THE EFFECT OF VISCOSITY ON THE PHASE SEPARATION DYNAMICS OF BINARY IMMISCIBLE MIXTURE COUPLED WITH REVERSIBLE REACTION

2010 ◽  
Vol 21 (12) ◽  
pp. 1479-1488 ◽  
Author(s):  
HUI LI ◽  
HONG LIU ◽  
ZHONG-YUAN LU ◽  
QIN WANG ◽  
CHIA-CHUNG SUN
Keyword(s):  
Phase Separation ◽  
Reaction Rate ◽  
Domain Size ◽  
Reaction Rates ◽  
Two Dimensions ◽  
Domain Growth ◽  
Reversible Reaction ◽  
Growth Exponent ◽  
High Reaction ◽  
Immiscible Mixture

The phase-separating system coupled with a simple reversible reaction A ⇌ B in a binary immiscible mixture due to critical quench is investigated with Lowe-Andersen temperature controlling method in two dimensions. The system viscosity strongly influences the asymptotic relationship between the excess energy (characterizing the domain growth) and the reaction rate. The competition between different dynamic factors results in the steady states with characteristic domain sizes. For low viscosities, the domain growth exponent approximates to 0.4 in the cases of low reaction rates and to 0.25 in the cases of high reaction rates, which shows the suppressing effects of high reversible reaction rates on the phase separation. However, in the cases of high viscosities, we find a 0.25 scaling with low reaction rates but a 0.5 scaling with high reaction rates. In these cases, high viscosities prevent mass transport in the binary mixture, consequently result in much smaller steady state domain sizes. Therefore the domain sizes with high viscosities and low reaction rates are very similar to those with low viscosities and high reaction rates, and the dependence of domain sizes on the reaction rates are similar. For the high-viscosity systems with high reaction rates, the domain sizes are predominantly controlled by the reaction rates, therefore we can observe stronger dependence of domain size on the reaction rate.

Lattice Boltzmann Method for Simulating Phase Separation of Sheared Binary Fluids with Reversible Chemical Reaction

2017 ◽  
Vol 10 (3) ◽  
pp. 656-670 ◽  
Author(s):  
Xiaoyu Wang ◽  
Jie Ouyang ◽  
Heng Yang ◽  
Jianwei Liu
Keyword(s):  
Phase Separation ◽  
Lattice Boltzmann Method ◽  
Chemical Reaction ◽  
Lattice Boltzmann ◽  
Finite Size ◽  
Reaction Rates ◽  
Growth Exponent ◽  
Binary Fluids ◽  
Reversible Chemical Reaction ◽  
Boltzmann Method

AbstractA lattice Boltzmann method is utilized for governing equations which control phase separation of binary fluids with reversible chemical reaction in presence of a shear flow in this paper. We first present the morphology modeling of sheared binary fluids with reversible chemical reaction. We then validate the model by taking the unsheared binary fluids as an example. It is found that the results fit well with the references. The paper shows structures of the sheared system and gives the detailed analysis for the morphology of sheared binary fluids with reversible chemical reaction. The phase separation of the domain structures with different chemical reaction rates is discussed. Through simulations of the sheared binary fluids, two interesting phenomena are observed, which do not exist in a binary mixture without reversible chemical reaction. One is that the same results appear in both low and high viscosity, and the other is that the domain growth exponent with both low and high viscosities presents wave due to the competition of the viscosity and phase separation. In addition, we find that the finite size effects resulting in the growth exponent decreasing appear faster than that of the unsheared blend at a large time when the size of domains is comparable with the lattice size.

scholarly journals Anomalous Phase Separation Kinetics Observed in a Micelle System

1994 ◽  
Vol 366 ◽  
Author(s):  
J. P. Wilcoxon ◽  
J. E. Martin
Keyword(s):  
Phase Separation ◽  
Domain Size ◽  
Anomalous Behavior ◽  
Domain Growth ◽  
Cube Root ◽  
Phase Separation Kinetics ◽  
Scattering Study ◽  
Evolution Of Structure ◽  
Spherical Micelles ◽  
Micelle System

ABSTRACTWe report a real-time, two-dimensional light scattering study of the evolution of structure of a two component nonionic micelle system undergoing phase separation. The micelles act like molecular slug-a-beds whose domain growth is pathetically lathargic (i.e. slower than the cube root of time prediction for simple binary fluids). In fact, the growth kinetics can be empirically described as a stretched exponential approach to a pinned domain size. Although the kinetics are not yet understood, this anomalous behavior may be due to the ability of the spherical micelles to reorganize into more complex structures.

