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Freundlich equation
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The Freundlich equation or Freundlich adsorption isotherm, an adsorption isotherm, is an empirical relationship between the quantity of a gas adsorbed into a solid surface and the gas pressure. The same relationship is also applicable for the concentration of a solute adsorbed onto the surface of a solid and the concentration of the solute in the liquid phase. In 1909, Herbert Freundlich gave an expression representing the isothermal variation of adsorption of a quantity of gas adsorbed by unit mass of solid adsorbent with gas pressure.[1] This equation is known as Freundlich adsorption isotherm or Freundlich adsorption equation. As this relationship is entirely empirical, in the case where adsorption behavior can be properly fit by isotherms with a theoretical basis, it is usually appropriate to use such isotherms instead (see for example the Langmuir and BET adsorption theories). The Freundlich equation is also derived (non-empirically) by attributing the change in the equilibrium constant of the binding process to the heterogeneity of the surface and the variation in the heat of adsorption.[2]

Freundlich adsorption isotherm

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Freundlich's original data for adsorption of organic acids (page 391-393 in [3]). Continous lines: Data according to Freundlich's fit for exponential law. Dotted lines: Data according to optimization, see table.


The Freundlich adsorption isotherm is mathematically expressed as

In Freundlich's notation (used for his experiments dealing with the adsorption of organic acids on coal in aqueous solutions), signifies the ratio between the adsorbed mass or adsorbate and the mass of the adsorbent , which in Freundlich's studies was coal. In the figure above, the x-axis represents , which denotes the equilibrium concentration of the adsorbate within the solvent.


Freundlich's numerical analysis of the three organic acids for the parameters and according to equation 1 were:

acid type K n
acetic 2.606 2.35
propionic 3.463 2.82
succinic 4.426 3.65

Freundlich's experimental data can also be used in a contemporary computer based fit. These values are added to appreciate the numerical work done in 1907.

Computer based fit (according to eq. 1 ) with Freundlich's experimental data
acid type K △ K n △ n
acetic 2.56 0.035 2.565 0.075
propionic 3.292 0.0471 3.005 0.104
succinic 4.28 0.11 3.884 0.21

△ K and △ n values are the error bars of the computer based fit. The K and n values itself are used to calculate the dotted lines in the figure.

Equation 1 can also be written as

Sometimes also this notation for experiments in the gas phase can be found:

x = mass of adsorbate
m = mass of adsorbent
p = equilibrium pressure of the gaseous adsorbate in case of experiments made in the gas phase (gas/solid interaction with gaseous species/adsorbed species)

K and n are constants for a given adsorbate and adsorbent at a given temperature (from there, the term isotherm needed to avoid significant gas pressure fluctuations due to uncontrolled temperature variations in the case of adsorption experiments of a gas onto a solid phase).

K = distribution coefficient
n = correction factor

At high pressure 1/n = 0, hence extent of adsorption becomes independent of pressure.

The Freundlich equation is unique; consequently, if the data fit the equation, it is only likely, but not proved, that the surface is heterogeneous. The heterogeneity of the surface can be confirmed with calorimetry. Homogeneous surfaces (or heterogeneous surfaces that exhibit homogeneous adsorption (single site)) have a constant ΔH of adsorption.[4] On the other hand, heterogeneous adsorption (multi-site) have a variable ΔH of adsorption depending on the percent of sites occupied. When the adsorbate pressure in the gas phase (or the concentration in solution) is low, high-energy sites will be occupied first. As the pressure in the gas phase (or the concentration in solution) increases, the low-energy sites will then be occupied resulting in a weaker ΔH of adsorption.[5]

Limitation of Freundlich adsorption isotherm

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Experimentally it was determined that extent of gas adsorption varies directly with pressure, and then it directly varies with pressure raised to the power 1/n until saturation pressure Ps is reached. Beyond that point, the rate of adsorption saturates even after applying higher pressure. Thus, the Freundlich adsorption isotherm fails at higher pressure.

