Thermodynamic Study of the Role of Interface Curvature on Multicomponent Vapor–Liquid Phase Equilibrium

Shardt, Nadia; Elliott, Janet A.W.

doi:10.1021/acs.jpca.5b10450

Cited by 32 publications

(35 citation statements)

References 64 publications

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“…In order to gain insight into the potential mechanism which fixes this hole size R H , let us consider the different pressures acting in the bubble layer during the drying process − as sketched for the cross‐section of one bubble in Figure b. Let us associate a pressure drop Δ P between the liquid pressure P L and the ambient pressure P 0 , leading to a mean curvature C of the air/liquid interface between the bubbles

Δ P = P_{0} - P_{normalL} = γ C

where γ is the surface tension . Since we can consider γ as constant everywhere, the bubble cap has the form of a section of a sphere whose radius of curvature R is related to the bubble pressure P B and the atmospheric pressure via the Laplace law

P_{normalB} - P_{0} = \frac{4 γ}{R} .

…”

Section: Resultsmentioning

confidence: 99%

“…Nevertheless, it raises one important question: which physical mechanism could fix a characteristic, bubble‐size‐independent pressure drop Δ P of the order of 2 000 Pa between the liquid and the surrounding air at the final drying stage? One possibility could be that the rather monodisperse latex size leads to a characteristic dimension of the liquid meniscus between the latex particles at the final drying stage whose curvatures could be sufficiently strong to influence the vapor pressure . Another possibility may be that the disjoining pressure in the thin film (which is typically of the order of a few thousand Pa) plays a role in fixing the pressure relations.…”

Section: Resultsmentioning

confidence: 99%

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Structuring Solid Surfaces with Bubble Coatings

et al. 2016

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Providing solid surfaces with a surface roughness or a porosity can improve drastically their properties. A main challenge remains in finding techniques, which establish well-controlled surface modifications over large areas at low cost. Here, we show that this may be achieved by coating surfaces with initially liquid foams, which are then solidified. To obtain insight into the main mechanisms, we use microfluidics to generate latex foams with equal volume bubbles, which selforder into periodic structures due to strong capillary forces. During the drying process, the bubble caps rupture in a well-controlled manner, giving rise to a final surface modification with regularlyspaced holes.

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Δ P = P_{0} - P_{normalL} = γ C

P_{normalB} - P_{0} = \frac{4 γ}{R} .

…”

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Structuring Solid Surfaces with Bubble Coatings

et al. 2016

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“…used one rigorous EOS model and capillary pressure equation to calculate the phase envelope of multicomponent mixtures, and concluded that small pore sizes result in great change in the phase envelope. Shardt and Elliott analyzed the effect of interface curvature on multicomponent vapor–liquid equilibrium phase envelopes and phase compositions diagrams. Zhang et al .…”

Section: Introductionmentioning

confidence: 99%

“…Sandoval et al 29 used one rigorous EOS model and capillary pressure equation to calculate the phase envelope of multicomponent mixtures, and concluded that small pore sizes result in great change in the phase envelope. Shardt and Elliott 30 analyzed the effect of interface curvature on multicomponent vapor-liquid equilibrium phase envelopes and phase compositions diagrams. Zhang et al 25 studied the effect of capillary pressure on the phase behavior of CO 2 /hydrocarbons in unconventional reservoirs, and the results indicated that reduction in the nano pore size causes a noticeable difference in the two-phase envelope.…”

Section: Introductionmentioning

confidence: 99%

Impact of fluid property shift and capillarity on the recovery mechanisms of CO₂injection in tight oil reservoirs

