scholarly journals Some experiments on thermal diffusion

It has been shown theoretically by Dr. S. Chapman that a temperature gradient applied to a uniform mixture of two gases will tend to produce non-uniformity of composition, the heavier and larger molecules diffusing towards the cooler side, and the smaller and lighter molecules diffusing towards the hotter side. This phenomenon was termed “thermal diffusion.” The difference in composition due to thermal diffusion increases until it is balanced by the opposite effects of ordinary diffusion, when a steady state will be reached. The effect will be greatest when the gases are mixed in nearly equal proportions by volume, and will be greater the more unequal are the masses and diameters of the gas molecules. It was also shown that the extent of the effect would vary with the character of the gas molecules, being at a maximum when the molecules behave like rigid elastic spheres. In the case where molecules behave like fifth power centres of force the effect would disappear entirely. Experiments made by Chapman and Dootson established the existence of the phenomenon. The results were chiefly qualitative, the nature and order of magnitude being in agreement with the theory. In no case were the differences equal to the theoretical values obtained on the assumption that gas molecules behave like rigid elastic spheres. Although the results are not claimed to be exact, the general effect could be regarded as rather less than a half of this calculated effect. The character of the gas molecule required to give this result would, however, be in agreement with that obtained for the actual gas molecules from the investigation of the variation of viscosity with temperature.

2013 ◽  
Vol 78 (8) ◽  
pp. 1189-1202 ◽  
Author(s):  
Jelena Lovic ◽  
Dusan Tripkovic ◽  
Ksenija Popovic ◽  
Vladislava Jovanovic ◽  
Amalija Tripkovic

Formic acid oxidation was studied on two Pt-Bi catalysts, Pt2Bi and polycrystalline Pt modified by irreversible adsorbed Bi (Pt/Biirr) in order to establish the difference between the effects of Biirr and Bi in alloyed state. The results were compared to pure Pt. It was found that both bimetallic catalysts were more active than Pt with the onset potentials shifted to more negative values and the currents at 0.0 V vs. SCE (under steady state conditions) improved up to two order of magnitude. The origin of Pt2Bi high activity and stability is increased selectivity toward formic acid dehydrogenation caused by the ensemble and electronic effect and suppression of Bi leaching from the surface during formic acid oxidation. However, although Pt/Biirr also shows remarkable initial activity compared to pure Pt, dissolution of Bi is not suppressed and the poisoning of the electrode surface induced by dehydration path is observed. Comparison of the initial quasi-steady state and potentiodynamic results obtained for these two Pt-Bi catalysts revealed that the electronic effect, existing only in the alloy, contributes earlier start of the reaction, while the maximum current density is determined by the ensemble effect.


2008 ◽  
Vol 19 (12) ◽  
pp. 1829-1845 ◽  
Author(s):  
J. F. VALENZUELA ◽  
C. MONTEROLA

We examine the segregation and mixing dynamics of a dilute bidisperse suspension of particles in a fluid subjected to a temperature gradient. Configurations corresponding to varying uniform bottom wall temperatures, as well as various bottom wall temperature profiles, are examined. Measures of spatial segregation and aggregation are discussed and used to analyze the suspension's dynamics. The results show that the difference in mass lead to transient segregation at short time scales, together with long-term intermixing and aggregation. Comparison of the segregation and aggregation among different configurations reveal that the strength of the temperature gradient is the primary influence on both segregation and aggregation. The particles are driven the fastest into the long – term steady state in the uniform and Gaussian bottom temperature profiles. In addition, the qualitative features of transient segregation do not change if the difference in mass is varied. The results suggest that a fluid undergoing thermal convection can be used to segregate particles, but only at short times, as fluid reaches its steady state. Keeping a fluid indefinitely in a transient state may improve the duration of segregation.