See also

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References

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Further reading

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Revisions and contributorsEdit on WikipediaRead on Wikipedia

Freundlich equation

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The Freundlich equation, also known as the Freundlich adsorption isotherm, is an empirical mathematical model that describes the equilibrium relationship between the amount of a gas or solute adsorbed onto a solid surface and the or concentration of the adsorbate at constant . It applies particularly to adsorption processes on heterogeneous surfaces, where the adsorption capacity varies with concentration, and is expressed in the form qe=KFCe1/nq_e = K_F C_e^{1/n}, with qeq_e representing the adsorption capacity at equilibrium (in mg/g), CeC_e the equilibrium concentration (in mg/L), KFK_F the Freundlich constant indicative of adsorption capacity, and 1/n1/n the heterogeneity factor reflecting adsorption intensity (typically between 0 and 1 for favorable adsorption). First proposed by German physical chemist Herbert Freundlich (whose surname means "friendly" in German, derived from "Freund" meaning "friend") in 1907, the equation originated from experimental observations of gas adsorption on solids and solute adsorption in solutions, such as dyes on , providing a foundational tool for understanding non-ideal adsorption behaviors without assuming a fixed maximum capacity. The equation's empirical nature stems from Freundlich's work in Kapillarchemie (), where it was formulated to fit logarithmic plots of adsorption data, yielding a linear relationship in the transformed form log⁡qe=log⁡KF+1nlog⁡Ce\log q_e = \log K_F + \frac{1}{n} \log C_e, which facilitates parameter estimation via . Unlike the Langmuir isotherm, which assumes coverage on uniform sites and predicts a saturation limit (qmq_m), the Freundlich model accommodates multilayer adsorption and site energy heterogeneity, making it suitable for real-world systems like or soils where surface irregularities dominate. Theoretical derivations, such as those based on an of adsorption energies or kinetics, have since provided mechanistic insights, though the original remains largely empirical. Key parameters KFK_F (with units depending on 1/n1/n) quantify the system's affinity, while 1/n<11/n < 1 signals cooperative or favorable adsorption, and values approaching 1 indicate linear partitioning akin to simpler distribution models. In practice, the Freundlich equation is extensively applied in environmental science and engineering for modeling pollutant removal, such as heavy metals or organic contaminants from wastewater using adsorbents like peat or activated carbon, and in soil chemistry to predict ion retention (e.g., zinc or phosphate sorption). It also finds use in gas-phase separations, membrane technologies, and pharmaceutical analyses, often outperforming other isotherms in fitting data for micropollutants due to its flexibility with concentration-dependent nonlinearity. However, limitations include its inapplicability at very high concentrations, where it may overestimate adsorption without a theoretical maximum, and challenges in multi-component systems requiring extensions like the ideal adsorbed solution theory. Ongoing research integrates it with linear free-energy relationships to predict parameters from molecular descriptors, enhancing its predictive power in sustainable remediation strategies.

History and Background

Discovery and Development

Herbert Freundlich, a German physical chemist specializing in colloid and surface science whose surname derives from the German adjective freundlich meaning "friendly", "kind", "nice", or "pleasant" (from "Freund" meaning "friend" + the suffix "-lich", cognate with English "friendly"), and is also a common German and Ashkenazi Jewish surname, developed the empirical model for adsorption during his early career studies under at the University of Leipzig, where he earned his doctorate in 1903. His foundational work culminated in the 1907 publication "Über die Adsorption in Lösungen" in Zeitschrift für Physikalische Chemie, which introduced an empirical relationship derived from experimental data on solute adsorption from solutions. This paper stemmed from Freundlich's habilitation research, emphasizing practical observations over theoretical derivations in the emerging field of physical chemistry. Freundlich's investigations focused on the adsorption of organic acids, including succinic, acetic, and propionic acids, onto charcoal or coal as adsorbents, conducted between 1907 and 1909. These experiments involved measuring the amount of acid removed from aqueous solutions by the solid materials under varying equilibrium concentrations, highlighting deviations from simple proportionality in adsorption processes. For instance, in studies with acetic acid on charcoal, Freundlich reported fitted parameters from his data yielding K = 2.606 and n = 2.35, illustrating the model's applicability to specific systems. The core insight arose from Freundlich's empirical observation that plotting the logarithm of the adsorbed amount per unit mass, log(x/m), against the logarithm of the equilibrium concentration, log(c), produced a straight line across the tested conditions. This linear relationship in logarithmic space indicated a power-law dependence, providing a more flexible description than the linear form of Henry's law, which failed to capture the non-ideal, concentration-dependent behaviors seen in his charcoal-acid systems. Freundlich's approach was motivated by the limitations of earlier models in accounting for such nonlinearities in solution adsorption, marking a key empirical advance in understanding surface interactions.