Sarma

et al. 2019

Greenhouse Gases

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The phase equilibria with the confinement effect could shift in nano‐pores, which could have a great impact on the recovery mechanisms of CO2 injection in tight oil reservoirs; this has not been systematically studied. In this paper, the confinement effect with property shift and capillarity effect is introduced into the flash calculation of confined fluids. The Soave modification of the Redlich–Kwong equation of state is extended by the molecular‐wall collision parameter to describe the shifted pressure–volume–temperature properties of confined fluid, and the Young–Laplace equation is applied to evaluate the capillary pressure. This developed model could effectively be applied for phase equilibrium calculation in tight porous media because of the verification of experimental results. A binary mixture is investigated to study the different effect of capillary pressure and property shift on phase equilibria. Subsequently, a typical hydrocarbon fluid from Middle Bakken tight oil reservoirs is studied with CO2 injection. Results illustrate that the confinement effect could play an increasingly important part in the phase equilibrium state. The CO2 solubility and mass transfer driving force in tiny pores would be greater than those in large pores under the same conditions. The gas phase saturation would be smaller with the same compositions, which could extend the single‐phase region of fluid flow in porous media. Furthermore, bubble‐point pressure, the minimum miscible pressure of CO2/hydrocarbon, and the viscosity of tight oil dissolved with CO2 both decrease with the pore size, which has a good influence on tight oil recovery. In general, the confinement effect could effectively reinforce the recovery mechanisms of CO2 injection, which is conducive to the enhancement of tight oil recovery. © 2019 Society of Chemical Industry and John Wiley & Sons, Ltd.

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“…A relatively small number of papers have been devoted to nanoscale phase equilibria of two-component systems [16][17][18][19][20][21][22][23][24][25][26][27][28][29][30][31][32][33][34][35]. For binary and multi-component solutions, the configurational entropy is one of the basic terms of the Gibbs energy of the solution phases, and thus its precise knowledge is crucial for nano-equilibrium calculations.…”

Section: Introductionmentioning

confidence: 99%

On the Configurational Entropy of Nanoscale Solutions for More Accurate Surface and Bulk Nano-Thermodynamic Calculations

Dezso

Kaptay

2017

Entropy

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Abstract:The configurational entropy of nanoscale solutions is discussed in this paper. As follows from the comparison of the exact equation of Boltzmann and its Stirling approximation (widely used for both macroscale and nanoscale solutions today), the latter significantly over-estimates the former for nano-phases and surface regions. On the other hand, the exact Boltzmann equation cannot be used for practical calculations, as it requires the calculation of the factorial of the number of atoms in a phase, and those factorials are such large numbers that they cannot be handled by commonly used computer codes. Herewith, a correction term is introduced in this paper to replace the Stirling approximation by the so-called "de Moivre approximation". This new approximation is a continuous function of the number of atoms/molecules and the composition of the nano-solution. This correction becomes negligible for phases larger than 15 nm in diameter. However, the correction term does not cause mathematical difficulties, even if it is used for macro-phases. Using this correction, future nano-thermodynamic calculations will become more precise. Equations are worked out for both integral and partial configurational entropies of multi-component nano-solutions. The equations are correct only for nano-solutions, which contain at least a single atom of each component (below this concentration, there is no sense to make any calculations).

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Thermodynamic Study of the Role of Interface Curvature on Multicomponent Vapor–Liquid Phase Equilibrium

Cited by 32 publications

References 64 publications

Structuring Solid Surfaces with Bubble Coatings

Structuring Solid Surfaces with Bubble Coatings

Impact of fluid property shift and capillarity on the recovery mechanisms of CO₂injection in tight oil reservoirs

On the Configurational Entropy of Nanoscale Solutions for More Accurate Surface and Bulk Nano-Thermodynamic Calculations

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Thermodynamic Study of the Role of Interface Curvature on Multicomponent Vapor–Liquid Phase Equilibrium

Cited by 32 publications

References 64 publications

Structuring Solid Surfaces with Bubble Coatings

Structuring Solid Surfaces with Bubble Coatings

Impact of fluid property shift and capillarity on the recovery mechanisms of CO2injection in tight oil reservoirs

On the Configurational Entropy of Nanoscale Solutions for More Accurate Surface and Bulk Nano-Thermodynamic Calculations

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Product

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Impact of fluid property shift and capillarity on the recovery mechanisms of CO₂injection in tight oil reservoirs