The metachors of polyvalent and associated electrolytes in aqueous solutions

1984 ◽  
Vol 49 (5) ◽  
pp. 1079-1089
Author(s):  
Jiří Čeleda ◽  
Stanislav Škramovský ◽  
Jana Žilková

The quantity metachor introduced in the preceding paper was evaluated from the experimental data on surface tension of the aqueous solutions for a set of polyvalent and weak electrolytes. The almost complete concentration independence of the metachor and its direct proportionality to the number of the free charges in a dissociated molecule (observed and theoretically substantiated in the above cited paper for strong 1,1-, 1,2- and 2,1-valent electrolytes) has been verified in the present paper also for electrolytes of the higher valency types. The metachor values of fully dissociated 1,1-, 1,2-, 1,3- and 1,4-valent electrolytes follow a ratio (5 ± 1) : (10 ± 1.5) : 15 : 22 cm3 mol-1. Association of the electrolytes decreases correspondingly the metachor value as one can see on the case of electrolytes with bulky ions (NH4SCN, KCH3COO, Na2S2O3, hexacyanoferrates(II) or with the free acids H2SO4, H2CrO4, H3PO4 etc. A weak, in the investigated concentration range neglibility dissociated oxalic acid, consisting of small hydrated hydrophilic molecules, exhibits metachor values close to zero. Dibasic organic acids with a larger number of hydrophobic CH2 groups reach very high negative metachor values, however, their salts again possess metachor values close to 10 cm3 mol-1 - in accordance with the values found for strong 1,2-valent electrolytes. The metachors of ZnCl2 and CdCl2 decrease sharply from the last mentioned value, with increasing concentration while the metachor value of zinc perchlorate remains unchanged at the level corresponding to the fully dissociated salt. This is in agreement with the well known sequence of tendency of the d10-cations to form complexes with the Cl- and ClO-4 anions. All these facts have verified that the metachor can be, in principle, applied for a diagnostic states of the electrolytes in aqueous solutions.

2019 ◽  
Vol 64 (12) ◽  
pp. 5049-5056
Author(s):  
Mohsin Ali Raza ◽  
Paul D. Hallett ◽  
Xiangyang Liu ◽  
Maogang He ◽  
Waheed Afzal

2011 ◽  
Vol 11 (8) ◽  
pp. 3895-3911 ◽  
Author(s):  
M. Frosch ◽  
N. L. Prisle ◽  
M. Bilde ◽  
Z. Varga ◽  
G. Kiss

Abstract. We have investigated CCN properties of internally mixed particles composed of one organic acid (oxalic acid dihydrate, succinic acid, adipic acid, citric acid, cis-pinonic acid, or Nordic reference fulvic acid) and one inorganic salt (sodium chloride or ammonium sulphate). Surface tension and water activity of aqueous model solutions with concentrations relevant for CCN activation were measured using a tensiometer and osmometry, respectively. The measurements were used to calculate Köhler curves and critical supersaturations, which were compared to measured critical supersaturations of particles with the same chemical compositions, determined with a cloud condensation nucleus counter. Surfactant surface partitioning was not accounted for. For the aqueous solutions containing cis-pinonic acid and fulvic acid, a depression of surface tension was observed, but for the remaining solutions the effect on surface tension was negligible at concentrations relevant for cloud droplet activation. The surface tension depression of aqueous solutions containing both organic acid and inorganic salt was approximately the same as or smaller than that of aqueous solutions containing the same mass of the corresponding pure organic acids. Water activity was found to be highly dependent on the type and amount of inorganic salt. Sodium chloride was able to decrease water activity more than ammonium sulphate and both inorganic salts are predicted to have a smaller Raoult term than the studied organic acids. Increasing the mass ratio of the inorganic salt led to a decrease in water activity. Water activity measurements were compared to results from the E-AIM model and values estimated from both constant and variable van't Hoff factors. The correspondence between measurements and estimates was overall good, except for highly concentrated solutions. Critical supersaturations calculated with Köhler theory based on measured water activity and surface tension, but not accounting for surface partitioning, compared well with measurements, except for the solutions containing sodium chloride and oxalic acid or one of the more surface active organic compounds. In such cases, significantly lower values were obtained from Köhler theory than the measured critical supersaturations with deviations above 50% for a 60 nm particle containing 50% (dry mass) of Nordic reference fulvic acid, suggesting that surfactant partitioning and/or an effect of sodium chloride on solubility of the organic component is important.