Numerical investigation of the growth kinetics for macromolecular microsphere composite hydrogel based on the TDGL equation

2016 ◽  
Vol 15 (08) ◽  
pp. 1650064
Author(s):  
Dating Wu ◽  
Hui Zhang
Keyword(s):  
Phase Separation ◽  
Numerical Investigation ◽  
Growth Kinetics ◽  
Pair Correlation ◽  
Domain Size ◽  
Time Dependent ◽  
Domain Growth ◽  
Ginzburg Landau ◽  
Tdgl Equation ◽  
Kinetics Of

We present results of a detailed numerical investigation of the phase separation kinetic process of the macromolecular microsphere composite (MMC) hydrogel. Based on the Flory-Huggins-de Gennes-like reticular free energy, we use the time-dependent Ginzburg–Landau (TDGL) mesoscopic model (called MMC-TDGL model) to simulate the phase separation process. Domain growth is investigated through the pair correlation function. Then we obtain the time-dependent characteristic domain size, which reflects the growth kinetics of the MMC hydrogel. The results indicate that the growth law based on the MMC-TDGL equation is consistent with the modified Lifshitz–Slyozov theory.

scholarly journals Tunable thermo-reversible bicontinuous nanoparticle gel driven by the binary solvent segregation

2021 ◽  
Vol 12 (1) ◽  
Author(s):  
Yuyin Xi ◽  
Ronald S. Lankone ◽  
Li-Piin Sung ◽  
Yun Liu
Keyword(s):  
Phase Separation ◽  
Domain Size ◽  
Binary Solvent ◽  
Colloidal Systems ◽  
Colloidal Assembly ◽  
Structures And Properties ◽  
Wide Range ◽  
Equilibrium Process ◽  
Equilibrium Structures ◽  
Non Equilibrium

AbstractBicontinuous porous structures through colloidal assembly realized by non-equilibrium process is crucial to various applications, including water treatment, catalysis and energy storage. However, as non-equilibrium structures are process-dependent, it is very challenging to simultaneously achieve reversibility, reproducibility, scalability, and tunability over material structures and properties. Here, a novel solvent segregation driven gel (SeedGel) is proposed and demonstrated to arrest bicontinuous structures with excellent thermal structural reversibility and reproducibility, tunable domain size, adjustable gel transition temperature, and amazing optical properties. It is achieved by trapping nanoparticles into one of the solvent domains upon the phase separation of the binary solvent. Due to the universality of the solvent driven particle phase separation, SeedGel is thus potentially a generic method for a wide range of colloidal systems.

Location-thinking, value-thinking, and graphical forms: combining analytical frameworks to analyze inferences made by students when interpreting the points and trends on a reaction coordinate diagram

2021 ◽  
Author(s):  
Alexander P. Parobek ◽  
Patrick M. Chaffin ◽  
Marcy H. Towns
Keyword(s):  
Reaction Rate ◽  
Research Study ◽  
Reaction Rates ◽  
Reaction Coordinate ◽  
Structured Interviews ◽  
Chemistry Students ◽  
Qualitative Research Study ◽  
The Impact ◽  
Analytical Frameworks ◽  
Chemical Representations

Reaction coordinate diagrams (RCDs) are chemical representations widely employed to visualize the thermodynamic and kinetic parameters associated with reactions. Previous research has demonstrated a host of misconceptions students adopt when interpreting the perceived information encoded in RCDs. This qualitative research study explores how general chemistry students interpret points and trends on a RCD and how these interpretations impact their inferences regarding the rate of a chemical reaction. Sixteen students participated in semi-structured interviews in which participants were asked to interpret the points and trends along provided RCDs and to compare relative reaction rates between RCDs. Findings derived from this study demonstrate the diversity of graphical reasoning adopted by students, the impact of students’ interpretations of the x-axis of a RCD on the graphical reasoning employed, and the influence of these ideas on inferences made about reaction rate. Informed by analytical frameworks grounded in the resources framework and the actor-oriented model of transfer, implications for instruction are provided with suggestions for how RCDs may be presented to assist students in recognizing the critical information encoded in these diagrams.