Role in Early Adsorption Studies

Prior to the development of the Freundlich equation, adsorption modeling in the late 19th century was dominated by simpler approaches like , which posited a linear relationship between the amount adsorbed and the equilibrium concentration, valid primarily at low coverages where interactions between adsorbates are negligible. This model, derived from ideal gas assumptions, adequately described dilute systems but exhibited significant limitations on real-world adsorbents, where surface heterogeneity—arising from varying site energies and non-uniform distributions—led to non-linear uptake behaviors at higher concentrations. The inadequacy of highlighted the need for empirical models capable of capturing the complexities of heterogeneous surfaces, particularly in early studies of gas-solid and solution-solid interactions, where adsorption deviated from ideality due to energetic variations across the adsorbent. The Freundlich equation emerged as a pivotal empirical advancement in 1907, offering a power-law formulation that transcended the restrictive ideal gas assumptions of prior models by accommodating the decreasing affinity of adsorption sites as coverage increased. This flexibility proved instrumental in advancing research on physisorption, where weak van der Waals forces dominate on heterogeneous substrates, and chemisorption, involving stronger chemical bonds on varied catalytic surfaces, enabling researchers to fit experimental data from diverse systems without presupposing uniform site energies. By addressing the inherent non-idealities of real adsorbents, it shifted focus toward practical interpretations of adsorption kinetics and equilibria in colloidal and surface chemistry. In the 1910s and 1920s, the equation underwent early validations through its application in gas adsorption experiments, where it effectively rationalized multilayer formation on non-uniform surfaces by predicting concave downward isotherms indicative of site heterogeneity. For instance, studies on charcoal demonstrated its utility in correlating uptake data across pressure ranges, outperforming linear models in heterogeneous catalysis contexts. However, criticisms emerged regarding its purely empirical basis, absence of a theoretical foundation linking to molecular mechanisms, and failure to predict saturation limits, which some researchers argued undermined its predictive power for high-coverage regimes. Key publications following the initial 1907 work, including extensions in Zeitschrift für Physikalische Chemie, solidified the equation's role as a benchmark for heterogeneous catalysis research, with applications in analyzing activated carbons and metal oxides that influenced subsequent experimental designs in surface science. These efforts, building on Freundlich's dye solution experiments that first revealed the logarithmic relationship, established it as an indispensable tool for interpreting adsorption on irregular substrates during this formative era.

Mathematical Formulation

The Core Equation

The Freundlich equation, also known as the Freundlich adsorption isotherm, is an empirical model that describes the relationship between the amount of a substance adsorbed onto a solid surface and its equilibrium concentration in the adjacent fluid phase at a constant temperature. Originally proposed by Herbert Freundlich based on experimental observations of adsorption behavior, it captures a power-law dependence suitable for heterogeneous surfaces. The core form of the equation is expressed as: xm=K⋅c1/n\frac{x}{m} = K \cdot c^{1/n} where xm\frac{x}{m} represents the adsorption capacity, defined as the mass of adsorbate (xx) per unit mass of adsorbent (mm); cc is the equilibrium concentration of the adsorbate in the solution (or equilibrium pressure pp for gas-phase systems); KK is the Freundlich constant, which relates to the adsorption capacity of the material; and nn is the heterogeneity factor, typically ranging from 1 to 10, indicating the degree of surface nonuniformity. This formulation assumes multilayer adsorption on energetically heterogeneous sites without a fixed saturation limit. For practical analysis, the equation is often linearized by taking the logarithm of both sides, yielding: log⁡(xm)=log⁡K+1nlog⁡c\log \left( \frac{x}{m} \right) = \log K + \frac{1}{n} \log c This logarithmic form allows for graphical determination of the parameters KK and nn by plotting log⁡(xm)\log \left( \frac{x}{m} \right) against log⁡c\log c, where the intercept is log⁡K\log K and the slope is 1n\frac{1}{n}. The model applies to both liquid-solid adsorption, using concentration cc, and gas-solid adsorption, using partial pressure pp in place of cc, under isothermal conditions. As an empirical relation, the lacks a rigorous theoretical derivation and instead arises from observed power-law trends in adsorption data on heterogeneous adsorbents.

