Sorbents isotherms

Total Porosities. The total pore volume of a microporous crystal can usually be estimated from the amounts of water (polar sorbents) or N2 (polar or non-polar sorbents) which fill the pores. With polar sorbents isotherms of water are very rectangular at room temperature with all sorbents this is true of N2 at liquid nitrogen temperatures. The flat tops of the isotherms then permit estimates of saturation uptakes. From these amounts, if one assumes that the co-volumes of H2O and N2 are the same as in their liquids at the respective experimental temperatures, the pore volumes per g. or per cm3 Qf crystal can be found. Total pore volumes can also be estimated from the calculated free volume of each cavity and the number of cavities per g. or per cm3 of crystal. Table 4 gives, for zeolites, approximate total pore volumes derived from ideal compositions quoted by Meier and Olson [22]. Nitrogen monolayer equivalent areas per cm3 of crystal are also derived, assuming a co-volume of N2 at-195°C of 55.2 x 10-24 cm3 per molecule, and a 00-area of 16.2 x 10 16 cm2. The porosities and areas in Table 4 place the zeolites among high capacity sorbents. 

The working capacity of a sorbent depends on fluid concentrations and temperatures. Graphical depiction of soration equilibrium for single component adsorption or binary ion exchange (monovariance) is usually in the form of isotherms [n = /i,(cd or at constant T] or isosteres = pi(T) at constant /ij. Representative forms are shown in Fig. I6-I. An important dimensionless group dependent on adsorption equihbrium is the partition ratio (see Eq. 16-125), which is a measure of the relative affinities of the sorbea and fluid phases for solute. 

Adsorption with strongly favorable isotherms and ion exchange between strong electrolytes can usually be carried out until most of the stoichiometric capacity of the sorbent has been utilized, corresponding to a thin MTZ. Consequently, the total capacity of the bed is... 

The (I)-(III)-samples sorption ability investigation for cationic dyes microamounts has shown that for DG the maximum rate of extraction is within 70-90 % at pH 3. The isotherm of S-type proves the physical character of solution process and a seeming ionic exchange. Maximal rate of F extraction for all samples was 40-60 % at pH 8 due to electrostatic forces. The anionic dyes have more significant affinity to surface researching Al Oj-samples comparatively with cationic. The forms of obtained soi ption isotherms atpH have mixed character of H,F-type chemosorption mechanism of fonuation of a primary monolayer with the further bilayers formation due to H-bonds and hydrophobic interactions. The different values of pH p for sorbents and dyes confirm their multifunctional character and distinctions in the acid-base properties of adsoi ption centers. 

The capacity factors of SN-SiO, for metal ions were determined under a range of different conditions of pH, metal ions concentrations and time of interaction. Preconcentration of Cd ", Pb ", Zn " and CvS were used for their preliminary determination by flame atomic absorption spectroscopy. The optimum pH values for quantitative soi ption ai e 5.8, 6.2, 6.5, 7.0 for Pb, Cu, Cd and Zn, respectively. The sorption ability of SN-SiO, to metal ions decrease in line Pb>Cu> >Zn>Cd. The soi ption capacity of the sorbent is 2.7,7.19,11.12,28.49 mg-g Hor Cd, Zn, Pb, andCu, respectively. The sorbent distribution coefficient calculated from soi ption isotherms was 10 ml-g for studied cations. All these metal ions can be desorbed with 5 ml of O.lmole-k HCl (sorbent recovery average out 96-100%). 

BBT solution on unmodified sorbents of different nature was studied. Silica gel Merck 60 (SG) was chosen for further investigations. BBT immobilization on SG was realized by adsoi ption from chloroform-hexane solution (1 10) in batch mode. The isotherm of BBT adsoi ption can be referred to H3-type. Interaction of Co(II), Cu(II), Cd(II), Ni(II), Zn(II) ions with immobilized BBT has been studied in batch mode as a function of pH of solution, time of phase contact and concentration of metals in solution. In the presence of sodium citrate absorbance (at X = 620 nm) of immobilized BBT grows with the increase of Cd(II) concentration in solution. No interference was observed from Zn(II), Pb(II), Cu(II), Ni(II), Co(II) and macrocomponents of natural waters. This was assumed as a basis of soi ption-spectroscopic and visual test determination of Cd(II). Heavy metals eluted from BBT-SG easily and quantitatively with a small volume of HNO -ethanol mixture. This became a basis of soi ption-atomic-absoi ption determination of the total concentration of heavy metals in natural objects. 

Isotherms have been eonstrueted and quantities of maximum sorbent eapaeity have been ealeulated for all the dyes. For instanee, isotherms of astrazone violet 3R and astrafloxin FF dyes sorption refer to S2 type. Maximum sorbent eapaeities made up 0,761 and 1,264 p.mol/g eorrespondingly. 

Fig. 2. Schematics of adsorption isotherms for polymers, where the adsorbed mass r per unit area of the sorbent surface is plotted against the polymer concentration cp in solution. The steep initial slope of the isotherms indicates...

Fig. 3. Schematics of the influence of electrostatic interactions on adsorption isotherms of polyelectrolytes. Effect of charge contrast between the polyelectrolyte and the sorbent surface in media of (a) low and (b) high ionic strength.