scholarly journals Perborate Oxidation of Substituted 5-Oxoacids in Aqueous Acetic Acid Medium: A Kinetic and Mechanistic Study

2014 ◽  
Vol 2014 ◽  
pp. 1-7 ◽  
Author(s):  
S. Shree Devi ◽  
B. Muthukumaran ◽  
P. Krishnamoorthy
Keyword(s):  
Acetic Acid ◽  
Acid Medium ◽  
Reaction Rate ◽  
Reaction Medium ◽  
Activation Parameters ◽  
Reaction Rates ◽  
Mechanistic Study ◽  
Aqueous Acetic Acid ◽  
Sodium Perborate ◽  
Acetic Acid Medium

Kinetics and mechanism of oxidation of substituted 5-oxoacids by sodium perborate in aqueous acetic acid medium have been studied. The reaction exhibits first order both in [perborate] and [5-oxoacid] and second order in [H+]. Variation in ionic strength has no effect on the reaction rate, while the reaction rates are enhanced on lowering the dielectric constant of the reaction medium. Electron releasing substituents in the aromatic ring accelerate the reaction rate and electron withdrawing substituents retard the reaction. The order of reactivity among the studied 5-oxoacids is p-methoxy ≫ p-methyl > p-phenyl > –H > p-chloro > p-bromo > m-nitro. The oxidation is faster than H2O2 oxidation. The formation of H2BO3+ is the reactive species of perborate in the acid medium. Activation parameters have been evaluated using Arrhenius and Eyring’s plots. A mechanism consistent with the observed kinetic data has been proposed and discussed. Based on the mechanism a suitable rate law is derived.

3D Calculations of PWR Vessels Neutron Fluence With EFLUVE 3D Code

2013 ◽  
Author(s):  
Cécile-Aline Gosmain ◽  
Sylvain Rollet ◽  
Damien Schmitt
Keyword(s):  
Monte Carlo ◽  
Fast Neutron ◽  
Pressure Vessel ◽  
Reaction Rate ◽  
Neutron Fluence ◽  
Neutron Transport ◽  
Reaction Rates ◽  
Surveillance Program ◽  
Monte Carlo Code ◽  
Neutron Sources

In the framework of surveillance program dosimetry, the main parameter in the determination of the fracture toughness and the integrity of the reactor pressure vessel (RPV) is the fast neutron fluence on pressure vessel. Its calculated value is extrapolated using neutron transport codes from measured reaction rate value on dosimeters located on the core barrel. EDF R&D has developed a new 3D tool called EFLUVE3D based on the adjoint flux theory. This tool is able to reproduce on a given configuration the neutron flux, fast neutron fluence and reaction rate or dpa results of an exact Monte Carlo calculation with nearly the same accuracy. These EFLUVE3D calculations does the Source*Importance product which allows the calculation of the flux, the neutronic fluence (flux over 1MeV integrated on time) received at any point of the interface between the skin and the pressure vessel but also at the capsules of the pressurized water reactor vessels surveillance program and the dpa and reaction rates at different axial positions and different azimuthal positions of the vessel as well as at the surveillance capsules. Moreover, these calculations can be carried out monthly for each of the 58 reactors of the French current fleet in challenging time (less than 10mn for the total fluence and reaction rates calculations considering 14 different neutron sources of a classical power plant unit compared to more than 2 days for a classic Monte Carlo flux calculation at a given neutron source). The code needs as input: - for each reaction rate, the geometric importance matrix produced for a 3D pin by pin mesh on the basis of Green’s functions calculated by the Monte Carlo code TRIPOLI; - the neutron sources calculated on assemblies data (enrichment, position, fission fraction as a function of evolution), pin by pin power and irradiation. These last terms are based on local in-core activities measurements extrapolated to the whole core by use of the EDF core calculation scheme and a pin by pin power reconstruction methodology. This paper presents the fundamental principles of the code and its validation comparing its results to the direct Monte Carlo TRIPOLI results. Theses comparisons show a discrepancy of less than 0,5% between the two codes equivalent to the order of magnitude of the stochastic convergence of Monte Carlo results.

scholarly journals mTORC1 controls phase-separation and the biophysical properties of the cytoplasm by tuning crowding