Author(s):  
Mowbray Ritchie

SummaryAn elementary theory of thermal diffusion applicable to gaseous and liquid systems has been developed. This is based on the difference of diffusional characteristics of a molecule considered as diffusing through two different temperature regions, when the pressure is constant throughout.For gaseous systems, the resultant expression is shown to be in general accordance with experimental variation of temperature, mass, and diameter factors, and is further developed to include isotopic separation, change of sign of separation with concentration, and general force law considerations.A similar approach to thermal diffusion in solution, combined with the convection effect of a “cascade” system, gives an expression which is in general agreement with the results of experimental variation of mean temperature and temperature gradient for aqueous solutions of sucrose, glucose and glycerol. The simple expression does not account rigidly for the sign of separation or the effect of altered concentrations. These discrepancies are discussed in relation to the general formula; it is concluded that in addition to the diffusion diameters, the relative thermal expansions of solute and solvent are of importance in this connection.


Cells ◽  
2021 ◽  
Vol 10 (4) ◽  
pp. 811
Author(s):  
Camille Boisson ◽  
Minke A. E. Rab ◽  
Elie Nader ◽  
Céline Renoux ◽  
Celeste Kanne ◽  
...  

(1) Background: The aim of the present study was to compare oxygen gradient ektacytometry parameters between sickle cell patients of different genotypes (SS, SC, and S/β+) or under different treatments (hydroxyurea or chronic red blood cell exchange). (2) Methods: Oxygen gradient ektacytometry was performed in 167 adults and children at steady state. In addition, five SS patients had oxygenscan measurements at steady state and during an acute complication requiring hospitalization. (3) Results: Red blood cell (RBC) deformability upon deoxygenation (EImin) and in normoxia (EImax) was increased, and the susceptibility of RBC to sickle upon deoxygenation was decreased in SC patients when compared to untreated SS patients older than 5 years old. SS patients under chronic red blood cell exchange had higher EImin and EImax and lower susceptibility of RBC to sickle upon deoxygenation compared to untreated SS patients, SS patients younger than 5 years old, and hydroxyurea-treated SS and SC patients. The susceptibility of RBC to sickle upon deoxygenation was increased in the five SS patients during acute complication compared to steady state, although the difference between steady state and acute complication was variable from one patient to another. (4) Conclusions: The present study demonstrates that oxygen gradient ektacytometry parameters are affected by sickle cell disease (SCD) genotype and treatment.


The present paper describes an investigation of diffusion in the solid state. Previous experimental work has been confined to the case in which the free energy of a mixture is a minimum for the single-phase state, and diffusion decreases local differences of concentration. This may be called ‘diffusion downhill’. However, it is possible for the free energy to be a minimum for the two-phase state; diffusion may then increase differences of concentration; and so may be called ‘diffusion uphill’. Becker (1937) has proposed a simple theoretical treatment of these two types of diffusion in a binary alloy. The present paper describes an experimental test of this theory, using the unusual properties of the alloy Cu 4 FeNi 3 . This alloy is single phase above 800° C and two-phase at lower temperatures, both the phases being face-centred cubic; the essential difference between the two phases is their content of copper. On dissociating from one phase into two the alloy develops a series of intermediate structures showing striking X-ray patterns which are very sensitive to changes of structure. It was found possible to utilize these results for a quantitative study of diffusion ‘uphill’ and ‘downhill’ in the alloy. The experimental results, which can be expressed very simply, are in fair agreement with conclusions drawn from Becker’s theory. It was found that Fick’s equation, dc / dt = D d2c / dx2 , can, within the limits of error, be applied in all cases, with the modification that c denotes the difference of the measured copper concentration from its equilibrium value. The theory postulates that D is the product of two factors, of which one is D 0f the coefficient of diffusion that would be measured if the alloy were an ideal solid solution. The theory is able to calculate D/D 0 , if only in first approximation, and the experiments confirm this calculation. It was found that in most cases the speed of diffusion—‘uphill’ or ‘downhill’—has the order of magnitude of D 0 . * Now with British Electrical Research Association.


1979 ◽  
Vol 11 (01) ◽  
pp. 240-255 ◽  
Author(s):  
Per Hokstad

The asymptotic behaviour of the M/G/2 queue is studied. The difference-differential equations for the joint distribution of the number of customers present and of the remaining holding times for services in progress were obtained in Hokstad (1978a) (for M/G/m). In the present paper it is found that the general solution of these equations involves an arbitrary function. In order to decide which of the possible solutions is the answer to the queueing problem one has to consider the singularities of the Laplace transforms involved. When the service time has a rational Laplace transform, a method of obtaining the queue length distribution is outlined. For a couple of examples the explicit form of the generating function of the queue length is obtained.


