Isothermic processes Freundlich isotherm

Adsorption This is the most widely used of the physical-chemical treatment processes. It is used primarily for the removal of soluble organics with activated carbon serving as the adsorbent. Most liquid-phase-activated carbon adsorption reactions follow a Freundlich Isotherm [Eq. (25-21)]. 

Spirodela intermedia, L. minor, and P. stratiotes were able to remove Pb(II), Cd(II), Ni(II), Cu(II), and Zn(II), although the two former ions were removed more efficiently. Data fitted the Langmuir model only for Ni and Cd, but the Freundlich isotherm for all metals tested. The adsorption capacity values (K ) showed that Pb was the metal more efficiently removed from water solution (166.49 and 447.95 mg/g for S. intermedia and L. minor, respectively). The adsorption process for the three species studied followed first-order kinetics. The mechanism involved in biosorption resulted in an ion-exchange process between monovalent metals as counterions present in the macrophytes biomass and heavy metal ions and protons taken up from water.112... 

Sorption and desorption are usually modeled as one fully reversible process, although hystersis is sometimes observed. Four types of equations are commonly used to describe sorption/desorption processes Langmuir, Freundlich, overall and ion or cation exchange. The Langmuir isotherm model was developed for single layer adsorption and is based on the assumption that maximum adsorption corresponds to a saturated monolayer of solute molecules on the adsorbent surface, that the energy of adsorption is constant, and that there is no transmigration of adsorbate on the surface phase. 

Predominantly, Freundlich s fitted adsorption isotherms computed by means of simple linear regression were proposed for the mathematical description of the process studied. Unlike the Langmuir equation, the Freundlich model did not reduce to a linear adsorption expression at very low nor very high solute concentrations, as above resulted. 

Abstract Removal of the pesticide metobromuron from aqueous solutions by adsorption at the high area activated carbon cloth was investigated. Kinetics of adsorption was followed and adsorption isotherms of the pesticide was also be determined. In kinetic studies a special V-shaped cell with an UV cuvette attached to it was used for adsorption processes. With this cell it was possible to follow the concentration of pesticide molecule by in situ UV spectroscopy as it is adsorbed at the activated carbon cloth. The obtained absorbance vs time data were converted into concentration vs time data and these data were treated according to pseudo-first-order and psendo-second-order kinetic models. Adsorption of that pesticide was fonnd to follow second-order kinetic model with k 87.35 g mol min. Adsorption isotherms were derived at 25°C on the basis of batch analysis. Isotherm data were treated according to Langmuir and Freundlich models. The fits of experimental data to these equations were examined and founded that the adsorption isotherm was well represented by Frenndlich model. 

Sorption is most commonly quantified using distribution coefficients (Kd), which simplistically model the sorption process as a partitioning of the chemical between homogeneous solid and solution phases. Sorption is also commonly quantified using sorption isotherms, which allow variation in sorption intensity with triazine concentration in solution. Sorption isotherms are generally modeled using the empirical Freundlich equation, S = K CUn, in which S is the sorbed concentration after equilibration, C is the solution concentration after equilibration, and Kt and 1 In are empirical constants. Kd and K are used to compare sorption of different chemicals on one soil or sorbent, or of one chemical on several sorbents. Kd and K are also commonly used in solute leaching models to predict triazine interactions with soils under various environmental conditions. 

From the scientific point of view, however, all approaches in the sense of the Kd concept (Henry, Freundlich or Langmuir isotherm) are unsatisfactory, since the complex processes on surfaces cannot be described by empirical fitting parameters. Boundary conditions like pH value, redox potential, ionic strength, competition reactions for binding sites are not considered. Thus results from laboratory and field experiments are not transferable to real systems. They are only advisable to provide a suitable prognosis model, if no changes concerning boundary conditions are to be expected and if no parameters for deterministic or mechanistic approach can be determined. 

Equilibrium between solution and adsorbed or sorbed phases is a condition commonly used to evaluate adsorption or sorption processes in soils or soil-clay minerals. As previously stated, equilibrium is defined as the point at which the rate of the forward reaction equals the rate of the reverse reaction. Two major techniques commonly used to model soil adsorption or sorption equilibrium processes are (1) the Freundlich approach and (2) the Langmuir approach. Both involve adsorption or sorption isotherms. A sorption isotherm describes the relationship between the dissolved concentration of a given chemical species (adsorbate) in units of micrograms per liter (pg L 1), milligrams per liter (mg L-1), microequivalents per liter (pequiv L-1), or millimoles per liter (mmol L-1), and the sorbed quantity of the same species by the solid phase (adsorbent) in units of adsorbate per unit mass of adsorbent (solid) (e.g., pg kg-1, mg kg-1, peq kg-1, or mmol kg 1) at equilibrium under constant pressure and temperature. Sorption isotherms have been classified into four types, depending on their general shape (Fig. 4.13) ... 

A number of solute-solid isotherms were determined over the next 20 years including those for the uptake of iodine and various dyes by charcoal and other adsorbents, but many of the investigators still believed that the process involved penetration into the solid structure. Freundlich, in 1907, was one of the first to... 

As seen from the previous discussion, Langmuir and Freundlich, the most-applied isotherms to describe the adsorption processes, assume that the surface sites have certain properties. The Langmuir isotherm assumes an ideal homogeneous surface with no interaction between adsorbed particles. The Freundlich isotherm considers a heterogeneous surface where the energy distribution (heat... 

Adsorption and desorption processes of F in soils and soil components has been studied extensively. Bar-Yosef et al. (1988) studied F sorption by montmorillonite and kaolinite and reported that F affinity was greatest in K-kaolinite and least with Ca-montmorillonite. These authors also concluded that the Langmuir model satisfactorily fit F sorption by these adsorbents. Fluoride sorption in soils has been described by both Langmuir and Freundlich isotherms (Omuetti and Jones, 1977 Chhabra et al., 1980 Morshina, 1980 Gupta et al., 1982). Peek and Volk (1985) reported that the Langmuir isotherm is applicable only for limited concentrations of F in soils. 

Molecular or ion-pair adsorption The adsorption of potassium bromate on the surface of barium sulfate appears to involve the simultaneous occupation of adjacent sites on the crystal surface by potassium ions and bromate ions this is called an equivalent adsorption because equal amounts of the two ions are adsorbed. Such adsorptions, and in fact many molecular adsorption processes, follow an empirical equation known as the Freundlich adsorption isotherm ... 

Theory The Freundlich isotherm developed in 1924 by Freundich (16) is widely used to study oil processing adsorption. It is applied as an empirical expression to describe the reversible adsorption of a single solute from aqueous solution at equilibrium at a fixed temperature, and it is expressed as... 

Obstacles to practical application of the Langmuir and Freundlich isotherm theories include the following (1) These isotherms do not effectively address adsorption versus degradation and competitive adsorption (2) the conclusions are not all inclusive i.e., adsorption constants and coefficients do not hold true in all cases within similar oil types let alone across different oil types (3) the process has so many variables that the additive variance is commonly too great to prove any subtle difference between clays other than a vastly different level of activity (this problem is especially true when using log vs. log plots with incremental changes on the order of 0.1%) and (4) the adsorption constants and coefficients have limited use for the refiner. 

Of course, other types of adsorption isotherms commonly represent the adsorption processes in heterogeneous catalysis, for example, the Freundlich isotherm and, especially in electrode processes, the Temkin and Frumkin isotherms (99). In the latter case... 

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