr erhebliche, beim Mangan und beim Nickel aber eine an der Grenze der Nachweisbarkeit liegende Bildung von gasförmigem Trichlorid. Beim Chrom und Eisen gewinnt man das gesuchte Gleichgewicht MeCl2 gas + ½ Cl2 = MeCl3 gas aus Literaturdaten. Für die Reaktion MeCl2 gas + Cl = MeCl3 gas besteht in der Reihe Cr, Mn, Fe, Co, Ni ein gleichsinniger Gang der Reaktionsenthalpien mit den Ionisierungsspannungen Me2+ = Me3+ + e-.
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    Zeitschrift für anorganische Chemie 283 (1956), S. 330-337 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Darstellung und Eigenschaften folgender Ferrate(IV) werden beschrieben: Na4FeO4, Sr2FeO4, Ba2FeO4, Ba3FeO5.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 31-35 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach einer kurzen Übersicht über die bisher bekannten Wolfram- und Molybdän-Phosphorsäureverbindungen werden Temperversuche von WO3—NaPO3- und MoO3—NaPO3-Schmelzen, insbesondere aber die Verbindungen Na2O · 2 WO3 · P2O5 und Na2O · 2 MoO3 · P2O5 beschrieben.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 20-30 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wurden die Zersetzungstemperaturen verschiedener Sulfate der Elemente bzw. Übergangselemente der I., II. und III. Gruppe des Periodensystems mittels gravimetrischer Thermoanalyse (GTA) in Luftatmosphäre bei Atmosphärendruck zwischen 20 bis 1000°C ermittelt. Parallel wurden in demselben Temperaturbereich auch die Gewicht-Temperatur-Kurven (GTK) des Reduktionsablaufes derselben Sulfate in strömendem reinen Wasserstoff sowie in 30% Wasserstoff enthaltendem Stickstoff aufgenommen.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 47-59 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nachdem in einer früheren Mitteilung(1) gezeigt werden konnte, daß saure Sulfitlösungen, wie sie durch Auflösen von Disulfiten oder Halbneutralisieren von Schwefligsäurelösungen hergestellt werden, bei absolutem Luftausschluß auch im Licht keinerlei zeitlichen Veränderungen ihrer Konstitution unterliegen, wird an Hand von Raman-Aufnahmen an belichteten und vor Licht geschützten, bei Gegenwart von Luftsauerstoff aufbewahrten, sauren Sulfitlösungen der Beweis geführt, daß das von K. SCHAEFER und Mitarbeitern(2) aufgefundene „Zeitphänomen der Bisulfite“ in einer langsamen Photooxydation der Hydrogensulfitionen besteht, wodurch Schwefeldioxydhydrat, neutrales Sulfat und Dithionat entstehen.Es wird weiterhin nachgewiesen, daß die bei den UV-Absorptionsspektren beobachtete Bande bei 257 mμ dem S2O2-5-Ion zugehört und die „Vertikalverschiebung der Absorptionskurven“ mit der Verdünnung durch Umwandlung von S2O2-5-Ionen in HSO-3-Ionen bedingt ist, während die Bande bei 276 mμ dem O2S…OH2 zugehört, das in den sauren Sulfiten nur bei Luftzutritt über die durch Oxydation gebildete stärkere Säure HSO-4 in Freiheit gesetzt. wird.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 36-46 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die RAMAN-Spektren gesättigter saurer Sulfitlösungen im Gleichgewicht mit festem Alkalidisulfit MeI2S2O5 zeigen, ebenso wie früher an verdünnteren Lösungen beobachtet, sowohl die Frequenzen des S2O2-5-Ions als auch HSO-3-Ions, woraus folgt, daß bei der zunehmenden Konzentrierung verdünnterer Lösungen das Löslichkeitsprodukt der stets auskristallisierenden reinen Disulfite, zumindest der des Kaliums und Natriums, bereits erreicht wird, bevor die vollständige Dehydratisierung der HSO-3-Ionen nach \documentclass{article}\pagestyle{empty}\begin{document}$$ 2{\rm HSO} - {\rm H}_2 {\rm O} \to {\rm S}_2 {\rm O}_3^2 $$\end{document} stattgefunden hat.Teilweise alkalisierte saure Sulfitlösungen