2000 ◽  
Vol 351 (3) ◽  
pp. 833-838 ◽  
Author(s):  
Dominik STOLL ◽  
Shouming HE ◽  
Stephen G. WITHERS ◽  
R. Antony J. WARREN

Incubation of the β-mannosidase Man2A from Cellulomonas fimi with 2-deoxy-2-fluoro-β-d-mannosyl fluoride (2FManβF) resulted in time-dependent inactivation of the enzyme (inactivation rate constant ki = 0.57min-1, dissociation constant for the inactivator Ki = 0.41mM) through the accumulation of a covalent 2-deoxy-2-fluoro-α-d-mannosyl–β-mannosidase 2A (2FMan–Man2A) enzyme intermediate, as observed by electrospray ionization mass spectrometry. The stoichiometry of inactivation was 1:1. Removal of excess inactivator and regeneration of active enzyme by transglycosylation of the covalently attached inhibitor to gentiobiose [Glcβ(1–6)Glc] demonstrated that the covalent intermediate was catalytically competent. Comparison by MS of the peptic digests of 2FMan–Man2A with peptic digests of native Man2A revealed a peptide of m/z 1520 that was unique to 2FMan–Man2A, and one of m/z 1036.5 that was unique to a Man2A peptide. Their sequences, determined by collision-induced fragmentation, were CSEFGFQGPPTW and FGFQGPPTW, corresponding to residues 517–528 and 520–528 of Man2A respectively. The difference in mass of 483.5 between the two peptides equals the sum of the masses of the tripeptide CSE plus that of 2-fluoromannose. It was concluded that in 2FMan–Man2A, the 2-fluoromannose esterified to Glu-519 blocks hydrolysis of the Glu-519–Phe-520 peptide bond, and that Glu-519 is the catalytic nucleophile in this enzyme. This residue is conserved in all members of family 2 of the glycosyl hydrolases. This represents the first ever labelling and identification of an active-site nucleophile in a β-mannosidase.


2014 ◽  
Vol 790-791 ◽  
pp. 97-102
Author(s):  
Zoltán Erdélyi ◽  
Zoltán Balogh ◽  
Gabor L. Katona ◽  
Dezső L. Beke

The critical nucleus size—above which nuclei grow, below dissolve—during diffusion controlled nucleation in binary solid-solid phase transformation process is calculated using kinetic Monte Carlo (KMC). If atomic jumps are slower in an A-rich nucleus than in the embedding B-rich matrix, the nucleus traps the A atoms approaching its surface. It doesn’t have enough time to eject A atoms before new ones arrive, even if it would be favourable thermodynamically. In this case the critical nucleus size can be even by an order of magnitude smaller than expected from equilibrium thermodynamics or without trapping. These results were published in [Z. Erdélyi et al., Acta Mater. 58 (2010) 5639]. In a recent paper M. Leitner [M. Leitner, Acta Mater. 60 (2012) 6709] has questioned our results based on the arguments that his simulations led to different results, but he could not point out the reason for the difference. In this paper we summarize our original results and on the basis of recent KMC and kinetic mean field (KMF) simulations we show that Leitner’s conclusions are not valid and we confirm again our original results.


1966 ◽  
Vol 21 (9) ◽  
pp. 1377-1384
Author(s):  
A. V. Willi

Kinetic carbon-13 and deuterium isotope effects are calculated for the SN2 reaction of CH3I with CN-. The normal vibrational frequencies of CH3I, the transition state I · · · CH3 · · · CN, and the corresponding isotope substituted reactants and transition states are evaluated from the force constants by solving the secular equation on an IBM 7094 computer.Values for 7 force constants of the planar CH3 moiety in the transition state (with an sp2 C atom) are obtained by comparison with suitable stable molecules. The stretching force constants related to the bonds being broken or newly formed (fCC, fCC and the interaction between these two stretches, /12) are chosen in such a way that either a zero or imaginary value for νʟ≠ will result. Agreement between calculated and experimental methyl-C13 isotope effects (k12/ k13) can be obtained only in sample calculations with sufficiently large values of f12 which lead to imaginary νʟ≠ values. Furthermore, the difference between fCI and fCC must be small (in the order of 1 mdyn/Å). The bending force constants, fHCI and fHCC, exert relatively little influence on k12/k13. They are important for the D isotope effect, however. As soon as experimental data on kH/kD are available it will be possible to derive a value for fHCC in the transition state if fHCI is kept constant at 0.205 mdynA, and if fCI, fCC and f12 are held in a reasonable order of magnitude. There is no agreement between experimental and calculated cyanide-C13 isotope effects. Possible explanations are discussed. — Since fCI and fCC cannot differ much it must be concluded that the transition state is relatively “symmetric”, with approximately equal amounts of bond making and bond breaking.