Parameter Interpretation

The parameter KK (often denoted as KFK_F) in the Freundlich equation serves as a measure of the adsorbent's adsorption capacity and affinity for the adsorbate, particularly at low equilibrium concentrations. Its value reflects the overall strength of the adsorption interaction, with higher KK values indicating greater capacity and stronger binding. The units of KK are not fixed and depend on the exponent nn, commonly expressed as (mg/g)/(mg/L)1/n(\mathrm{mg/g}) /(\mathrm{mg/L})^{1/n} in liquid-phase systems or analogous forms in gas-phase contexts, ensuring dimensional consistency with the isotherm's empirical form. The parameter nn is a dimensionless exponent that characterizes the surface heterogeneity of the adsorbent and the intensity of the adsorption process. It arises from the assumption of an exponentially decaying distribution of adsorption site energies, where lower-energy sites are more abundant, leading to multilayer adsorption on non-uniform surfaces. Higher nn values suggest a more homogeneous energy distribution and cooperative adsorption, while lower values indicate greater heterogeneity. Specifically, n>1n > 1 (equivalently, 0<1/n<10 < 1/n < 1) describes favorable adsorption with concave-down isotherms, promoting efficient uptake; n=1n = 1 results in a linear relationship equivalent to Henry's law limit; and n<1n < 1 ( 1/n>11/n > 1) signifies unfavorable adsorption with at higher concentrations. The criterion 0<1/n<10 < 1/n < 1 acts as a dimensionless indicator of process favorability, derived directly from nn without additional equilibrium terms. Both parameters exhibit temperature dependence influenced by the adsorption mechanism. For physisorption, which is exothermic, KK typically decreases with increasing temperature as thermal energy disrupts weak van der Waals forces, reducing overall capacity. In contrast, for chemisorption, an endothermic process involving chemical bonds, KK often increases with temperature, enhancing reactivity. The exponent nn generally decreases with rising temperature across both types, as higher thermal agitation amplifies the effects of surface heterogeneity and reduces adsorption intensity.

