scholarly journals The equivalence of quasi-chemical and statistical description of adsorbate molecule association in a localised adsorption monolayer on a homogeneous solid surface

2018 ◽  
Vol 65 (4) ◽  
pp. 25-38
Author(s):  
Jerzy K. Garbacz ◽  
Mariusz Kozakiewicz

Abstract The analysis of Berezin and Kiselev’s concept assuming linear association of molecules in a localised adsorption monolayer on the homogeneous surface of a solid adsorbent was carried out. An inconsistency due to the lack of consideration of equilibrium concentration of free adsorption sites in the formulation of the expression for the association constant has been pointed out. It was shown that the correct form of this function leads to the final adsorption equation being identical to the specific case of the Fowler-Guggenheim equation. The obtained result has been generalised to cases of branched adsorbateadsorbate associations. A new adsorption equation limiting the association to at most the dimers has been introduced. Critical conditions for the two-dimensional condensation of the adsorption layer were determined. By applying the formalism of canonical ensemble, full equivalence of the phenomenological and statistical methods was demonstrated in the description of the intermolecular interactions in the localised adsorption monolayer.

2018 ◽  
Vol 64 (3) ◽  
pp. 25-38
Author(s):  
Jerzy K. Garbacz ◽  
Ewa Kopkowska ◽  
Barbara Rymian

Abstract The subsequent stages of the process of formulation of the equation for gas adsorption on a homogenous surface of a solid adsorbent were presented based on the general expression for the canonical ensemble of the mobile single-component adsorption monolayer. The method of formulating the configuration integral of the proposed model was discussed in detail where the role both of the attraction and repulsion between adsorbed molecules was emphasised. The expression for the probability of finding a molecule in a specified point on a surface of an adsorbent was modified by determining its magnitude by the adsorbent concentration. The expression for the so-called effective surface of the adsorbent was obtained by adapting a two-dimensional analogue equation of state hard spheres – Van der Waals equation (2D-vdW) and Reis-Frisch-Lebowitz equation accordingly (2D-RFL). As a result, two new adsorption equations were formulated which differ in detail concerning the adsorbate-adsorbate repulsion. On each of these equations theoretical analysis was performed in terms of two-dimensional phase transformation. In both cases it was proved that the proposed solution allows for the presence of two-phase transformations of the first type which is the gas-liquid condensation and solidification liquid-solid. The verification of the given approach was supplemented by the description of the experimental data given in reference literature and by obtaining a very good correlation between the theory and experiment.


2019 ◽  
Vol 69 (4) ◽  
pp. 33-44
Author(s):  
Jerzy K. Garbacz ◽  
Jerzy Ciechalski ◽  
Mariusz Kozakiewicz

AbstractThis paper characterises the concept of monolayer mobile gas adsorption on a homogeneous surface of a solid. The theoretical basis of the phenomenological variant of the description of adsorption equilibrium in the system in question are discussed. The essential features of the solutions to date are discussed, and the effect of the free surface of adsorbent on the form of the final adsorption equation is stressed.An alternative concept of the free surface based on the modified two-dimensional analogue of Reiss, Frisch and Lebowitz equations is also presented. The obtained adsorption equation was tested for critical parameters of two-dimensional condensation of the adsorption layer, and then used to describe the experimental data available in literature. The verification carried out confirmed the correctness and usefulness of the proposed concept.


2021 ◽  
Author(s):  
Nadežda Stojanov ◽  
Tijana Zeremski ◽  
Snežana Maletić ◽  
Milorad Živanov ◽  
Jelena Tričković

