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Title: Transactions of the Faraday Society

Journal of the Chemical Society, Faraday Transactions (1990-1996)

Journal of the Chemical Society, Faraday Transactions I: Physical Chemistry in Condensed Phases (1972-1989)

Journal of the Chemical Society, Faraday Transactions II: Molecular and Chemical Physics (1972-1989)

Transactions of the Faraday Society (1905-1971)

Full Journal Title: Transactions of the Faraday Society

ISO Abbreviated Title: J. Chem. Soc.

JCR Abbreviated Title: J Chem Soc

ISSN: 0014-7672

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: Impact Factor

? Firth, J.B. (1921), Sorption of iodine by carbon. Transactions of the Faraday Society, 16, 434-452.

Full Text: -1959\Tra Far Soc16, 434.pdf

Abstract: Iodine is dissolved in benzene (solubility 103.9 gm. per litre at 15°C.) or chloroform (36.2 gm.) and absorbed by lamp-black, sugar carbon, blood charcoal, animal charcoal, and coconut charcoal, both from the fruit and the shell, to study the influence of time (up to five years), size of particles, and previous treatment; most of the experiments are made at 25°C. The paper is largely tabular. There is a rapid surface condensation (adsorption) followed by a slow diffusion into the interior (absorption). The former is mostly instantaneous and is complete in a few hours; the latter may continue for years. The rate of sorption is influenced by the natures of both the solvent and the sorbing solid. In blood charcoal the adsorption is very high; in coconut charcoal absorption is the predominating factor. The concentration of the dissolved iodine decreases to a minimum, and then remains almost constant; the initial adsorption is the greater, the smaller the carbon particles. Blood charcoal in chloroform sorbs 90% of the total iodine, coconut (fruit) charcoal less than 3%; the time taken to reach the concentration minimum amounts to 6 days in the former case (6 or 8 gm. of carbon per cm.3 of solution) and 5 years in the latter; in sugar carbon the minimum was not reached after 5 years. Fine powdering much increases the rate of sorption of coconut carbon; the relative amounts of adsorption and absorption depend to some extent on the size of the particles, and absorption may only cease to be a factor when the carbon particles approach molecular dimensions. The presence of water in the carbon lowers the adsorption capacity, especially in lamp-black.

? Freundlich, H.M.F. (1932), Of the adsorption of gases. Section II. Kinetics and energetics of gas adsorption. Introductory paper to section II. Transactions of the Faraday Society, 28, 195-201.

Full Text: -1959\Tra Far Soc28, 195.pdf

? Polanyi, M. (1932), Theories of the adsorption of gases. A general survey and some additional remarks. Introductory paper to section III. Transactions of the Faraday Society, 28, 316-333.

Full Text: -1959\Tra Far Soc28, 316.pdf

Notes: highly cited

? Lennard-Jones, J.E. (1932), Processes of adsorption and diffusion on solid surfaces. Transactions of the Faraday Society, 28, 333-358.

Full Text: -1959\Tra Far Soc28, 333.pdf

Notes: highly cited

? Evans, M.G. and Polanyi, M. (1935), Some applications of the transition state method to the calculation of reaction velocities, especially in solution. Transactions of the Faraday Society, 31 (1), 875-893.

Full Text: -1959\Tra Far Soc31, 875.pdf

Barrer, R.M. (1936), The rates of interaction of proto- and deutero-hydrogen and methane with charcoal. Transactions of the Faraday Society, 32, 481-486.

Full Text: -1959\Tra Far Soc32, 481.pdf

Barrer, R.M. (1936), The interaction of ligh and heavy water with aluminum carbide and calcium phosphide. Transactions of the Faraday Society, 32, 486-490.

Full Text: -1959\Tra Far Soc32, 486.pdf

Barrer, R.M. (1936), The thermal decomposition of light and heavy ammonia and phosphine on tungsten. Transactions of the Faraday Society, 32, 490-501.

