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By J. B. Austin, R. L. Rickett

MEASUREMENTS Of the rate of decomposition of austenite at constant temperature are commonly represented by plotting the percentage transformed on linear coordinates against time on either a linear or a logarithmic scale, a method that yields a curve that in shape resembles an integral sign (Fig. 1). A graph of this kind is not always convenient because extrapolation to the beginning or end of the transformation, or even interpolation, may be uncertain unless there are a large number of observations, which seldom happens; furthermore, the degree of consistency of a set of measurements is difficult to judge from such a curve. It is desirable therefore to find some mode of plotting, or even better to find a standard variety of graph paper, that gives a straight line instead of the integral shape. The straight line has many advantages; the number of readings required to fix the position of the curve is greatly reduced, interpolation is easy and rapid, extrapolation can be carried out with greater confidence and, finally, the consistency of the measurements is readily estimated from the scatter of the points. The last advantage is particularly valuable when the data are obtained by direct microscopic examination alone, because they are influenced by the skill of the observer in estimating the relative size of areas, possibly also by undetected inhomogeneity of the specimen. A search for ways of representing the observations as a straight line yielded two methods which are described in this paper. The paper also includes an account of some interesting relations brought to light in applying these methods to the available experimental data. Usually the best way to derive such a method of plotting is to base it on established principles of chemistry and physics, as has been done, for example, for the temperature variation of the equilibrium constant of a chemical reaction. But so little is known of the mechanism of the decomposition of austenite, and so little is available in the way of well established background for changes of this kind, that it is simpler to rely upon purely empirical means. The general plan therefore is to study existing data with a view to finding some function of the direct observations that will

Jan 1, 1938

By J. B. Austin

MEASUREMENTS of the rate of decomposition of austenite at constant temperature are commonly represented by plotting the percentage trans-formed on linear coordinates against time on either a linear or a logarith-mic scale, a method that yields a curve that in shape resembles an integral sign (Fig. 1). A graph of this kind is not always convenient because extrapolation to the beginning or end of the transformation, or even inter-polation, may be uncertain unless there are a large number of observations, which seldom happens; furthermore, the degree of consistency of a set of measurements is difficult to judge from such a curve. It is desirable therefore to find some mode of plotting, or even better to find a standard variety of graph paper, that gives a straight line instead of the integral shape. The straight line has many advantages; the number of readings required to fix the position of the curve is greatly reduced, interpolation is easy and rapid, extrapolation can be carried out with greater confidence and, finally, the consistency of the measurements is readily estimated from the scatter of the points. The last advantage is particularly valu-able when the data are obtained by direct microscopic examination alone, because they are influenced by the skill of the observer in estimating the relative size of areas, possibly also by undetected inhomogeneity of the specimen. A search for ways of representing the observations as a straight line yielded two methods which are described in this paper. The paper also includes an account of some interesting relations brought to light in applying these methods to the available experimental data. Usually the best way to derive such a method of plotting is to base it on established principles of chemistry and physics, as has been done, for example, for the temperature variation of the equilibrium constant of a chemical reaction. But so little is known of the mechanism of the decom-position of austenite, and so little is available in the way of well established background for changes of this kind, that it is simpler to rely upon purely empirical means. The general plan therefore is to study existing data with a view to finding some function of the direct observations that will