2017 ◽  
Author(s):  
M. Delarue ◽  
G.P. Brittingham ◽  
S. Pfeffer ◽  
I.V. Surovtsev ◽  
S. Ping-lay ◽  
...  
Keyword(s):  
Phase Separation ◽  
Fluorescent Protein ◽  
Effective Diffusion ◽  
Reaction Rates ◽  
Biophysical Properties ◽  
Cell Interior ◽  
Profound Impact ◽  
Mtorc1 Pathway

Summary (Abstract)Macromolecular crowding has a profound impact on reaction rates and the physical properties of the cell interior, but the mechanisms that regulate crowding are poorly understood. We developed Genetically Encoded Multimeric nanoparticles (GEMs) to dissect these mechanisms. GEMs are homomultimeric scaffolds fused to a fluorescent protein. GEMs self-assemble into bright, stable fluorescent particles of defined size and shape. By combining tracking of GEMs with genetic and pharmacological approaches, we discovered that the mTORC1 pathway can tune the effective diffusion coefficient of macromolecules ≥15 nm in diameter more than 2-fold without any discernable effect on the motion of molecules ≥5 nm. These mTORCI-dependent changes in crowding and rheology affect phase-separation both in vitro and in vivo. Together, these results establish a role for mTORCI in controlling both the biophysical properties of the cytoplasm and the phase-separation of biopolymers.

scholarly journals Phase Separation Can Increase Enzyme Activity by Concentration and Molecular Organization

2020 ◽  
Author(s):  
William Peeples ◽  
Michael K. Rosen
Keyword(s):  
Phase Separation ◽  
Enzymatic Reaction ◽  
Reaction Rates ◽  
Quantitative Model ◽  
Mass Action ◽  
Molecular Organization ◽  
Scaffolding Proteins ◽  
Enzyme Cascade ◽  
Separation Threshold ◽  
Liquid Liquid Phase Separation

AbstractBiomolecular condensates concentrate macromolecules into discrete cellular foci without an encapsulating membrane. Condensates are often presumed to increase enzymatic reaction rates through increased concentrations of enzymes and substrates (mass action), although this idea has not been widely tested and other mechanisms of modulation are possible. Here we describe a synthetic system where the SUMOylation enzyme cascade is recruited into engineered condensates generated by liquid-liquid phase separation of multidomain scaffolding proteins. SUMOylation rates can be increased up to 36-fold in these droplets compared to the surrounding bulk, depending on substrate KM. This dependency produces substantial specificity among different substrates. Analyses of reactions above and below the phase separation threshold lead to a quantitative model in which reactions in condensates are accelerated by mass action and by changes in substrate KM, likely due to scaffold-induced molecular organization. Thus, condensates can modulate reaction rates both by concentrating molecules and by physically organizing them.

scholarly journals Monitoring the Interfacial Polymerization of Piperazine and Trimesoyl Chloride with Hydrophilic Interlayer or Macromolecular Additive by in-situ FT-IR Spectroscopy

2019 ◽  
Author(s):  
Xi Yang
Keyword(s):  
Ir Spectroscopy ◽  
Reaction Rate ◽  
Interfacial Polymerization ◽  
Reaction System ◽  
Reaction Rates ◽  
Water Permeation ◽  
Ft Ir ◽  
Trimesoyl Chloride ◽  
Ft Ir Spectroscopy

The interfacial polymerization (IP) of piperazine (PIP) and trimesoyl chloride (TMC) has been extensively utilized to synthesize the nanofiltration (NF) membrane. However, it is still a huge challenge to monitor the IP reaction, because of the fast reaction rate and the formed ultra-thin film. Herein, two effective strategies are applied to reduce the IP reaction rate: (1) the introduction of hydrophilic interlayers between the porous substrate and the formed polyamide layer; (2) the addition of macromolecular additives in the aqueous solution of PIP. As a result, in-situ FT-IR spectroscopy was firstly used to monitor the IP reaction of PIP/TMC reaction system, with hydrophilic interlayers or macromolecular additives. Moreover, we study the formed polyamide layer growth on the substrate, in a real-time manner. The in-situ FT-IR experimental results confirm that the IP reaction rates are effectively suppressed and the formed polyamide thickness reduces from 138±24 nm to 46±2 nm. Furthermore, the optimized NF membrane with excellent performance are consequently obtained, which include the boosted water permeation flux about 141~238 (L·m2·h/MPa) and superior salt rejection of Na2SO4 > 98.4%.

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