Full Text: -1959\Tra Far Soc32, 490.pdf

Notes: highly cited

? Evans, M.G. and Polanyi, M. (1936), Further considerations on the thermodynamics of chemical equilibria and reaction rates. Transactions of the Faraday Society, 32 (2), 1333-1359.

Full Text: -1959\Tra Far Soc32, 1333.pdf

Notes: highly cited

? Evans, M.G. and Polanyi, M. (1938), Inertia and driving force of chemical reactions. Transactions of the Faraday Society, 34 (1), 11-23.

Full Text: -1959\Tra Far Soc34, 11.pdf

? McBain, J.W., Mills, G.F. and Ford, T.F. (1940), The interferometer method for measuring absolute adsorption in the surface of solutions. Transactions of the Faraday Society, 36, 930-935.

Full Text: -1959\Tra Far Soc36, 930.pdf

Keywords: Adsorption, Method, Solutions, Surface

? Duncan, J.F. (1949), The determination of the surface area of a solid from an adsorption isotherm. Transactions of the Faraday Society, 45 (9), 879-891.

Full Text: -1959\Tra Far Soc45, 879.pdf

Abstract: The Harkins method, and the Brunauer, Emmett and Teller method of estimating the surface area of a solid from the adsorption isotherm of a suitable gas are applied to isotherms of ethylene at liquid air temperature. It is shown that both methods lead to the same results for a given isotherm. The isotherm equation of Harkins, and the Brunauer, Emmett and Teller equation as modified by Anderson are reduced to the form p/p_o = C(I - v m / (D V)); it is shown that from the Anderson constant K, and assuming a given value for the area occupied by an adsorbed molecule, the Harkins constant K may be estimated approximately. A more accurate value of k is obtained from the plot of p/po against I/V for isotherms of nitrogen and ethylene. A quick method of determining the surface areas of large numbers of solids to about 20 yo accuracy is suggested, based on the assumption of a value for the Anderson constant, and the linearity of the p / p o - I/V plot over the range of p/p_o from 0.25 to 0.75.

? Fergusson, R.R. and Barrer, R.M. (1950), Derivation and development of Hüttig’s multilayer sorption isotherm. Transactions of the Faraday Society, 46 (4-5), 400-407.

Full Text: -1959\Tra Far Soc46, 400.pdf

Abstract: A statistical derivation has been given of the most generalized form of sorption isotherm based on Hüttig’s view of the evaporation-condensation properties of a sorbed molecule. From this general equation a number of characteristic isotherm equations have been obtained analogous to the various modifications of the B.E.T. isotherm. From calculations based upon these Hüttig-type multilayer sorption isotherms it has been shown possible to obtain curves corresponding to isotherms of types I, III and to some extent V, of Brunauer’s classiffication, but not to types II and IV. It is also possible to obtain limiting values of the sorption corresponding to less or much more than the two layers given by Hüttig’s original isotherm equation.

? Eley, D.D. (1953), The kinetics of unimolecular processes in condensed phases, including adsorption. Transactions of the Faraday Society, 49 (6), 643-649.

Full Text: -1959\Tra Far Soc49, 643.pdf

Abstract: A kinetic equation is deduced for a unimolecular process occurring in a condensed phase, which, as a result of molecular interactions, possesses a free energy of activation which increases during the course of the reaction.

The equation is shown to fit certain data on elastic, magnetic, and volume creep in solids. It also fits some data on the rate of desorption of gases on metals, and on the activated adsorption of gases on oxides. A tentative conclusion is that the interaction effect is more marked for metals than oxides. The equation does not fit data on dielectric creep, which is known to be described by a Gaussian distribution of unimolecular processes.

? Gkueckauf, E. (1955), Theory of chromatography. Part 10. Formulae for diffusion into spheres and their application to chromatography. Transactions of the Faraday Society, 51 (11), 1540-1551.