Jan 1, 1938

By R. B. Anderson

As a part of a Bureau of Mines program on the conversion of coal to liquid and gaseous fuels, the kinetics of the Fischer-Tropsch synthesis on iron catalysts was investigated. Nitrided catalysts were studied at 21.4 atmospheres using feed gases ranging from 2H2+1CO to 0.25H2+1CO, and at 7.8 to 21.4 atmospheres using 1H2+1CO gas. The overall apparent activation energy increased with increasing carbon monoxide content of the feed gas from 19.5 kcal/mole for 2H2+1CO to 23.7 for 0.7H2+1CO. The rate of synthesis with 1H2+1CO feed increased linearly with operating pressure from 7.8 to 21.4 atmospheres. A semifundamental rate equation of the form [r=a'PH2 0.6pco 0.4- ?r0.5PH200.5] was shown to fit the data satisfactorily. The relative usage of hydrogen to carbon monoxide decreased with increasing conversion, passed a minimum, and then increased. Apparently water is the principal primary product and carbon dioxide is produced by subsequent water-gas shift reaction. In another group of experiments water, carbon dioxide, argon, and methane were added to 1H2+1CO feed to a nitrided iron catalyst. Argon and methane were only diluents. Carbon dioxide was a slight inhibitor and water vapor was a strong inhibitor to the rate of synthesis. Water accelerated the water-gas shift and usually increased methane production. Important factors of catalyst geometry in determining rate were found to be particle size and extent of reduction. Apparently the active portion of the catalyst is confined to a layer of 0.01 to 0.02 cm from the external surface of particles. A special solution was made of differential equations relating re¬action at the catalyst surface to diffusion in pores of the catalyst for spherical particles with an active layer surrounding an inert core. The equation derived expressed the experimental data reasonably well. Diffusivities determined by this equation varied from 3 to 24X10-6 cm2/sec; these values are of the same magnitude as observed for the diffusion of gases in liquid. The appendix presents a group of synthesis experiments at pressures of 21.4 to 103 atmospheres. In this range the rate of synthesis on nitrided iron catalysts increased with pressure to the 0.74 to 0.84 power.

Jan 1, 1964

By Matthew Novak, J. Brent Hiskey

It is well known that when chalcopyrite is put in direct contact with copper in an acidic medium a galvanic cell is created. Chalcopyrite is reduced to iron and sulfur deficient defect phases such as bornite, chalcocite, and at very low potentials to elemental copper. Galvanic conversion experiments were performed using three chalcopyrite concentrates. The first chalcopyrite contained less than 10% impurity phases. The second concentrate had a high concentration of pyrite, and the third concentrate had a high concentration of pyrrhotite. The effect of temperature, acid concentration, chalcopyrite grain size, copper grain size, and agitation on the rate of chalcopyrite conversion was studied.

Jan 1, 2014

The widely accepted kinetic model for the gaseous reduction of hematite is critically examined. The formation of the wustite layer during internal reduction cannot be explained in terms of solid-state diffusion. Present evidence indicates the existence of a micropore system in the wustite adjacent to the magnetite with the gas/solid type of reaction occurring not only at the iron/wustite interface but also at the wustite/magnetite interface. During the partial reduction of dense hematite pellets, in a controlled atmosphere, porous magnetite and wustite are formed as products. The mean pore size, as measured by mercury injection, increases with time at constant temperature and with temperature increase over the range 6500C to 950°C. The sizes of the pores indicate that Knudsen diffusion is the principal gaseous transport mechanism across thick layers of magnetite or wustite.The kinetics of the gaseous reduction to iron are consistent with a mixed control mechanism involving the interaction of gaseous diffusion effects with a first order reversible chemical reaction at the iron/wustite interface. Because of the larger pore sizes in the iron layers, ordinary molecular gaseous diffusion must be the principal transport mechanism. The usual experimental methods used for establishing the validity of chemical rate ~ontrol are incapable of differentiating between the mixed control- mechanism and exclusive chemical control.Some implications of mixed control kinetics are developed, including a predicted independence of rate on reducing gas pressure at higher pressures.INTRODUCTIONAn extensive literature review of the reduction of iron oxides has been compiled recently by Themelis and Gauvin (1962). From the large number of papers published and the widely divergent opinions of workers in this field, it appears that a simple unified quantitative analysis of reduction kinetics is not possible. The aim of the present paper is to show that a major cause of confusion is due to the attempts of many workers to interpret experimentally observed reaction rates in terms of a single rate controlling mechanism without due regard to other rate processes which must occur simultaneously.Some of the differences in behaviour reported for particles...