erfahren bei Gegenwart von festem Alkalidisulfit die auf Grund der bisher entwickelten Auffassung über die Konstitution der reinen, sauren Salzlösungen und deren Verhalten gegenüber Alkalizusätzen zu erwartenden spektralen Veränderungen. Aus diesen ist zu entnehmen, daß die durch die Lauge neutralisierten HSO-3-Ionen durch Spaltung von S2O2-5-Ionen nachgebildet und neue S2O2-5-Ionen aus dem Bodenkörper nachgeliefert werden.Weiterhin wird der Einfluß von überschüssigem SO2 auf die Gleichgewichte in sauren Sulfitlösungen untersucht. Auch hier sind die Ergebnisse mit der vorausgesagten Gleichgewichtsverschiebung zugunsten des S2O2-5-Ions gemäß den Gleichungen in Einklang.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 73-82 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Einkristallaufnahmen von Natriumamid und ihre Auswertung durch Patterson- und Fourier-Synthese haben zu folgenden Ergebnissen geführt:Natriumamid kristallisiert rhombisch mit den Gitterkonstantena = 8,044 b = 8,911 c = 10,406 kX.Raumgruppe D242h mit 16 Formeleinheiten im Elementarkörper. Es sind folgende Punktlagen besetzt:Na in (16 g) mit z = 0,142NH2 in (16 e) mit x = 0,233.Die NH2-Ionen bilden eine stark deformierte, kubisch dichte Anordnung, die Natrium-Ionen befinden sich in Tetraederlücken.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 83-96 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird eine neue Methode der calorimetrischen Direktbestimmung der Wärmetönungen von Hochtemperaturprozessen beschrieben, bei der die zu untersuchenden Substanzen in der Calorimeterbombe in einem elektrischen Öfchen in sehr kurzer Zeit auf die gewünschte Reaktionstemperatur erhitzt werden.Bei Verwendung eines entsprechenden Wattsekundenzählers ist es möglich, die Heizenergie mit so großer Genauigkeit festzulegen, daß die Meßergebnisse denen anderer calorimetrischer Methoden gleichkommen. Angewandt wurde die Methode, um die Wärmetönungen der Carbonat- und Hydroxydschmelze von Natriumdisilicat und Natriummetasilicat sowie um die Entglasungswärmen der Natriumsilicate und deren Umwandlungswärmen zu bestimmen.
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    Zeitschrift für anorganische Chemie 284 (1956), S. 131-141 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Volumenänderungen beim Schmelzen von NaCl, NaBr, NaJ, KCl, KBr, KJ, RbCl, RbBr, CsCl wurden gemessen. Es wurden zum Teil sehr hohe Werte gefunden und ihr Zusammenhang mit den Entropieänderungen beim Schmelzen, der Gitterenergie u. a. untersucht. In den einzelnen Gruppen der Alkalihalogenide wachsen die in % ausgedrückten Δv-Werte mit den Schmelzentropien, sie nehmen proportional den Gitterenergien zu. Auch andere Eigenschaften, so z. B. die Radienquotienten und die Polarisierbarkeiten sind in die Diskussion einzubeziehen.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 70-73 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Herstellung und Eigenschaften der Verbindungen [Hg(NS)]x und Hg2(NS7)2 werden beschrieben.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 103-112 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Germanium reagiert mit CO2 bei erhöhter Temperatur unter Bildung von Germanium(II)-oxyd und Kohlenmonoxyd. Die Reaktion beginnt bei 700° C und verläuft bei Temperaturen über 800° C mit großer Geschwindigkeit. Darauf gründet sich eine einfache Darstellungsweise für GeO.Man kann auch Germanium in einem Luftstrom auf Temperaturen über 700° C unter stark vermindertem Druck erhitzen. Es bildet sich mit dem Luftsauerstoff oberflächlich GeO2, welches von dem überschüssigen Germanium zu GeO reduziert wird. Nach dieser Methode können leicht größere Mengen GeO dargestellt werden.