Full Text: -1959\Tra Far Soc51, 1540.pdf

? Frumkin, A.N. (1959), Influence of cation adsorption on the kinetics of electrode processes. Transactions of the Faraday Society, 55 (1), 156-167.

Full Text: -1959\Tra Far Soc55, 156.pdf

Abstract: The influence of cation adsorption on the rate of the electroreduction and formation of cations as well as on the electroreduction of anions is discussed. The effects observed are correlated with changes of the ₁-potential, but whereas in reactions with the participation of cations average values of the ₁-potential can be used, in the anion electroreduction the dependence oL the ₁-potential on the distance between the reacting anion and the cation which is its next neighbour must be taken into account. The electroreduction of the PtC₄^2- anion which has a flat configuration shows a much smaller sensitivity towards cations than the electroreduction of the S₂O₈^2- and Fe(CN)₆^3- anions.

Measurements of reaction rates and differential capacities in the presence of Cs⁺ ions indicate a certain specific adsorbability of the Cs⁺ ion. If both the cation and the anion are surface-active, that effect of the adsorption on reaction rates which prevails at a definite potential is still enhanced.

? Scholten, J.J.F., Zwietering, P., Konvalinka, J.A, and Deboer, J.H. (1959), Chemisorption of nitrogen on iron catalysts in connection with ammonia synthesis. Part 1. The kinetics of the adsorption and desorption of nitrogen. Transactions of the Faraday Society, 55 (12), 2166-2179.

Full Text: -1959\Tra Far Soc55, 2166.pdf

Abstract: An extensive gravimetric study was made of both the adsorption and desorption kinetics of nitrogen on a highly reduced singly promoted iron catalyst. The activation energy of adsorption rises linearly with coverage up to 0 21 0.22. Above this value the activation energy remains constant at 23 kcal/mole. The activation energy of desorption decreases gradually with the coverage over the whole range investigated. The kinetics are discussed in terms of the absolute reaction rate theory. It appears that the chemisorptive behaviour of the catalyst approaches the behaviour of iron films.

With the help of the isotherms found by equalizing the adsorption and desorption rates, a computation is made of the entropy of the adsorbed particles. The results lead to a picture of the state of nitrogen molecules on the surface which is in agreement with the kinetic data.

? Miller, I.R. (1961), Kinetic of adsorption of unionized polymethacrylic acid (PMA) and polylysine in mercury-water interface. Transactions of the Faraday Society, 57 (2), 301-311.

Full Text: 1960-80\Tra Far Soc57, 301.pdf

Abstract: The differential capacity of the electrical double layer at the Hg/electrolyte solution interface in the presence of added unionized polymethacrylic acid and polylysine has been measured. The surface concentration of the partly covered surface has been calculated by assuming a diffusion-controlled adsorption process. The linear relation between capacity, surface charge density and surface tension and between polymer surface concentration has been found and discussed. The linear plot of capacity or surface tension against polymer concentration when the surface was only partially covered was extrapolated towards concentrations at which there is full coverage of the surface exposed to the adsorption process for a certain time t. This procedure allows the determination of the concentration of a fully compact but non-compressed polymeric surface film. As the amount of segments anchored in the mercury surface can be estimated from capacity or surface charge density data, the anchored segment fraction p can be evaluated.

? Thomas, J.G. (1961), Kinetics of electrolytic hydrogen evolution and adsorption of hydrogen by metals. Transactions of the Faraday Society, 57 (9), 1603-1611.