Jan 1, 1964

By Y. Topkaya, R. E. Johnson, B. R. Palmer, Jia-Jun Ke, Da-Ping Kang

The kinetics of the leaching of antimony oxide ore (Sb2O4) in aqueous hydrochloric acid solutions has been investigated. This dissolution reaction is a heterogeneous solid-liquid reaction. It has been found that the leaching temperature and the concentration of hydrochloric acid turn out to be the significant influencing factors on the leaching rate. The apparent activation energy for the leaching reaction was determined to be 63.5 W/mol within the experimental temperature region of 50O to 90O C. The experimental results indicate that the leaching process is controlled by the rate of the chemical reaction.

Jan 1, 1993

PRECEDING chapters on thermochemistry, and the reactions in and between metal and slag phases in the bath of the furnace tend to emphasize the equilibrium or "static" conditions in the furnace and process, such as the total amounts of heat from fuel combustion or from certain bath reactions, the concentration relationships between slag and metal at the steady state for certain reactions, and the like. Such data are obtained essentially by means of the logic of thermo- dynamics, which helps to determine the energy change between initial and final states in a process as well as to define its equilibrium or steady-state condition, but which is not concerned with the rate of change in the process or with the mechanisms or path followed between initial and final states. These questions of just "how it works" and "how fast" belong to the kinetic aspect of any process; their answers are helpful in speeding up or slowing down and thus controlling intelligently its operation, and also to understand certain natural limitations which are especially important in many high-temperature processes. The kinetic aspects of interest here comprise mainly (1) the flow of gases through the furnace system, (2) the flow of heat in the system, and (3) the mechanisms and rate factors in the various chemical reactions. A really adequate discussion of the first two subjects would require at least three or four times the space available here; it has been tried, therefore, in this and the next chapter to outline but a few fundamentals necessary to an intelligent approach and to indicate some of the conditions of heat and gas flow more or less peculiar to the open hearth, since several good general discussions on these subjects may be found in the literature.(1) For the designer of open-hearth furnaces, the principles of gas flow are of paramount importance.(2,3,4,5) They are also important to the operation of the process, however, at least to the extent of a general qualitative picture of the movement of gases in the system, which is all that is attempted here.

Jan 1, 1944

THE problem of reaction rates in the open-hearth process is essentially that of trying to form a fairly clear picture of the "chemical mechanisms" in the bath. Quantitative data on reaction rates would not be very useful even if they were available; however, what few , approximate data there are, can be used in combination with data given in Chapters XVI and XVII to sketch a picture of the "chemical mechanics" of the open-hearth process that is consistent with essentially all the present available evidence. The result may later be found incorrect in many details but even so it will illustrate certain useful methods for obtaining a clearer understanding of the process. As discussed in the last portion of Chapter XIII chemical reactions in general involve the following factors: 1. The reacting molecules are mixed together in space in such fashion as to favor collisions among them. 2. A certain number of collisions occur per unit time among the reagent molecules, depending on their concentration and on temperature. 3. A certain percentage of these collisions result in reaction, these being the collisions between those molecules possessing at the moment energy levels above certain minimum values. The temperature factor enters mainly through (3), and its effect is very marked. (What is called temperature is really the mean energy content of all the molecules of the substance involved; at any one temperature a certain proportion of the molecules will have much higher energy content than the mean value.) Various reaction rates measured at around room temperatures have been found to be speeded from 1.6 to 4.0 times by an increase of only 15 to 20°F., simply because increasing temperature produces a rapidly increasing percentage of molecules with energy levels above the minimum needed to produce chemical reaction in a collision.