<p>Biochar is promising material used to enhance organic matter content in soil and to mitigate climate change through carbon sequestration. In addition to that, biochar increases crop yield by means of improving soil capacity for water- and nutrient-holding capacity, and due to its adsorption capacity, it decreases mobility and bioavailability of organic pollutants and heavy metals. Biochar (BC) is a carbon-rich and porous material produced by pyrolysis of biomass under oxygen-limited conditions. The unwanted spread of pesticides to the environment and their leaching into the groundwater is of great concern. The aim of this work is to investigate the potential of BC to improve the adsorption capacity for two triazine herbicides in three different soil types with various organic matter (OC) content. Triazine herbicides (terbuthylazine and atrazine) were chosen as the most widely used pesticides in recent decades. The main difference among between three different soils types used in the study is in their OM content, which was 0.48%, 2.34% and 4.12%, respectively for Soil1, Soil2, and Soil3. The BC used in this work is commercially available compost-activated biochar produced by pyrolysis of beechwood chips at 700 <sup>o</sup>C. A batch adsorption experiments were conducted to investigate herbicide adsorption in soil without BC and with the amendment of BC (0, 1, 5, and 10%). The concentration of herbicides in the aqueous phase at equilibrium (which is achieved after 72 h) was determined by GC-MS. The adsorption isotherms were well described with the Freundlich model (R<sup>2</sup> values range from 0.714 to 0.998). Values of Freundlich exponent <em>n</em> were less than 1 (from 0.314 to 0.897), which indicates that the isotherms are of L-type. This shows that with the increase of compound concentration relative adsorption decreases because of the saturation of adsorption sites. Single-point distribution coefficients (<em>K<sub>d</sub></em>) were calculated at selected equilibrium concentration (<em>c<sub>e</sub></em>= 100 µg dm<sup>–3</sup>). <em>K<sub>d</sub></em> values increased with an increase of BC content, especially for 5% and 10% of BC amendment. <em>K<sub>d</sub></em> values of atrazine in Soil1 were in the range 1.91–14.55, in Soil2 from 4.76–15.65, and in Soil3 from 4.79–20.11, while <em>K<sub>d</sub></em> values of terbuthylazine ranged from 1.14–30.92 in Soil1, from 14.13–50.74 in Soil2, and from 12.65–47.03 in Soil3. In unamended Soil1 the adsorption of both herbicides was lower in comparison to unamended Soil2 and Soil3, which is in accordance with the well-known fact that the OC content of soil primarily affects the adsorption of pesticides. The adsorption capacity of Soil 2 and Soil 3 was not significantly different. It is observed that the adsorption of terbuthylazine is higher in all soil types, which is in accordance with its lower solubility and higher affinity for OM in comparison to atrazine. It is shown that sorption capacity of soil for pesticides could be improved by adding biochar into the soil, thus reducing herbicide mobility into the environment. Further studies will be conducted by column experiments to investigate more realistic environmental scenarios.</p>


2007 ◽  
Vol 61 (3) ◽  
pp. 123-128 ◽  
Author(s):  
Dusan Stosic ◽  
Vera Dondur ◽  
Vladislav Rac ◽  
Vesna Rakic ◽  
Joanna Zakrzewska

The plant alkaloid, nicotine, is a strongly toxic heterocyclic compound: the lethal dose for an adult human being (40-60 mg) is importantly lower in comparison with the other known poisons such as arsenic or strychni?ne. Cigarettes represent "the most toxic and addictive form of nicotine". Besides the negative effects of nicotine on public health produced by self-administration, recently another potentially very dangerous effect has been recognized: because of its miscibility with water, nicotine can be found in industrial wastewaters, and consequently, in groundwater. Therefore, the problem of nicotine removal from aqueous solutions has became an interesting topic. In this work, the removal of nicotine has been probed by adsorption on solid materials. Adsorption of nicotine on different zeolites (clinoptilolite, ZSM-5 and ? zeolite) and on activated carbon was investigated from aqueous solutions, at 298 K. The obtained results are presented as adsorption isotherms: the amount of adsorbed nicotine as a function of equilibrium concentration. These data were obtained from the residual amount of nicotine in the aqueous phase, by the use of UV spectroscopy. The highest amounts of adsorbed nicotine was found for activated carbon and p zeolite (~ mmol?g-1). The attempt to modify the adsorption properties of ZSM-5 zeolite has been also done: ZSM-5 was modified by ion-exchange with VIII group metal (Cu2+ and Fe3+). In addition, the adsorption of nicotine on ZSM-5 zeolite with different Si/Al ratios has been done. It has been noticed that ion-exchange did not improve the adsorption possibilities, while the adsorption was importantly lower in the case of higher silicon content in ZMS-5 structure. 13C NMR spectra were collected for suspensions formed of solid adsorbent and aqueous solution of nicotine; in this way, the part of nicotine molecule which is most probably connected with the adsorbent was recognized.