Full Text: 1960-80\Tra Far Soc57, 1603.pdf

Abstract: For metals where the electrolytic hydrogen evolution reaction gives a Tafcl line of low slope, e.g., 2.3 RT/2F or 2.3 RUF, the formulation of the reaction kinetics oil the assumption that the adsorbed hydrogen atoms obey a Lzngmuir isotherm is not in good agreenient with espcriniental data on surfxe coverage and reaction rates. A more consistent kinetic scheme is obtained by taking into account the variation with coierage of the heat of adsorption and activation energies for adsorption and desorption of hydrogen 011 metals. A Tafel slope of 2.3 RT/2F corresponds to a fast discharge reactloii fdhwed by a ratedetermining combination reaction, where the chemisorption of hydrogeir by tile metal is not activated. A Tafel slope of 2.3 RTIF corresponds to a fast discharge reaction followed by either a rate-deterrninii2g combiiiation reaction, where the chemisorption of hydrogen by the metal is activated, or by a rate-deiermining ioniatom reaction. It is possible to distinguish these alternatives by considering the change in Tafel slope at high current densities.

? Everett, D.H. (1964), Thermodynamics of adsorption from solution. Part 1. Perfect systems. Transactions of the Faraday Society, 60 (502P), 1803-1813.

Full Text: 1960-80\Tra Far Soc60, 1803.pdf

Abstract: The preferential adsorption of molecules from a perfect solution by a Langmuir-type adsorbing surface is discussed. Equations are given for the chemical potentials of the adsorbed species and for the adsorption isotherms. The adsorption equation is found to represent satisfactorily the data for several simple systems and leads to a new method of estimating the surface areas of solids. A possible method is suggested for the correlation of adsorption phenomena at the solid/vapour, solid/liquid and liquid/vapour interfaces. A discussion is also given of the relationship between heats of immersion of solids in solutions and the corresponding adsorption isotherms.

? Gilman, S. (1965), Studies of hydrocarbon surface processes by multipulse potentiodynamic method. Part 1. Kinetics and mechanisms of ethane adsorption on platinum. Transactions of the Faraday Society, 61, 2546-2560.

Full Text: 1960-80\Tra Far Soc61, 2546.pdf

Abstract: A pulse sequence was devised to allow the study of ethanc adsorption on a clean platinum surface under well-defined conditions. A charge QE, quantitatively related to the surface coverage with ethane, may be measured by means of a linear anodic sweep of proper speed. Lf the desorption processes are minimized, the rate of adsorption of ethane is initially constant and then follows an empirical Elovich relationship. The data may be interprcted as indicative of an adsorption rate-determining step which is second-order in free surface sites, and first order in dissolved ethane concentration. This applies from zero to high fractional surface coverages. Departure from this law at highest surface coverages may be due to steric hindrance effects.

? Gilman, S. (1966), Studies of hydrocarbon surface processes by multipulse potentiodynamic method. Part 3. Kinetics of adsorption of ethylene and acetylene on platinum and structure of adsorbed layer at low potentials. Transactions of the Faraday Society, 62, 466-480.

Full Text: 1960-80\Tra Far Soc62, 466.pdf

Abstract: A sequence of potential pulses may be used to effect the reproducible adsorption of ethylene or of acetylene from perchloric acid solution. During the course of adsorption (smooth platinum micro-electrode) at 0.4 V and 30°C, measurement was made of the charge corresponding to adsorbed hydrocarbon (through oxidation to CO₂ and H₂O), the charge corresponding to hydrogen co-deposition, and the current corresponding to hydrogen dissociated from ethylene. The results suggest similar compositions of the ad-layers (probably corresponding to the composition C₂H₂) for the two different adsorbates, under the specific conditions employed. The adsorption rate conforms well to a simple diffusion law, establishing the quantitative validity of the MPP measurement technique for these systems.

? Eley, D.D. and Leslie, R.B. (1966), Kinetics of adsorption of water vapour and electrical conduction in bovine plasma albumin. Transactions of the Faraday Society, 62, 1002-1014.