Jan 1, 1944

By Alexandre Bonan

This paper reports the results of a kinetic study on the oxidation of free cyanide and Cu-cyanide complex ions with HO,. The variables and respective ranges studied were the following: [CN] total =10 - 500 mg/l; pH=10-11; (H2O2/CN) mole ratio = 1- 3; (Cu/CN) mole ratio = 0.10 - 0.25. The results were interpreted by a semi-empirical model that incorporates the useful oxidation reactions and the parallel alkaline decomposition of H2O2

Jan 1, 1994

The oxidation of ferrous ions by oxygen in sulphate solutions is a very slow process, but it tills long been known that the addition of sulphur dioxide increases the rate of reaction very significantly. The kinetics and mechanism of the process were investigated in the laboratory and the results confirmed the advantage of adding small amounts of sulphur dioxide to the oxygen stream for the removal of iron from solutions. The effect of various parameters on the overall rate of iron oxidation and precipitation was studied. In particular, temperature, acidity and composition of the gas mixture were considered and the optimum conditions for the precipitation of goethite were determined.

Jan 1, 1991

By J. R. Donald

Electric arc furnace (EAF) dust, which can be considered as a by-product of the steel recycling process, contains significant quantities of recoverable zinc and iron, as well as hazardous elements such as cadmium, lead and chromium, which can be leached by ground water. The zinc in the EAF dust is found almost entirely in the form of either zinc oxide or zinc ferrite, the latter accounting for 20 to 50 percent of the total zinc. It is important that an efficient process be developed which renders the dust inert, while reclaiming the valuable metals to off-set processing costs. During the conventional carbothermic reduction processes, iron is formed, and this iron can participate in the reduction of the zinc oxide in zinc ferrite. In the present work, the reduction of the zinc oxide in zinc ferrite by iron according to the following reaction: ZnO-Fe2O3(s,s) + 2 Fe(s) = Zn(g) + 4 FeO(s) was studied in an argon atmosphere using a thennogravimetric technique. First, a thermodynamic analysis was performed using the F*A*C*T computational system. Then, the effects of briquette aspect ratio (lid), temperature, zinc ferrite particle size, amount of iron added, as well as additions such as lime, sodium chloride, and calcium fluoride were investigated. It was found that, initially, the reaction was chemically controlled with an activation energy of 178.1 kJ/mol. Then, after a product layer had formed on the outer surface of the briquette, the reaction was restricted by the diffusion of zinc gas away from the reaction interface. The parabolic rate law was fitted to the experimental data, and the parabolic rate constant was found to be: = -6.2275 + 0.0054 T (K)

Jan 1, 1995

By Lo-Ching Chang, Kenneth M. Goldman

INTRODUCTION THE kinetics and mechanism of transfer of a constituent across a slag-metal interface are fundamentally important because many metallurgical processes involve the existence of a slag phase and a metal phase. Industrial processes seldom proceed to equilibrium, and information of the rates and modes of reactions are therefore often of greater practical importance than equilibrium data. A study of the kinetics of sulphur transfer across a slag-metal interface under reducing conditions will contribute a great deal toward a better understanding of desulphurization in the blast furnace process. The general principles existing in the transfer of a constituent, such as sulphur, across a slag-metal interface can be extended to similar transfer phenomena in other metallurgical processes. The present paper will demonstrate how such studies will lead to fruitful results from both the practical and theoretical standpoints. EXPERIMENTAL METHOD The apparatus used was simple. A graphite crucible 1 5/8-in. id, a wall 1/8-in. thick, and a depth of 4 in., was packed in an outer fused silica tube with powdered magnesia. The crucible assembly was rotated at a speed of 235 rpm inside an induction coil. A charge of 250 g of Armco ingot iron was introduced into the graphite crucible and melted by induction heating. The melt was held at a desired temperature [ ] for 3-5 min., after which 7.5 g of granular ferrous sulphide was added and the bath was held for another 3-5 min. A metal sample was then taken by means of a fused silica tube and a rubber suction bulb. Immediately after the metal sample was taken, 30 g of a prefused and crushed slag were introduced. The slag reached the temperature of the furnace in 1 to 1 1/ 2 min. Slag