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    Zeitschrift für anorganische Chemie 285 (1956) 
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    Keywords: Chemistry ; Inorganic Chemistry
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    Zeitschrift für anorganische Chemie 285 (1956), S. 113-113 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
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    Topics: Chemistry and Pharmacology
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    Zeitschrift für anorganische Chemie 285 (1956), S. 114-117 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der Reaktion zwischen Schwefeltrioxyd und Antimonpentachlorid in Sulfurylchlorid-Lösung entsteht neben Disulfurylchlorid, S2O5Cl2, die Verbindung Sb2Cl8SO4. Diese Verbindung dürfte als [SbCl4]2SO4 aufzufassen sein.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 181-190 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Bei der thermischen Spaltung von S4N4-Dampf entsteht S2N2, eine gut kristallisierte, farblose Substanz, die leicht sublimiert, oberhalb + 30° explosionsartig in die Elemente zerfällt und sich sowohl zu S4N4 als auch zu Polyschwefelstickstoff, (SN)x, polymerisieren kann. (SN)x ist ein fester Stoff, der Metallglanz und ein beträchtliches Leitvermögen für den elektrischen Strom besitzt.
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    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: 1Die Kristallisationsgeschwindigkeit des unterkühlten Glycerins wird im Ultraschallfeld nur infolge der Erwärmung des Glycerins durch die Schallabsorption verändert. Bei geringer Unterkühlung wird sie also herabgesetzt.2Die Kristallisationsgeschwindigkeit des unterkühlten Benzophenons wird durch Ultraschall immer erhöht, und zwar wahrscheinlich durch Beseitigung der Wärmestauung vor der Phasengrenze.3Das unterschiedliche Verhalten von Glycerin und Benzophenon wird verursacht durch die Verschiedenheit der in der Zeiteinheit beim Erstarrungsvorgang freiwerdenden Wärmemengen. Beim Glycerin kommt es zu keiner Wärmestauung.4Beim Benzophenon läßt sich im Ultraschallfeld bei sehr geringer Unterkühlung die Erstarrung so leiten, daß ihr lineares Fortschreiten überwiegend durch sonophoretisches Vorwandern kleiner Kristalle bestimmt wird. Die Körnigkeit der erstarrten Schmelze wechselt dann in Abständen von einer halben Wellenlänge.5Die bekannten, sehr großen Erhöhungen der Erstarrungsgesch windigkeit im Ultraschallfeld sind an einen Gasgehalt der Schmelze gebunden. Sie kommen durch turbulente Vorgänge zustande, welche die Gasabscheidung bei der Erstarrung begleiten.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 205-211 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Basenreaktion des Rheniumpentacarbonyls führt unter Verwendung alkoholischer Lauge zur Entstehung von 1 Mol H2 und 1/2 Mol CO3-- -- pro Atom Re zu einem Kalium-μ-dioxohydrogen-octacarbonylo-dirhenat, entsprechend Das Kohlenoxyd reagiert hierbei unter Formiatbildung. Die Struktur des zweikernigen Komplexes wird durch Leitfähigkeit, Fällungsreaktionen und Diamagnetismus sichergestellt; die koordinativ 6zähligen Re-Atome besitzen eine abgeschlossene Edelgaskonfiguration.Bei der Basenreaktion des Rheniumchlorocarbonyls wird in Bestätigung dieses Reaktionsverlaufs ohne Entbindung von Wasserstoff dieselbe μ-Dioxoverbindung gebildet: \documentclass{article}\pagestyle{empty}\begin{document}$$ 2{\rm Re}({\rm CO})_5 {\rm Cl} + 3{\rm KOH} \to {\rm Re(CO)}_{\rm 8} {\rm O}_{\rm 2} {\rm HK} + 2{\rm KCl} + 2{\rm CO} + {\rm H}_{\rm 2} {\rm O} $$\end{document}Auch mit Thiophenol erhält man bei der Reaktion von Rheniumchlorocarbonyl einen diamagnetischen zweikernigen Komplex, [(CO)4Re(SC6H5)]2, dem Nichtelektrolytstruktur zukommt.