1984 ◽  
Vol 49 (5) ◽  
pp. 1061-1078 ◽  
Author(s):  
Jiří Čeleda ◽  
Stanislav Škramovský

Based on the earlier paper introducing a concept of the apparent parachor of a solute in the solution, we have eliminated in the present work algebraically the effect which is introduced into this quantity by the additivity of the apparent molal volumes. The difference remaining from the apparent parachor after substracting the contribution corresponding to the apparent volume ( for which the present authors suggest the name metachor) was evaluated from the experimental values of the surface tension of aqueous solutions for a set of 1,1-, 1,2- and 2,1-valent electrolytes. This difference showed to be independent of concentration up to the very high values of the order of units mol dm-3 but it was directly proportional to the number of the free charges (with a proportionality factor 5 ± 1 cm3 mol-1 identical for all studied electrolytes). The metachor can be, for this reason, a suitable characteristic for detection of the association of ions and formation of complexes in the solutions of electrolytes, up to high concentrations where other methods are failing.


2021 ◽  
Vol 11 (1) ◽  
Author(s):  
Ilyas Al-Kindi ◽  
Tayfun Babadagli

AbstractThe thermodynamics of fluids in confined (capillary) media is different from the bulk conditions due to the effects of the surface tension, wettability, and pore radius as described by the classical Kelvin equation. This study provides experimental data showing the deviation of propane vapour pressures in capillary media from the bulk conditions. Comparisons were also made with the vapour pressures calculated by the Peng–Robinson equation-of-state (PR-EOS). While the propane vapour pressures measured using synthetic capillary medium models (Hele–Shaw cells and microfluidic chips) were comparable with those measured at bulk conditions, the measured vapour pressures in the rock samples (sandstone, limestone, tight sandstone, and shale) were 15% (on average) less than those modelled by PR-EOS.


Entropy ◽  
2020 ◽  
Vol 22 (12) ◽  
pp. 1337
Author(s):  
Xiangfeng Tian ◽  
Lemeng Wang ◽  
Pan Zhang ◽  
Dong Fu

The surface tension and viscosity values of N-methyldiethanolamine (MDEA) aqueous solutions promoted by tetramethylammonium arginate ([N1111][Arg]) were measured and modeled. The experimental temperatures were 303.2 to 323.2 K. The mass fractions of MDEA (wMDEA) and [N1111][Arg] (w[N1111][Arg]) were 0.300 to 0.500 and 0.025 to 0.075, respectively. The measured surface tension and viscosity values were satisfactorily fitted to thermodynamic models. With the aid of experimentally viscosity data, the activation energy (Ea) and H2S diffusion coefficient (DH2S) of MDEA-[N1111][Arg] aqueous solution were deduced. The surface entropy and surface enthalpy of the solutions were calculated using the fitted model of the surface tension. The quantitative relationship between the calculated values (surface tension, surface entropy, surface enthalpy, viscosity, activation energy, and H2S diffusion coefficient) and the operation conditions (mass fraction and temperature) was demonstrated.


Data in Brief ◽  
2021 ◽  
Vol 35 ◽  
pp. 106869
Author(s):  
Behzad Rahimi ◽  
Nayereh Rezaie-Rahimi ◽  
Negar Jafari ◽  
Ali Abdolahnejad ◽  
Afshin Ebrahimi

2018 ◽  
Author(s):  
Theodora Nah ◽  
Hongyu Guo ◽  
Amy P. Sullivan ◽  
Yunle Chen ◽  
David J. Tanner ◽  
...  

