XXXII.—An Elementary Treatment of Thermal Diffusion in Gaseous and Liquid Systems

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.

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.


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.


2010 ◽  
Vol 6 (3) ◽  
pp. 1229-1265
Author(s):  
S. Sepulcre ◽  
L. Vidal ◽  
K. Tachikawa ◽  
F. Rostek ◽  
E. Bard

Abstract. This study aimed at documenting climate changes in tropical area in response to the Mid-Pleistocene Transition (MPT) by reconstructing past hydrologic variations in the Northern Caribbean Sea and its influence on the stability of the Atlantic Meridional Overturning Circulation (AMOC) during the last 940 kyr. Using core MD03-2628, we estimated past changes in sea surface salinity (SSS) using Δδ18O, the difference between the modern and the past δ18O of seawater (obtained by combining alkenone thermometer data with the δ18O of the planktonic foraminifera Globigerinoides ruber (white) and corrected for ice-sheet volume effects). Today, the lowest SSS values in the studied area are associated with the northernmost location of the Inter-Tropical Convergence Zone (ITCZ). The Δδ18O record exhibits glacial/interglacial cyclicity with higher values during all glacial periods spanning the last 940 kyr, indicating increased SSS. At a longer timescale, the Δδ18O exhibits a shift toward lower values for interglacial periods during the last 450 kyr, when compared to interglacial stages older than 650 kyr. A rise in SSS during glacial stages may be related to the southernmost location of the ITCZ, which is induced by a steeper interhemispheric temperature gradient and associated with reduced northward cross equatorial oceanic transport. Therefore, the results suggest a permanent link between the tropical salinity budget and the AMOC during the last 940 kyr. Following the MPT, lower salinities during the last five interglacial stages indicate a northernmost ITCZ location, forced by changes in the interhemispheric temperature gradient that is associated with the poleward position of Southern Oceanic Fronts that amplified the transport of heat and moisture to the North Atlantic. These processes may have contributed to amplification of the climate cycles that followed the MPT.


2021 ◽  
Vol 0 (0) ◽  
Author(s):  
Xiaoyu Chen ◽  
Ruquan Liang ◽  
Lichun Wu ◽  
Gan Cui

Abstract Equimolar mixtures composed of isomers were firstly used to investigate the molecular branching effect on thermal diffusion behavior, which was not disturbed by factors of molecular mass and composition in this work. Eight heptane isomers, including n-heptane, 2-methylhexane, 3-methylhexane, 2,2-dimethylpentane, 2,3-dimethylpentane, 2,4-dimethylpentane, 3,3-dimethylpentane and 3-ethylpentane, were chosen as the researched mixtures. A non-equilibrium molecular dynamics (NEMD) simulation with enhanced heat exchange (eHEX) algorithm was applied to calculate the Soret coefficient at T = 303.15 T=303.15  K and P = 1.0 atm P=1.0\hspace{0.1667em}\text{atm} . An empirical correlation based on an acentric factor was proposed and its calculation coincides with the simulated results, which showed the validity of the NEMD simulation. It is demonstrated that the isomer with higher acentric factor has a stronger thermophilic property and tends to migrate to the hot region in the heptane isomer mixture, and the extent of thermal diffusion is proportional to the difference between the acentric factors of the isomers.


1988 ◽  
Vol 110 (3) ◽  
pp. 254-256 ◽  
Author(s):  
E. H. Wissler

Presented in this paper is a solution for countercurrent heat exchange between two parallel vessels embedded in an infinite medium with a linear temperature gradient along the axes of the vessels. The velocity profile within the vessel is assumed to be parabolic. This solution describes the temperature field within the vessels, as well as in the tissue, and establishes that the intravessel temperature is not uniform, as is generally assumed to be the case. An explicit expression for the intervessel thermal resistance based on the difference between cup-mixed mean temperatures is derived.


1994 ◽  
Vol 186 (Part_1) ◽  
pp. 113-117 ◽  
Author(s):  
R. Haase ◽  
K.-H. Dücker ◽  
H. Buchner ◽  
J. Schwinum

1950 ◽  
Vol 46 ◽  
pp. 517 ◽  
Author(s):  
E. Whalley ◽  
E. R. S. Winter

1983 ◽  
Vol 4 ◽  
pp. 3-9 ◽  
Author(s):  
E. E. Adams ◽  
R. L. Brown

A heat conduction equation for the determination of the temperature profile in a snowpack is developed. The magnitude of the temperature gradient tends to increase as the snow surface is approached, with local minima through layers of high snow density and local maxima above and below these layers. Calculations are made of the difference in vapor density in the pore and over the ice grain surfaces which border the pore. In the presence of sufficient temperature and temperature gradient, faceted crystals will develop near the top of the pore, as ice is sublimed away from the surfaces in the lower region. There will be a reduction in the percentage of rounded grains as the faceted form develops. The process is demonstrated to be enhanced at warm temperatures and large temperature gradients in low density snow.


1973 ◽  
Vol 28 (2) ◽  
pp. 290-292 ◽  
Author(s):  
T.K.S. Narayanan ◽  
G. Dickel

The thermal diffusion factor a of hydrogen-carbondioxide mixtures has been determined in two different ways by measuring the mole fractions as well as the partial pressures using a two bulb apparatus. The difference between the values of α has also been calculated thermodynamically and found to agree with the difference of the above values within experimental error.


2021 ◽  
Author(s):  
Akiyuki Ono ◽  
Kosei Yamaguchi ◽  
Eiichi Nakakita

<p> It is an essential problem for forecasting Mesoscale Convection Systems to understand the mechanism of interaction between atmospheric flow and vortices with the development of cumulonimbus clouds using a numerical weather model. In this research, potential temperature gradient based vorticity which is the expression of baroclinic is obtained to analyze the energy structure of the vorticity field in developing cumulonimbus. First, applying the variational method enables us to obtain a diagnostic equation in which the equation of motion, conservation law of mass, and entropy are considered as constraints. Second, Fourier analysis was performed on the vorticity field in the cross-section of the convective core in the isolated cumulonimbus simulation. The temporal change of the spectrum of the vorticity field indicates that the rotational intensity of potential temperature gradient based vorticity increases at the same time as the degree of baroclinicity increases. It was also found that the same tendency can be seen in the analysis of the vorticity field of developing clouds using the environment of the heavy rainfall event in the Kuma River basin that occurred on July 4, 2020. We are planning to analyze the vorticity field in the cluster of cumulonimbus clouds and consider the difference in the energy structure of the vorticity field due to the difference in model resolution. Third, we conducted the data assimilation experiment assuming the use of vertical vorticity estimated by doppler radar observation. As a result, the change in the potential temperature and vertical wind through the error covariance matrix generates coherent convection in the computations.</p>


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