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 212-220 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Ni3N leitet metallisch mit dem spezifischen Widerstand ϱ0 = 2,8 · 10-3 Ω. cm und dem Temperaturkoeffizienten des Widerstandes α = +0,73 · 10-3 Grad-1, es gehört zu den Nitriden der Übergangsmetalle von metallischem Charakter.Cu3N ist ein Halbleiter mit ϱ0 = 6,0 · 102 Ω · cm und der Ablösearbeit der Elektronen von Δ∊ = 0,23 eV.Zn3N2 ist ebenfalls ein Halbleiter mit ϱ0 = 4,5 · 103 Ω · cm und Δ∊ = 0,09 eV.Während GaN ein Halbleiter mit ϱ20 = 4,0 · 108 Ω · cm ist, leitet InN überraschend gut mit ϱ0 = 4,0 · 10-3 Ω · cm und α = +0,37 · 10-3 Grad-1.Ge3N4 hat einen spezifischen Widerstand von mehr als 108 Ω · cm.Die Sonderstellung des InN hat eine Parallele in der hohen Leitfähigkeit des CdO.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 221-235 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Das Verhalten des Benzols, unter anderem seine längstwelligen Absorptionsbanden und seine Resonanzenergie, kann durch wellenmechanische Modelle z. B. nach Foerster oder Platt gut verstanden werden. Als formelmäßiger Ausdruck dieser Modelle genügen in erster Näherung die beiden Kekulé-Formeln: . Beim Einführen von Substituenten kommen neue Grenzformeln hinzu, beim Anilin z. B.: , die unter anderem die Direktionskraft der Substituenten nach (ortho- und) para-Stellungen verständlich machen. Die prozentuale Beteiligung solcher Grenzformeln am Grundzustand ist nur gering, und die maximale Arbeit bei der Anlagerung eines Protons an das negativierte C-Atom in para-Atellung zur Aminogruppe reicht nicht aus, um das Proton hier, statt am einsamen Elektronenpaar des N-Atoms anzulagern.Es wurde nun auf Grund der Absorptions-Spektren vom symmetrischen Triamino- und Trioxybenzol festgestellt, daß bei diesen Verbindungen ein Proton an einem Ring-C-Atom angelagert wird, so daß die hierbei entstehende langwellige Absorptionsbande (3600 Å beim s-Triaminobenzolmonokation) einen Übergang vom aromatischen zu einem aliphatischen System anzeigt. Z. B.: Bei dieser Verbindung scheint ein Gleichgewicht zwischen den beiden formen zu existieren, die Resonanzenergien der beiden Formen A und B sind hier von vergleichbarer Größe.
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    Zeitschrift für anorganische Chemie 285 (1956), S. 303-308 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Durch Umsetzung von Hexamminchrom(III)- und Hexamminkobalt(III)-nitratmit Na-phenolat in flüssigem NH3 wurde Hexamminchrom(III)- und -kobalt(III)-phenolat erhalten. Der thermische Abbau der Cr-Verbindung führt unter NH3- und Phenolabspaltung zu dem ammonobasischen Phenolat H2N—Cr(OC6H5)2, das als hochpolymere Verbindung mit 6zähligem Cr aufzufassen ist. Ein analoger Abbau der Co-Verbindung gelingt nicht.