Full Text: 1960-80\Tra Far Soc62, 1002.pdf

Abstract: A vacuum microbalance has been constructed, and used to make rate and equilibrium studies of the adsorption of water vapour on bovine plasma albumin. A rapid rise of temperature occurs over the first few minutes, and thereafter the kinetics may be described by a modification of the Roginsky-Zeldovich equation. dmdt=Kp0.6exp –(‘mpRT). This equation is interpreted in terms of repulsive interaction between the charge-transfer dipoles of water molecules ‘adsorbed’ by hydrogen bonds on to >CO … H—N< groups. The model, which is generalized as an impurity semiconductor model, also gives a qualitative account of heat of adsorption and electrical conductance as a function of amount of water adsorbed.

? Griffith, R. and Pryde, J.A. (1967), Adsorption-absorption kinetics of nitrogen+tantalum system. Transactions of the Faraday Society, 63, 2522-2527.

Full Text: 1960-80\Tra Far Soc63, 2522.pdf

Abstract: The nitrogen sorption behaviour of tantalum has been studied using both constant pressure and constant volume techniques in the pressure and temperature ranges 10^–9–10^–4 toor and 295–1600°K respectively. Chemisorption at room temperature occurs with an initial sticking probability of 0.33 and ceases at a saturation coverage of about 5×10¹⁴ atoms cm^–2, which is independent of pressure in the range 5×10^–9–3×10^–7 torr. There is evidence for the existence of two binding states. Above about 500°K adsorption and absorption occur simultaneously, the energy barrier to gas entry into the metal from the surface being about 38 kcal (g atom)^–1.

? Baret, J.F., Armand, L., Bernard, M. and Danoy, G. (1968), Kinetics of adsorption at liquid/liquid interface - role of diffusion energy barrier and number of free sites when desorption is slight. Transactions of the Faraday Society, 64, 2539-2548.

Full Text: 1960-80\Tra Far Soc64, 2539.pdf

Abstract: The general equation describing the adsorption kinetics at an interface may be simplified when the desorption is slight. The number of solute molecules lying at the interface, at any time is given by the relation, n= 2C0(Dt/)½(SS/S) exp (b–a)/kT. The quantity 2C0(Dt/)½ comes from the diffusion equations, whereas SS/S brings in the fraction of free interface and exp[b–a/kT] is the transfer probability of a solute molecule over an adsorption energy barrier. The introduction of an interfacial equation of state allows one to test this theory with the experimental results obtained, with the aid of a pendant-drop tensiometer, for chlorophyll adsorbing at the paraffin oil/water interface. The influence of the temperature and of the introduction of a second polar solute (lauric alcohol) with the adsorption kinetics is studied.

? Giles, C.H. and Dsilva, A.P. (1969), Molecular sieve effects of powders towards dyes - Measurement of porosity by dye adsorption. Transactions of the Faraday Society, 65 (559P), 1943-1951.

Full Text: 1960-80\Tra Far Soc65, 1943.pdf

Abstract: p-Nitrophenol (PNP) in water or in benzene solution, and several dyes, have been used to measure the apparent specific surface of porous charcoals, silicas and alumina by adsorption. The results reveal a relation between the apparent surface and pore size distribution. The method measures the actual surface accessible through pores of given minimum radius, rather than the pore volume, which is the parameter measured by, e.g., benzene desorption or mercury porosimetry. Nevertheless, when allowance is made for the probable aggregate size of the adsorbed dye, there is reasonable agreement between results by the present method, and these other two methods. The present methods offer a simple means of determining pore size and area distribution in the transitional pore range, which is the range of most interest in treatments involving liquids.

Keywords: Adsorption, Dye, Dyes, Porosity

? Aharoni, C. and Tompkins, F.C. (1970), Rates of adsorption of hydrogen, carbon monoxide and their mixtures on zinc oxide. Transactions of the Faraday Society, 66, 434-446.