Experimental Determination

Linearization and Graphical Analysis

To determine the Freundlich parameters empirically, the nonlinear equation is transformed into a linear form by taking the logarithm (base 10) of both sides, yielding log⁡(xm)=log⁡K+1nlog⁡c\log\left(\frac{x}{m}\right) = \log K + \frac{1}{n} \log c, where xm\frac{x}{m} represents the amount of adsorbate per unit mass of adsorbent at equilibrium, cc is the equilibrium concentration of the adsorbate, KK is the Freundlich constant, and nn is the heterogeneity factor. This linear equation allows for graphical analysis by plotting log⁡(xm)\log\left(\frac{x}{m}\right) against log⁡c\log c, resulting in a straight line where the slope equals 1/n1/n and the y-intercept equals log⁡K\log K. Least-squares regression can then be applied to the plotted data to estimate these parameters accurately. For the linearization to be valid, experimental data must be collected under equilibrium conditions across a wide range of adsorbate concentrations, typically at constant temperature to ensure isotherm consistency. Additionally, the data should avoid extremes where saturation might occur at high concentrations or where deviations from linear behavior arise at very low concentrations, as the Freundlich model assumes heterogeneous surface sites with a logarithmic energy distribution without a fixed maximum capacity. The logarithmic transformation, while facilitating linear regression, can introduce errors by altering the error structure of the original data, particularly amplifying relative errors at low concentrations due to the compression of the scale and distortion of variance and normality assumptions required for least-squares fitting. This bias may lead to less reliable parameter estimates in such regimes, though alternatives like nonlinear regression are increasingly preferred for direct minimization of error functions without transformation. The step-by-step procedure for graphical analysis involves: first, conducting batch adsorption experiments at fixed temperature with varying initial adsorbate concentrations to measure equilibrium values; second, calculating xm\frac{x}{m} from the difference between initial and equilibrium concentrations using mass balance; third, computing log⁡(xm)\log\left(\frac{x}{m}\right) and log⁡c\log c for each data point; fourth, plotting these values and performing linear regression to obtain the slope and intercept; and finally, deriving n=1/slopen = 1/\text{slope} and K=10interceptK = 10^{\text{intercept}} while assessing fit quality via correlation coefficients or residual analysis.

Fitting to Data Examples

One of the earliest applications of the Freundlich equation involved fitting experimental data from the adsorption of organic acids onto charcoal, as reported in the seminal work by Freundlich. In a more contemporary example, the Freundlich equation was fitted to data from the adsorption of mercury(II) ions onto andesite, a natural volcanic rock adsorbent, across temperatures of 25–60 °C. The linearized plot in log-log space produced straight lines with correlation coefficients R2>0.99R^2 > 0.99, confirming the model's excellent fit and indicating multi-layer adsorption on heterogeneous surfaces. One set of conditions yielded n=1.85n = 1.85, suggesting moderate surface heterogeneity and favorable adsorption, as values of n>1n > 1 denote increasing adsorption capacity with concentration. Such high R2R^2 values near 1 demonstrate the Freundlich model's strong applicability to these datasets, particularly in mid-concentration ranges where the log-log plot exhibits a clear linear trend without significant deviations. In contrast, poorer fits (e.g., R2<0.9R^2 < 0.9) would signal model mismatch, prompting consideration of alternatives like the Langmuir isotherm. The sample log-log plot for mercury(II) on andesite shows a straight line with a slope of 1/n≈0.541/n \approx 0.54, validating the empirical form over the tested equilibrium concentrations of approximately 0.003–0.04 mg/L.

Applications

Gas-Solid Adsorption Systems

The Freundlich equation finds extensive application in modeling gas-solid adsorption processes, where it is adapted to use partial pressure pp in place of concentration, yielding the form q=kp1/nq = k p^{1/n}, with qq representing the equilibrium amount of gas adsorbed per unit mass of adsorbent, kk the adsorption capacity factor, and nn a heterogeneity parameter. This adaptation suits physisorption on heterogeneous surfaces, such as in vacuum systems where residual gases like nitrogen interact with materials like glass or stainless steel, influencing pumpdown rates and ultimate pressures. A prominent example is the adsorption of nitrogen on ; experimental data often fit well to the Freundlich model, particularly at low pressures, revealing multilayer coverage without strict monolayer constraints. In heterogeneous catalysis, the Freundlich equation effectively describes the adsorption of reactive gases like hydrogen or oxygen on catalyst surfaces, where the exponent 1/n1/n (typically between 0 and 1) quantifies variations in site energies due to surface nonuniformity. For instance, hydrogen physisorption on metal-organic frameworks or Prussian blue analogues follows the model closely, aiding predictions of uptake in catalytic hydrogenations. Similarly, oxygen adsorption on lanthanide oxides in oxidation catalysis aligns with Freundlich fits, capturing the decreasing affinity as coverage increases and reflecting kinetic mechanisms like Langmuir-Hinshelwood. The model's advantages shine in multilayer or porous adsorbents, where it empirically accounts for diminishing adsorption intensity at higher pressures without presupposing saturation limits, making it suitable for systems beyond ideal monolayer behavior. Historically, since its empirical formulation by Herbert Freundlich in 1909 for gas uptake on solids, the equation has underpinned industrial processes like gas storage in activated carbons and purification of air streams from volatile organics, enabling efficient design of adsorbents for energy and environmental applications.