Jan 1, 1948

By Xirneng Zhu

The electrochemical behavior of Pittsburgh and Illinois coal pyrite in basic and neutral borate/sulfate solutions was investigated. In the transpassive region, aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The formation of sulfur and polysulfides was identified by in-situ Raman spectroscopy. The growth kinetics of the reaction product film, resulting from transpassive oxidation of coal pyrites, were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The reaction rate was well correlated by a paralinear rate equation. The effects of electrode rotation speed, solution pH and temperature were examined. The kinetics were compared to those for mineral pyrite.

Jan 1, 1994

By Ximeng Zhu

In the transpassive region, about 0.4 to 0.8 V (SCE), aggressive oxidation of pyrite occurred. The reaction products in this region were Fe(III) oxide, sulfate ion and partially oxidized sulfur intermediates. The growth kinetics of the reaction product film, resulting from transpassive oxidation of pyrite were studied using chronoamperometry measurement with both stationary and rotating disk electrodes. The effect of electrode rotation speed, solution pH and temperature were examined. Potentiostatic measurements were well correlated by a paralinear rate equation, suggesting the formation of an intermediate passive film, associated with the simultaneous dissolution of the outer layer of the film. Activation energies of 66.17 kJ/mole (15.83 kcal/mole) and 38.67 kJ/mole (9.25 kcal/mole) were obtained for associated parabolic and linear rate constants respectively, at an applied potential of 0.6 V.

Jan 1, 1993

By Zhen Zhang, Jiang Diao, Xuan Liu, Tao Zhang, Bing Xie, Hong-Yi Li

Extracting vanadium from vanadium containing hot metal by LD process has been proven an effective solution for the utilization of vanadium-titanium magnetite ore, but the systematic analyses of vanadium extraction rate and mechanism by basic slag are seldom reported. In this study, mathematical model of vanadium transfer from metal to slag was formulated and the rates of vanadium extraction of hot metal with basic slag were investigated. The results indicated that the apparent vanadium extraction rate constant, kp, were in the range of 1.33~9.07×10-4g/(cm3·s). And the rate constant was increased with the increase of final slag basicity, reaction temperature and stirring gas flow. The apparent of mass transfer parameter decreases significantly from 0.13 cm3/ s to 0 cm3/ s in 20min, and the data changed as negative due to the decrease of slag oxidation and recovery of vanadium from slag to metal.

Jan 1, 2015

By Herry Poernomo, Agus Prasetya, Iga Trisnawati, Himawan Tri Bayu Murti Petrus, Gyan Prameswara, Panut Mulyono

We studied yttrium extraction from untreated zircon sand processing waste tailings. Xenotime mineral as the rare earth element source with an abundance of yttrium (REY) was detected in sufficient grade for extraction. As much as 9.03% yttrium exists in zircon tailings (analysed by X-ray fluorescence spectrometry). The presence of yttrium was confirmed by X-ray diffractometry in xenotime minerals, which are yttrium carriers (Y-PO4). The purpose of this research was to determine the effect of leaching conditions on yttrium recovery from zircon sand after alkaline fusion treatment. Alkaline fusion was chosen to decompose phosphate into hydroxide in the xenotimemineral,which will reduce further required hydrometallurgical processing.Alkaline fusionwas carried out for 3 h at 450 °C, with a ratio of sodium hydroxide to zircon tailings sand of ~ 1:1. The alkaline fusion product was leached with water, followed by hydrochloric acid treatment to leach the yttrium. Yttrium recovery reached 87% under optimum conditions (60 °C, 1MHCl, and solid-to-liquid ratio = 1/10 for 7.5 min). A suitable model for yttrium dissolution with hydrochloric acid was diffusion through a solid particle ash layer. The calculated activation energy (EA) for this model was 20.21 kJ/mol.