Full Text: 1960-80\Tra Far Soc66, 434.pdf

Abstract: The rates of adsorption of hydrogen on zinc oxide at 24.6°C at various pressure (50-300 Torr) have been measured. After an initial period of time, the Elovich equation was closely obeyed. Out-gassing at 410°C for 30 h (high temperature regeneration) did not reproduce the original surface and the rates continuously decreased with each high temperature regeneration. A detailed study was therefore made of the effect of the presence of residual absorbate left on the surface due to ineffective outgassing, viz., evacuation at 24.6°C. Neither a model of a surface having a site heterogeneity but absence of induced effects, nor one of a uniform surface on which induced heterogeneity was developed, can account for the kinetics of readsorption, but a combined model in which both site and induced effects are postulated gives an adequate representation of the experimental results. Some general features of the distribution of site activation energies can also be deduced.Carbon monoxide was rapidly adsorbed by zinc oxide at 24.6°C but the subsequent increase of adsorption with time was negligible. For a binary gaseous mixture of carbon monoxide and hydrogen, the rate of adsorption of hydrogen was decreased but an activated rate of adsorption subsequently developed. This mutual enhancement of the rate of adsorption of both gases is brought about by strong interaction between the two adsorbates on the surface. By introduction of an attractive potential into the analysis of the combined model, the kinetics of adsorption of each gas from a binary mixture can be adequately explained; furthermore, a comparison of the rates for the two components enables the empirical formula of the surface complex, viz., H₂CO, to be deduced. This method of detecting the presence of a surface compound formation and determining its composition should have general validity for simple systems.

? Pugh, D., Giles, C.H. and Duff, D.G. (1971), Determination of the aggregation number of anionic dyes by studies of deviation from Beer’s Law. Transactions of the Faraday Society, 67 (578), 563-573.

Full Text: 1960-80\Tra Far Soc67, 563.pdf

Abstract: The aggregation of four anionic azo dyes has been studied spectrophotometrically at high aqueous concentrations, using a cell of very small path length. The dyes all show apparent deviations from Beer's law and, using narrow particle size fractions of an azo pigment, apparent deviations from the law occur only when the particle size distribution of the absorbing species changes with concentration. On the basis of the stacking of the individual dye molecules behind one another to form aggregates, a theory has been developed relating the apparent deviation from Beer's law to the degree of aggregation, and average molecular weights have been evaluated for the four dyes.

Keywords: Adsorption, Aggregation, Determination, Dyes

? Horgan, A.M. and King, D.A. (1971), Kinetics of adsorption, replacement and catalysis in interaction of O₂ and CO with clean nickel surfaces. Transactions of the Faraday Society, 67, 2145-2157.

Full Text: 1960-80\Tra Far Soc67, 2145.pdf

Abstract: The kinetics of the interaction of O₂ with CO on Ni films under ultra-high vacuum conditions has been investigated utilizing an apparatus designed for sticking probability profile measurement. With it, absolute rates of adsorption, replacement and catalysis, and surface coverages in the reacting species were simultaneously measured. The results reveal marked differences in the chemical reactivity of the different binding states in the adlayer. The catalytic reaction of preadsorbed O₂ with gaseous CO to form CO₂ was found to proceed only when the coverage  in the preadsorbed O₂ layer was < ¼ monolayer. The catalytically active species ‘-O₂ is converted to a more tightly bound, inert species -O₂ at O₂ > ¼ monolayer, this transformation having a marked effect on the sticking probability profile for O₂ on Ni.4 Reaction kinetics indicate that the ‘-O₂ state is non-dissociatively adsorbed. When gaseous O₂ is introduced to Ni films with preadsorbed CO, the CO is efficiently and quantitatively displaced from the surface as Co and CO₂. The strongly bound -CO state yields CO₂ and a more weakly bound -CO state yields CO, both processes being preceded by a short induction period. Reaction mechanisms are proposed which are supported by infra-red data obtained from supported nickel-on-silica samples. The continuous catalytic reaction of CO with O₂ to form CO₂ to form CO₂ over O₂-presaturated Ni films was also examined, and a possible reaction mechanism is discussed.