Abstract. The implementation of stringent emission regulations has resulted in the decline of anthropogenic pollutants including sulfur dioxide (SO2), nitrogen oxides (NOx) and carbon monoxide (CO). In contrast, ammonia (NH3) emissions are largely unregulated, with emissions projected to increase in the future. We present real-time aerosol and gas measurements from a field study conducted in an agricultural-intensive region in the southeastern U.S. during the fall of 2016 to investigate how NH3 affects particle acidity and SOA formation via the gas-particle partitioning of semi-volatile organic acids. Particle water and pH were determined using the ISORROPIA-II thermodynamic model and validated by comparing predicted inorganic HNO3-NO3− and NH3-NH4+ gas-particle partitioning ratios with measured values. Our results showed that despite the high NH3 concentrations (study average 8.1 ± 5.2 ppb), PM1 were highly acidic with pH values ranging from 0.9 to 3.8, and a study-averaged pH of 2.2 ± 0.6. PM1 pH varied by approximately 1.4 units diurnally. Formic and acetic acids were the most abundant gas-phase organic acids, and oxalate was the most abundant particle-phase water-soluble organic acid anion. Measured particle-phase water-soluble organic acids were on average 6 % of the total non-refractory PM1 organic aerosol mass. The measured molar fraction of oxalic acid in the particle phase (i.e., particle-phase oxalic acid molar concentration divided by the total oxalic acid molar concentration) ranged between 47 and 90 % for PM1 pH 1.2 to 3.4. The measured oxalic acid gas-particle partitioning ratios were in good agreement with their corresponding thermodynamic predictions, calculated based on oxalic acid’s physicochemical properties, ambient temperature, particle water and pH. In contrast, gas-particle partitioning of formic and acetic acids were not well predicted for reasons currently unknown. For this study, higher NH3 concentrations relative to what has been measured in the region in previous studies had minor effects on PM1 organic acids and their influence on the overall organic aerosol and PM1 mass concentrations.


SPE Journal ◽  
2013 ◽  
Vol 18 (03) ◽  
pp. 440-447 ◽  
Author(s):  
C.C.. C. Ezeuko ◽  
J.. Wang ◽  
I.D.. D. Gates

Summary We present a numerical simulation approach that allows incorporation of emulsion modeling into steam-assisted gravity-drainage (SAGD) simulations with commercial reservoir simulators by means of a two-stage pseudochemical reaction. Numerical simulation results show excellent agreement with experimental data for low-pressure SAGD, accounting for approximately 24% deficiency in simulated oil recovery, compared with experimental data. Incorporating viscosity alteration, multiphase effect, and enthalpy of emulsification appears sufficient for effective representation of in-situ emulsion physics during SAGD in very-high-permeability systems. We observed that multiphase effects appear to dominate the viscosity effect of emulsion flow under SAGD conditions of heavy-oil (bitumen) recovery. Results also show that in-situ emulsification may play a vital role within the reservoir during SAGD, increasing bitumen mobility and thereby decreasing cumulative steam/oil ratio (cSOR). Results from this work extend understanding of SAGD by examining its performance in the presence of in-situ emulsification and associated flow of emulsion with bitumen in porous media.


2021 ◽  
Vol 1022 ◽  
pp. 194-202
Author(s):  
R.Kh. Dadashev ◽  
R.A. Kutuev

The experimental study results of the melts concentration dependence of the surface tension of the four-component indium-tin-lead-bismuth system and its constituent binary systems of indium-tin, indium-lead, indium-bismuth, tin-lead, tin-bismuth, lead-bismuth are presented in the paper. It is shown that the concentration dependence of the melts surface tension of the In-Sn-Pb-Bi four-component system can be predicted from the data on ST (surface tension) values of lateral binary systems. Features in the ST isotherms in the form of a minimum are observed only in the indium-tin lateral system from all lateral binaries. A distinctive feature of the detected minimum is that the minimum depth slightly exceeds the experimental error. Therefore, in addition to the fact that the area of average compositions was studied more thoroughly, we carried out the surface tension measurements by two independent methods. The experimental data obtained by both methods coincide within the experimental error and indicate the extremum availability on ST isotherms. Thus, ST experimental studies by two independent methods confirmed the presence of a flat minimum on ST isotherms of the indium-tin binary system increasing the reliability of the obtained data. The obtained outcomes and their comparison with experimental data have shown that the considered models for predicting surface properties based on data due to similar properties of lateral binary systems adequately reflect the experimental dependences. However, the prediction model based on Kohler's method of excess values describes the experimental curves more accurately.


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