Liquid-Solid Adsorption in Environmental Engineering

In environmental engineering, the is widely applied to model the adsorption of heavy metals from aqueous solutions onto natural clays, facilitating water purification processes. Recent studies have demonstrated its effectiveness in fitting isotherms for the removal of Ni(II), Cd(II), Pb(II), and Hg(II) ions using adsorbents such as kaolinite and andesite. For instance, adsorption of Ni(II) onto nano-kaolinite yielded Freundlich n values around 1.98, indicating favorable heterogeneous binding at 30°C. Similarly, for Cd(II) and Hg(II) on kaolinite-based clay, n values ranged from 1.28 to 1.75 across temperatures of 10–50°C, confirming favorable adsorption on heterogeneous surfaces. On andesite, Hg(II) adsorption showed an n value of 1.85 at 25°C, supporting its use in low-concentration remediation scenarios. These n values between 1 and 2 highlight the model's suitability for describing non-uniform site affinities in clay minerals, enabling prediction of breakthrough capacities in treatment systems. The Freundlich equation also plays a key role in wastewater treatment by modeling the adsorption of dyes and organic contaminants onto and , often integrated with kinetic and thermodynamic analyses for process optimization. In batch studies using activated biochar from post-coagulation sludge, Freundlich parameters (e.g., 1/n = 0.18–0.31, K_F = 23–65) effectively described the removal of synthetic dyes like Acid Red 18, Acid Green 16, and Reactive Blue 81, with pseudo-second-order kinetics (k_2 = 0.0001–0.007 g/mg·min) indicating chemisorption dominance and thermodynamic data revealing exothermic, spontaneous processes. For derived from mandarin peels, the model fitted Acid Red 73 dye adsorption, aligning with pseudo-second-order rates and negative Gibbs free energy values that confirm feasibility at ambient conditions. These integrations allow engineers to scale lab data to real effluents, predicting equilibrium loadings for heterogeneous carbon surfaces in industrial filters. In environmental remediation, the Freundlich equation aids in assessing phosphate adsorption in saline soils, addressing salinization impacts on nutrient retention and leaching risks. A study on Songnen Plain soils in China applied the model to fit phosphorus sorption data, showing good correlation (though slightly inferior to Langmuir) for heterogeneous binding in salt-affected profiles, with parameters reflecting increased adsorption capacity at higher salinity levels. This helps quantify phosphorus fixation, mitigating eutrophication from runoff. For engineering scalability, the equation informs fixed-bed column designs, as seen in mercury sorption onto natural zeolites, where Freundlich-fitted batch isotherms predicted column breakthrough curves under continuous flow, achieving >90% removal until saturation. Such applications extend to column systems for and organics, optimizing bed depth and flow rates based on n and K_F values. The Freundlich equation's empirical nature provides distinct benefits for heterogeneous natural adsorbents like clays and biochars, accurately accounting for variable binding sites and multi-layer coverage in real-world materials. Unlike homogeneous models, it captures the decreasing adsorption intensity at higher concentrations, essential for irregular surfaces in environmental matrices, thereby improving predictions for complex effluents without assuming uniform energetics.