Fig. 4. Influence of pH on the plateau-value /T of adsorption isotherms of polyampholytes. At either side of the isoelectric point, i.e.p., the polyampholyte attains a net charge causing intra- and intermolecular electrostatic repulsion. As a result, the mass of adsorbed polyampholyte, that can be accommodated per unit area of the sorbent surface, decreases. Electrostatic interactions are suppressed by increasing ionic strength, yielding /T less sensitive to pH.

As depicted in Fig. 5, both the protein molecule and the sorbent surface are electrically charged. In an aqueous environment, they are surrounded by counterions, which, together with the surface charge, form the so-called electrical double layer. The Gibbs energy of an electrical double layer, may be calculated as the isothermal, isobaric reversible work required to invoke the charge distribution in the double layer... 

Figure 9 shows adsorption isotherms for this protein on the various sorbents. As is usually observed for proteins at surfaces, the adsorption affinity is higher for the hydrophobic surfaces than for the hydrophilic ones. The adsorption plateau-values at silica and PS- (EO)8, approximately... 

Fig. 9. Adsorption isotherms where the adsorbed mass f/rngm 2, of various sorbent surfaces is plotted against the protein concentration cl g dm 3, in solution. Sorbents Teflon (o), polystyrene (x),... 

The enzymatic activities of O -chymotrypsin in solution and adsorbed at the different surfaces are presented in Fig. 11, where the specific enzymatic activity (defined as activity per unit mass of protein) is plotted as a function of temperature. The enzyme loses activity due to adsorption. On the hydrophobic Teflon and PS surfaces, the activity is completely gone, whereas on the hydrophilic silica surface, or-chymotrypsin has retained most of its biological function. These differences are in agreement with the adsorption isotherms and the circular dichroism spectra. The influence of the hydrophobicity of the sorbent surface on the affinity of the protein for the sorbent surface, as judged from the rising parts of the adsorption isotherms (Fig. 8), suggests that the proteins are more perturbed and, hence, less biologically active when adsorbed at hydrophobic surfaces. Also, the CD spectra indicate that adsorption-induced structural perturbations are more severe at hydrophobic surfaces. 

Fig. 6.10 shows idealized isotherms (at constant pH) for cation binding to an oxide surface. In the case of cation binding, onto a solid hydrous oxide, a metal hydroxide may precipitate and may form at the surface prior to their formation in bulk solution and thus contribute to the total apparent "sorption". The contribution of surface precipitation to the overall sorption increases as the sorbate/sorbent ratio is increased. At very high ratios, surface precipitation may become the dominant "apparent" sorption mechanism. Isotherms showing reversals as shown by e have been observed in studies of phosphate sorption by calcite (Freeman and Rowell, 1981). 

In addition to the dependence of sorption on the organic fraction of the sorbent, and the KQw of the sorbate, Chiou et al. (13) cite the following observations as support for the hypothesis that the sorptive mechanism is hydrophobic partitioning into the organic (humic) fraction of the sediments (1) the linearity of the isotherms as the concentration approaches solubility, (2) the small effect of temperature on sorption, and (3) the lack of competition between sorbates for the sorbent. These arguments also illustrate the applicability of the approach for modeling sorption on hydro-phobic compounds an approach which has been criticized when used in the context of adsorption of trace metals onto oxides (17). 

The reader will find adsorption equilibrium relationships presented in any of three typical forms. The form of equilibrium most frequently presented is the isotherm, the partial pressure as a function of the loading at a given constant sorbent temperature. An isobar implies a chart of the loading as a function of the temperature while the partial pressure of the sorbate is held constant. 

The simplest adsorption equation is Henry s Law, that is, the loading is directly proportional to the sorbate partial pressure. X= KP This linear isotherm equation adequately describes some adsorbents and, in the limit of low coverage, it actually describes most sorbents. For adsorption that is truly described by Henry s Hnear relationship, the loadings are low, the adsorption is bound to be essenhaUy isothermal and there are several published analytical solutions to describe both batch kinetics and column dynamic behavior for such systems. 

The Brunauer type I is the characteristic shape that arises from uniform micro-porous sorbents such as zeolite molecular sieves. It must be admitted though that there are indeed some deviations from pure Brunauer type I behavior in zeoHtes. From this we derive the concept of the favorable versus an unfavorable isotherm for adsorption. The computation of mass transfer coefficients can be accompHshed through the construction of a multiple mass transfer resistance model. Resistance modehng utilizes the analogy between electrical current flow and transport of molecular species. In electrical current flow voltage difference represents the driving force and current flow represents the transport In mass transport the driving force is typically concentration difference and the flux of the species into the sorbent is resisted by various mechanisms. 

Retention of organic contaminants on subsurface solid phase constituents in general is not completely reversible, so that release isotherms differ from retention isotherms. As a consequence, the extent of sorption depends on the nature of the sorbent. Subsurface constituents as well as the types of bonding mechanisms between contaminants and the sohd phase are factors that control the release of adsorbed organic contaminants. Saltzman et al. (1972) demonstrated the influence of soil organic matter on the extent of hysteresis. Adsorption isotherms of parathion showed hysteresis (or apparent hysteresis) in its adsorption and desorption in a water solution. In contrast, smaller differences between the two processes were observed when the soils were pretreated with hydrogen peroxide (oxidized subsamples) to reduce initial organic matter content. The parathion content of the natural... 

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