2019 ◽  
Vol 67 (2) ◽  
pp. 59-68
Author(s):  
Jerzy K. Garbacz ◽  
Karol Karpiński ◽  
Mariusz Kozakiewicz

Abstract Continuing the discussion on the description of adsorbate-adsorbate association on homogeneous surfaces of solids, an attempt was made to formulate an analytical form of adsorption equation for a multilayer adsorption phase. The validity of Berezin’s and Kiselev’s assumptions concerning the independence of adsorption in further layers from the model of the phenomenon in the first of them was discussed. The fundamental validity of this assumption has been demonstrated, simultaneously ridding it of its arbitrary character. The main aim of the study was to demonstrate the possibility of formulating a description assuming molecule association in the entire adsorption phase (and not only in the first layer). Theoretical considerations are confined to the case of dimerisation in the concentration range thus warranting the approximation characteristic of the Berezin and Kiselev model. The obtained final adsorption equation exhibits physically acceptable boundary properties; with adequate assumptions it amounts to the Brunauer, Emmett and Teller equation, the equation formulated earlier by one of the authors of this paper or the Langmuir equation.


2019 ◽  
Vol 80 (6) ◽  
pp. 1118-1124
Author(s):  
Githmi Gayani Pathberiya ◽  
G. Y. Jayasinghe ◽  
Rohana Chandrajith

Abstract Heavy metal contamination of water is a significant threat to organisms and to public health. Among them, chromium is one of the important heavy metals in the environment that originates mainly from anthropogenic activities. Natural red earth (NRE), a ferrous-coated natural sand, is one of the materials that could be used to remove heavy metals from contaminated water. Laboratory-scale simulated experiments were carried out to identify the retention behavior of Cr(VI) on NRE. The effects of solution pH, initial Cr(VI) concentration, the amount of NRE used and the contact time were examined. Almost 63% Cr(VI) was adsorbed within 20 minutes. When particle size ranged from 125 to 180 μm, the Cr adsorption data followed the Langmuir isotherm model, providing a higher R2 value of 0.9523, suggesting monolayer coverage on the homogeneous surface with a uniform distribution of energetic adsorption sites. The monolayer coverage of Cr on NRE is estimated as 11.35 mg/g. The data showed that NRE can be used to remove Cr(VI) from aqueous solutions effectively, and this method is found to be simple, effective, economical and environmentally friendly.


1966 ◽  
Vol 49 (4) ◽  
pp. 819-843 ◽  
Author(s):  
Gilbert Ning Ling ◽  
Margaret Mary Ochsenfeld

A comparison is made between the quantitative predictions of equilibrium ionic distribution in living cells according to the membrane theory (Donnan equilibrium) and according to the association-induction hypothesis. This comparison shows that both theories predict competitive effects of one permeant ion on the equilibrium concentration of another permeant ion; but within the limit of experimental accuracy only the association-induction model predicts quantitatively significant specific competition of one specified ion with the accumulation of another specified ion. The equilibrium distributions of K+, Rb+, and Cs+ ions in frog sartorius muscle were studied and quantitatively significant specific competition was demonstrated; these results favor the association-induction hypothesis (adsorption on cell proteins and protein complexes and partial exclusion from cell water). Based on this model we estimated that at 257deg;C, the apparent association constants for K+, Rb+, and Cs+ ion are 665, 756, and 488 (mole/liter)-1. We found that the total concentration of adsorption sites (no less than 240 mmole/kg of fresh cells) agrees with the analytically determined concentrations of ß- and γ-carboxyl groups of muscle cell proteins (260 to 288 mmole/kg).


1964 ◽  
Vol 11 (01) ◽  
pp. 222-229 ◽  
Author(s):  
Isaac Djerassi ◽  
Albert Roy ◽  
Jorge Alvarado ◽  

SummaryHuman platelets frozen at −195° C (liquid nitrogen) retain their morphological integrity and ability to promote clot retraction when 5% dimethyl-sulfoxide and 5% dextrose are added to the suspending plasma medium. Slow freezing was more effective than direct immersion in the liquid nitrogen. Although similar results may be achieved with dimethylsulfoxide alone with rigidly controlled freezing rates, the addition of sugars may permit freezing under less critical conditions.Dimethylsulfoxyd und 5% Dextrose dem Plasmamilieu hinzugefügt werden. Das langsame Einfrieren ist effektiver als das direkte Eintauchen in flüssigen Stickstoff. Obschon ähnliche Resultate mit Dimethylsulfoxyd allein unter exakter Kontrolle der Einfrierungsgeschwindig-keit erreicht werden können, erlaubt die Zugabe von Dextrose ein Einfrieren unter weniger kritischen Bedingungen.


Author(s):  
Elena V. Bespalova

Ancient lake sediments of Bibirevo section in the Yaroslavl and Kostroma Volga region are studied by means of graphical analysis of taxonomical structure of diatom complexes. This method allowed to record critical points (change of areas of stability) in the development of a Neopleistocene lake during the transition from stage to stage, as well as from phase to phase.


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