Model Comparisons

Differences from Langmuir Isotherm

The Langmuir isotherm, developed by Irving Langmuir in 1916, describes adsorption as a monolayer process occurring on a homogeneous surface with a finite number of identical sites, each accommodating one adsorbate molecule without lateral interactions between adsorbed species. The model assumes reversible adsorption-desorption equilibrium and constant adsorption energy across all sites, leading to the equation q=qmax⁡KLc1+KLcq = \frac{q_{\max} K_L c}{1 + K_L c}, where qq is the amount adsorbed per unit mass of adsorbent, cc is the equilibrium concentration, qmax⁡q_{\max} is the maximum adsorption capacity, and KLK_L is the Langmuir constant related to adsorption affinity. This results in a hyperbolic isotherm shape that approaches a saturation plateau at high concentrations, reflecting the limited site availability. In contrast, the Freundlich equation assumes adsorption on heterogeneous surfaces with non-uniform energy distribution, allowing for multilayer coverage and no inherent saturation limit, which produces a power-law isotherm shape that is typically concave upward at low concentrations and may continue increasing without a clear plateau. While the Langmuir model enforces a finite capacity due to monolayer constraints on uniform sites, the Freundlich approach accommodates irregular surfaces and varying affinities, making it more suitable for low-to-mid concentration ranges where heterogeneity dominates. These differences arise from Langmuir's kinetic derivation balancing adsorption and desorption rates, versus Freundlich's empirical fitting to experimental data without strict mechanistic assumptions. Selection between the models depends on the adsorbent's nature: the Langmuir isotherm excels for uniform, well-defined surfaces such as activated catalysts or metal oxides, where monolayer behavior prevails, whereas the better captures adsorption on natural or porous materials like soils, activated carbons, or zeolites with site heterogeneity. In transitional regimes, hybrid models combining elements of both, such as the Sips isotherm, may provide improved fits by incorporating Langmuir's saturation with Freundlich's heterogeneity. Historically, the Langmuir model's theoretical foundation, rooted in and published in 1916, contrasted sharply with the Freundlich equation's , first proposed by Herbert Freundlich in 1909 based on logarithmic plots of experimental adsorption data for solutes and gases. This rivalry highlighted a shift from data-driven correlations to mechanistic interpretations in adsorption studies, with Langmuir's approach gaining prominence for its predictive power on ideal systems, while Freundlich's persisted for its versatility in real-world heterogeneous scenarios.

Relation to BET Theory

The Brunauer-Emmett-Teller (BET) theory extends the Langmuir monolayer adsorption model to multilayer adsorption on solid surfaces, assuming that gas molecules form successive layers where the first layer binds with a and subsequent layers bind with energy equivalent to the heat of of the gas, potentially extending to infinite layers with no lateral interactions between adsorbed molecules. This model applies primarily within a relative range of 0.05 to 0.35, where it effectively describes Type II and Type III isotherms characterized by formation followed by multilayer buildup and in porous materials. The Freundlich equation relates to the BET model by providing an empirical approximation at low relative pressures, where adsorption behavior approaches a akin to and primarily involves sparse surface coverage, but it deviates at higher coverages as BET accounts for multilayer accumulation that Freundlich does not explicitly model. Both approaches address adsorbent heterogeneity—Freundlich through its nonlinear parameter reflecting varying adsorption site energies, and BET via multilayer dynamics on surfaces that may exhibit subtle nonuniformities—yet BET enables direct estimation of from experimental isotherms of Types II and III, offering a mechanistic link absent in the purely empirical Freundlich form. In terms of applicability, the Freundlich equation serves as a practical tool for empirical curve-fitting in non-ideal gas adsorption scenarios with significant surface irregularities, while excels in quantifying multilayer processes for precise surface area determination in porous solids such as activated carbons and zeolites. The development of in built upon the foundational empirical observations of Freundlich from 1909, advancing toward a theoretical framework that integrates multilayer kinetics for enhanced predictive power in adsorption studies.