May 26, 2020

By D. Quattrini

The aim of the present work is to present the gas chromatography (GC) as an alternative method of analysis in the thermal decomposition of calcium carbonate. Therefore, a furnace/GC on-line system was employed to study the kinetics of the reaction, measuring the CO2 produced in the decomposition. One of the advantages of the GC method is the possibility to perform an in-situ characterization and quantification of the gaseous products to obtain kinetic parameters, besides the method is simple and shows a good reproducibility. The decomposition of calcium carbonate was carried out in isothermal conditions at temperatures from 655 to 715°C with nitrogen as purge gas. Several gas velocities were used to determine the adequate flow that minimizes the effect of external mass diffusion as rate controlling step. It was made a preliminary analysis of the sample size influence on the reaction rate. The activation energy of the reaction was determined by Flynn method. The value obtained was in a good agreement with other authors. On the other hand, gravimetric measurements were employed for compare GC results.

Jan 1, 2006

By Ying Wang, Min Chen, Cuihuan Huang, Haohua Deng, Nan Wang, Ming Chen

Adding limestone directly into converter is considered to be favorable to energy conservation and emission reduction by transferring the decomposition reaction of limestone from the shaft or rotary kiln to the converter. In this paper, the kinetics of limestone decomposing in early converter slag was studied at 1300–1400 °C, and the effects of slag temperature and stirring speed introduced to the slag bath were examined. The kinetic results based on shrinking core model analysis showed that the limestone decomposition was a mixed rate control of chemical reaction and heat conduction through the lime layer, which could be promoted at higher slag temperature by supplying more heat to the converter bath. In addition, the chemical reaction rate constant and effective thermal conductivity were determined.

Mar 1, 2018

By Rui Xiang Yang, Cong Li, Jia Zeng, Rong Liang Zhang, Wei Zhang, Chao Fan Tang

This research took the roasted products obtained by leaching copper (Cu) refining slag using waste acids and roasting leaching residues with calcium oxide (CaO) as raw materials and used oxidative leaching to extract Cu from roasted products using waste acids. Influences of the leaching temperature, liquid–solid ratio, and sulfuric acid ( H2SO4) concentration in waste acids on the leaching rate of Cu in the oxidative leaching process of roasted products using waste acids were investigated. The unreacted-core shrinking model of heterogeneous reactions was adopted to reveal the leaching kinetics of Cu in the oxidative leaching process of roasted products using waste acids. Results show that the leaching rate of Cu reaches 91.68% when the leaching temperature, liquid–solid ratio, H2SO4 concentration in waste acids, and injected airflow are 80 ℃, 8:1, 1.5 mol/L, and 200 mL/min, respectively. If the leaching temperature is below 80 ℃, the leaching process of Cu is controlled by the solid-film diffusion, and the apparent activation energy Ea is 11.0835 kJ/mol; at a leaching temperature above 80 ℃, the leaching process of Cu is governed by the interfacial chemical reaction, with an apparent activation energy Ea of 42.3183 kJ/mol. The liquid–solid ratio can positively influence the reaction rate constant. The apparent order of the leaching reaction of Cu is 0.632.

Jan 11, 2023

By Ruiling DU, Xiao YUAN, Keng Wu, Daan XU, Changyao CHAO

To utilize low grade coals to produce high quality semi-coke which can be used in blast furnaces, the pyrolysis of low grade coals was studied in this paper. According to the characteristics of coal pyrolysis process, the temperature range was divided into three parts. The interfacial chemical reaction model, random pore model and the internal diffusion model with the shrinking volume of resultant were established to describe the different ranges of pyrolysis process respectively. The results showed that the experimental data was fitted well, and all the correlation coefficients (r2) exceeded 0.97. Finally, the kinetic parameters for each temperature range have been calculated, which laid a necessary foundation for the simulation and expanded production.

Jan 1, 2016