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 286 (1956) 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Zeitschrift für anorganische Chemie 285 (1956), S. 322-336 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird das Verhalten von Gemischen von Kaliumoxyd und Schwermetalloxyden beim Erhitzen in Sauerstoffatomosphäre untersucht.1Aus KOx + Fe2O3 erhielt man beim Verhältnis K:Fe = 1:1 bei 450° C grünes KFeO2, bei 2:1 K2FeO4 und bei 3:1 eine neue Verbindung K3FeO4, die möglicherweise fünfwertiges Eisen enthält.2Aus KOx + NiO bildete sich K2NiO3.3Mit Co3O4 erhielt man mit KOx und CsO2 im Verhältnis Me:Co = 1:1 Substanzen der Bruttozusammensetzung MeCoO3. Versuche mit Gemischen aus CsO2 + Co3O4 zeigten jedoch, daß es sich nicht um eine einheitliche Substanz handelt, sondern um Gemische von KO2 mit MeCoIIICoIVO4.
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    Zeitschrift für anorganische Chemie 286 (1956), S. 180-192 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die Umsetzung sehr reiner SO2/O2-Gemische in Glimmentladungen führte nur zu Polyschwefelperoxyden der Zusammensetzung um (SO3,2)x. Versuche, eine Verbindung der Formel SO4 erneut darzustellen, blieben trotz weitgehender Variation der Versuchsbedingungen ohne Erfolg. Ein Reaktionsprodukt mit ähnlichen analytischen und chemischen Eigenschaften entstand nur dann, wenn den reagierenden Gasen SO2 und O2 ein Bruchteil an N2 zugemischt wurde. Der größte Teil der Eigenschaften dieses früher als SO4 angesehenen Reaktionsproduktes läßt sich aus einer Formulierung als Mischung von Dinitrosyldisulfat mit Polyschwefelperoxyden geringen Oaktiv-Gehalts ableiten. Die Existenz einer monomeren SO4-Molekel ist auch von theoretischen Überlegungen her unwahrscheinlich, während sich ein polymeres (SO4)x verhältnismäßig gut darstellen läßt.
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    Zeitschrift für anorganische Chemie 286 (1956), S. 193-204 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die chemische Analyse der flüchtigen Reaktionsprodukte, die bei der exothermen Reaktion Si + 4 CuCl → SiCl4 + 4 Cu entstehen, hatte ergeben, daß sich neben dem Hauptprodukt SiCl4 als Nebenprodukte höhermolekulare Siliciumchloride mit (Si—Si)-Bindungen bilden und daß der Gesamtverlauf der Umsetzung autokatalytischen Charakter hat. Aus der thermischen Analyse des Reaktionsverlaufs war abgeleitet worden, daß die Reaktion mit einer Passivierung der Komponente Si beginnt. Als Überleitung von der Mitteilung I (die nur eine Übersicht über die Ergebnisse enthielt) wird in dieser Mitteilung II die Auswertung der thermischen Analyse ausführlich beschrieben. Anschließend wird gezeigt, daß die Befunde am System Si/CuCl in naher Beziehung stehen zu Erfahrungen über die Chlorierung von Silicium und über den Abbau höhermolekularer Siliciumchloride durch Cu bzw. CuCl, die bisher unabhängig von dem System Si/CuCl gewonnen wurden. Es werden experimentell gesicherte Teilreaktionen zusammengestellt, die auch beim Aufheizen des Systems Si/CuCl in der Grenzflächenzone der Komponente Si möglich sind. Diese liefern als Modellreaktionen Beiträge zum Verständnis des Reaktionsverlaufs bis zum sogenannten Sprungpunkt des Systems Si/CuCl.
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    Zeitschrift für anorganische Chemie 286 (1956), S. 237-242 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es wird über die Darstellung von gelbem, sublimierbarem Pb(C5H5)2 berichtet, welches sich nach einer neuen präparativen Methode durch Umsetzung von Na mit C5H6 in Tertiärbutanol und nachfolgende Reaktion des dabei erhältlichen NaC5H5 mit Pb(NO3)2 in Dimethylformamid erhalten läßt. Die diamagnetische Verbindung weist ein Dipolmoment von 1,63 Debye auf und stellt damit eine gewinkelte Molekel dar. Die Doppelkegelstruktur des Fe(C5H5)2 bildet sich nicht mehr aus.