Limitations and Extensions

Fundamental Limitations

The Freundlich equation, expressed as qe=KfCe1/nq_e = K_f C_e^{1/n}, where qeq_e is the amount adsorbed at equilibrium, CeC_e is the equilibrium concentration, and KfK_f and nn are empirical constants, inherently lacks a saturation limit for adsorption capacity. Unlike mechanistic models, it predicts that adsorption quantity increases indefinitely as concentration rises, which fails to capture real-world behavior at high pressures or concentrations approaching saturation, such as beyond the saturation pressure PsP_s in gas adsorption systems. This limitation arises because the model does not incorporate a finite number of adsorption sites or multilayer formation, leading to unphysical predictions in scenarios where surfaces become fully occupied. As a purely empirical relation derived from experimental observations rather than fundamental principles, the Freundlich equation provides no mechanistic into adsorption processes. The parameters KfK_f, representing adsorption capacity, and nn, indicating surface heterogeneity or adsorption intensity, serve primarily as fitting coefficients without direct physical interpretability, such as ties to molecular interactions or site energies. This empirical foundation assumes a constant degree of surface heterogeneity across conditions, which oversimplifies complex systems and limits the model's ability to extrapolate beyond fitted data ranges. Furthermore, it does not explicitly account for effects on nn, where experimental variations in this exponent with temperature reveal inconsistencies in describing influences on adsorption energetics. The model's validity breaks down at concentration extremes, performing poorly at very low CeC_e where adsorption often approaches linear behavior (deviating from the power-law form) and at very high CeC_e where monolayer constraints or saturation effects , which the equation ignores. Experimental studies, including adsorption , confirm surface heterogeneity through measured distributions, yet the Freundlich model cannot predict or derive these distributions, relying instead on post-hoc fitting that masks underlying variations in binding energies. These shortcomings highlight its suitability only for intermediate concentration ranges in heterogeneous systems, without broader predictive utility.

Contemporary Modifications

Recent adaptations of the Freundlich equation have incorporated dependence into the adsorption capacity constant KK to better account for variations between and processes across different . This modification typically employs an Arrhenius-like expression, K(T)=K0exp⁡(−ΔHRT)K(T) = K_0 \exp\left(-\frac{\Delta H}{RT}\right), where K0K_0 is a , ΔH\Delta H is the change, RR is the , and TT is the absolute , allowing the model to capture the exothermic nature of adsorption where higher reduce KK. Such forms have been applied in studies on activated carbons, demonstrating improved predictive accuracy for effects in gas and liquid systems. Generalized Freundlich models, often hybridized with the Langmuir isotherm, extend the original equation to describe dual-site adsorption mechanisms, particularly in heterogeneous surfaces like used for removal. The hybrid Freundlich-Langmuir form combines the multilayer heterogeneity of Freundlich with Langmuir's saturation, expressed as qe=qm(KLCe)n1+KLCeq_e = \frac{q_m (K_L C_e)^n}{1 + K_L C_e} (where qmq_m is , KLK_L is Langmuir constant, and nn is the Freundlich exponent), fitting data for complex systems such as or heavy metal adsorption on granular or bio-based hybrids. In studies from 2020 onward, this approach has been used to model the removal of organic like dyes and pharmaceuticals from , showing superior fit over single isotherms in cases of site-specific binding. The integration of Freundlich equation parameters into frameworks has enhanced predictive modeling for adsorption in environmental simulations, where fitted KK and nn values serve as key inputs for algorithms like random forests or artificial neural networks. These models train on experimental isotherm data to forecast adsorption capacities under varying conditions, such as or co-pollutant presence, achieving high accuracy (e.g., R² > 0.95) in predicting breakthrough curves for micropollutants in . Recent applications, including optimizations for and systems, demonstrate how Freundlich-derived features improve scalability for large-scale environmental risk assessments. Extensions of the Freundlich equation for and competitive adsorption in multi-solute systems modify the exponent nn or introduce competition factors to handle interactions among ions or solutes in processes. For instance, multicomponent Freundlich variants, such as the Sheindorf-Rebuhn-Sheintuch (SRS) equation qe,i=KiCe,i1/n(∑j=1NαijCe,j1/n)n−1q_{e,i} = K_i C_{e,i}^{1/n} \left( \sum_{j=1}^N \alpha_{ij} C_{e,j}^{1/n} \right)^{n-1} (where αij\alpha_{ij} are competition coefficients derived from , assuming equal n for all components), better describe selective uptake in resins or sorbents for like Cu²⁺ and Pb²⁺. These modifications have been validated in recent studies on activated carbons and zeolites, revealing affinity orders and improved equilibrium predictions for real scenarios with multiple contaminants.

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