2006 ◽  
Vol 9 (05) ◽  
pp. 530-542 ◽  
Author(s):  
Hadi Nasrabadi ◽  
Kassem Ghorayeb ◽  
Abbas Firoozabadi

Summary We present formulation and numerical solution of two-phase multicomponent diffusion and natural convection in porous media. Thermal diffusion, pressure diffusion, and molecular diffusion are included in the diffusion expression from thermodynamics of irreversible processes. The formulation and the numerical solution are used to perform initialization in a 2D cross section. We use both homogeneous and layered media without and with anisotropy in our calculations. Numerical examples for a binary mixture of C1/C3 and a multicomponent reservoir fluid are presented. Results show a strong effect of natural convection in species distribution. Results also show that there are at least two main rotating cells at steady state: one in the gas cap, and one in the oil column. Introduction Proper initialization is an important aspect of reliable reservoir simulations. The use of the Gibbs segregation condition generally cannot provide reliable initialization in hydrocarbon reservoirs. This is caused, in part, by the effect of thermal diffusion (caused by the geothermal temperature gradient), which cannot be neglected in some cases; thermal diffusion might be the main phenomenon affecting compositional variation in hydrocarbon reservoirs, especially for near-critical gas/condensate reservoirs (Ghorayeb et al. 2003). Generally, temperature increases with increasing burial depth because heat flows from the Earth's interior toward the surface. The temperature profile, or geothermal gradient, is related to the thermal conductivity of a body of rock and the heat flux. Thermal conductivity is not necessarily uniform because it depends on the mineralogical composition of the rock, the porosity, and the presence of water or gas. Therefore, differences in thermal conductivity between adjacent lithologies can result in a horizontal temperature gradient. Horizontal temperature gradients in some offshore fields can be observed because of a constant water temperature (approximately 4°C) in different depths in the seabed floor. The horizontal temperature gradient causes natural convection that might have a significant effect on species distribution (Firoozabadi 1999). The combined effects of diffusion (pressure, thermal, and molecular) and natural convection on compositional variation in multicomponent mixtures in porous media have been investigated for single-phase systems (Riley and Firoozabadi 1998; Ghorayeb and Firoozabadi 2000a).The results from these references show the importance of natural convection, which, in some cases, overrides diffusion and results in a uniform composition. Natural convection also can result in increased horizontal compositional variation, an effect similar to that in a thermogravitational column (Ghorayeb and Firoozabadi 2001; Nasrabadi et al. 2006). The combined effect of convection and diffusion on species separation has been the subject of many experimental studies. Separation in a thermogravitational column with both effects has been measured widely (Schott 1973; Costeseque 1982; El Mataaoui 1986). The thermogravitational column consists of two isothermal vertical plates with different temperatures separated by a narrow space. The space can be either without a porous medium or filled with a porous medium. The thermal diffusion, in a binary mixture, causes one component to segregate to the hot plate and the other to the cold plate. Because of the density gradient caused by temperature and concentration gradients, convection flow occurs and creates a concentration difference between the top and bottom of the column. Analytical and numerical models have been presented to analyze the experimental results (Lorenz and Emery 1959; Jamet et al. 1992; Nasrabadi et al. 2006). The experimental and theoretical studies show that the composition difference between the top and bottom of the column increases with permeability until an optimum permeability is reached. Then, the composition difference declines as permeability increases. The process in a thermogravitational column shows the significance of the convection from a horizontal temperature gradient.


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