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    Zeitschrift für anorganische Chemie 286 (1956), S. 243-246 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach den bisherigen Methoden schied man den in Schwefel enthaltenen Kohlenstoff durch langes Erhitzen auf niedere Temperaturen bis 445°C aus, und trennte ihn durch Adsorption oder Vakuumdestillation. Es ist besser, umgekehrt durch höhere Temperaturen auf allmählich entweichenden CS2 hinzuarbeiten, indem man einen elektrischen Heizer in den siedenden S steckt, wobei man den Vorteil hat, am Heizer noch vorhandenen C als schwarzen Beschlag direkt zu sehen. Man kann so in einigen Tagen aus umkristallisiertem S ohne Aufsicht und Manipulationen durch Vakuumdestillation des behandelten S auf C-Gehalte von weniger als 10-6% kommen.
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    Zeitschrift für anorganische Chemie 286 (1956), S. 265-267 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach Röntgenuntersuchungen ist der Zusammenhang zwischen den Modifikationen des Berylliumoxyacetats dadurch gegeben, daß die bekannte, bei Raumtemperatur instabile monokline Modifikation (β) nur über die eigentliche Hochtemperatur-Modifikation (γ) erhalten wird.
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    Zeitschrift für anorganische Chemie 286 (1956), S. 296-306 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Nach der Methode der Direktcalorimetrie wurden die Bildungsenthalpien der folgenden Cu - Se-Verbindungen bestimmt:
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    Zeitschrift für anorganische Chemie 286 (1956), S. 291-295 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Tri-acetate, tri-propionate and tri-butyrate of aluminium have been prepared by the reaction between aluminium alkoxides and the corresponding acid anhydrides either in the presence or absence of an inert solvent. When carried out in benzene, the initial product appears to be a mono-alkoxy di-acid compound of aluminium which, on further refluxing in the acid anhydride gives the tri-acid compound. Aluminium tri-acetate and tri-propionate are found to be insoluble in benzene, whereas the tri-butyrate resembles the higher tri-soaps in being soluble in this solvent. The mono-alkoxy di-acid compounds have been found to be water repellent, but give viscous solutions in benzene.
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    Weinheim : Wiley-Blackwell
    Zeitschrift für anorganische Chemie 287 (1956) 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
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    Zeitschrift für anorganische Chemie 287 (1956), S. 1-11 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Anstelle der Elektronegativitäten nach Pauling werden zur Abschätzung der Polarität einer chemischen Bindung Rumpfladungszahlen auf der Basis der Ionisierungsenergien abgeleitet.
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    Zeitschrift für anorganische Chemie 287 (1956), S. 24-27 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Die in der Literatur als “Amidoverbindung” beschriebene Substanz HgNH2F ist auf Grund chemischer und physikalischer Untersuchungen als (Hg2N)F · NH4F aufzufassen. Es liegt wie in der Millonschen Base und deren Salzen, (Hg2N)X, ein dreidimensionales (Hg2N)-Gerüst vor, in dessen Hohlräumen Fluor- und Ammoniumionen eingelagert sind.
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    Zeitschrift für anorganische Chemie 287 (1956), S. 28-32 
    ISSN: 0044-2313
    Keywords: Chemistry ; Inorganic Chemistry
    Source: Wiley InterScience Backfile Collection 1832-2000
    Topics: Chemistry and Pharmacology
    Notes: Es werden durch Direktmessungen die Glasbildungs- und Entglasungswärmen für die im System KNO3—Ca(NO3)2 auftretenden Gläser bestimmt und aus ihnen die auf die Bildung der Verbindung 4 KNO3 · Ca(NO3)2 entfallende Wärmetönung errechnet. Aus der übereinstimmung des Maximums der Entglasungswärmen mit dem Maximum der Glasigkeit ergibt sich das Stabilitätsmaximum der inkongruent schmelzenden Verbindung in den Gläsern bei einem Calciumnitratgehalt von 50,4%.
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