Journal of Chemistry
Volume 2017 (2017), Article ID 3039817, 11 pages
https://doi.org/10.1155/2017/3039817

Review Article

Modelling and Interpretation of Adsorption Isotherms

Nimibofa Ayawei, Augustus Newton Ebelegi, and Donbebe Wankasi

Department of Chemical Sciences, Niger Delta University, Wilberforce Island, Bayelsa State, Nigeria

Correspondence should be addressed to Nimibofa Ayawei; ayawei4acad@gmail.com

Received 2 May 2017; Accepted 1 August 2017; Published 5 September 2017

Academic Editor: Wenshan Guo

Copyright © 2017 Nimibofa Ayawei et al. This is an open access article distributed under the Creative Commons Attribution License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly cited.

Abstract.

The need to design low-cost adsorbents for the detoxification of industrial effluents has been a growing concern for most environmental researchers. So modelling of experimental data from adsorption processes is a very important means of predicting the mechanisms of various adsorption systems. Therefore, this paper presents an overall review of the applications of adsorption isotherms, the use of linear regression analysis, nonlinear regression analysis, and error functions for optimum adsorption data analysis.

1. Introduction

The migration of pollutant(s) in aqueous media and subsequent development of containment measures have resulted in the use of adsorption among other techniques [1, 2]. Adsorption equilibrium information is the most important piece of information needed for a proper understanding of an adsorption process.

A proper understanding and interpretation of adsorption isotherms is critical for the overall improvement of adsorption mechanism pathways and effective design of adsorption system [3].

In recent times, linear regression analysis has been one of the most applied tools for defining the best fitting adsorption models because it quantifies the distribution of adsorbates, analyzes the adsorption system, and verifies the consistency of theoretical assumptions of adsorption isotherm model [4].

Because of the inherent bias created by linearization, several error functions have been used to address this shortfall. Concomitant with the evolution of computer technology, the use of nonlinear isotherm modelling has been extensively used.

2. One-Parameter Isotherm

2.1. Henry’s Isotherms

This is the simplest adsorption isotherm in which the amount of surface adsorbate is proportional to the partial pressure of the adsorptive gas [4]. This isotherm model describes an appropriate fit to the adsorption of adsorbate at relatively low concentrations such that all adsorbate molecules are secluded from their nearest neighbours [5].

Thus, the equilibrium adsorbate concentrations in the liquid and adsorbed phases are related to the linear expression:

where is amount of the adsorbate at equilibrium (mg/g), is Henry’s adsorption constant, and is equilibrium concentration of the adsorbate on the adsorbent.

3. Two-Parameter Isotherm

3.1. Hill-Deboer Model

The Hill-Deboer isotherm model describes a case where there is mobile adsorption as well as lateral interaction among adsorbed molecules [6, 7].

The linearized form of this isotherm equation is as follows [8]:

where is Hill-Deboer constant (Lmg⁻¹) and is the energetic constant of the interaction between adsorbed molecules . Equilibrium data from adsorption experiments can be analyzed by plotting versus [8–10].

3.2. Fowler-Guggenheim Model

Fowler-Guggenheim proposed this isotherm equation which takes into consideration the lateral interaction of the adsorbed molecules [11]. The linear form of this isotherm model is as follows [8]:

where is Fowler-Guggenheim equilibrium constant , is fractional coverage, is universal gas constant (), is temperature (k), and is interaction energy between adsorbed molecules .

This isotherm model is predicated on the fact that the heat of adsorption varies linearly with loading. Therefore, if the interaction between adsorbed molecules is attractive, then the heat of adsorption will increase with loading because of increased interaction between adsorbed molecules as loading increases (i.e., = positive). However, if the interaction among adsorbed molecules is repulsive, then the heat of adsorption decreases with loading (i.e., = negative). But when then there is no interaction between adsorbed molecules, and the Fowler-Guggenheim isotherm reduces to the Langmuir equation.

A plot of versus is used to obtain the values for and .

It is important to note that this model is only applicable when surface coverage is less than 0.6 (.

Kumara et al. analyzed the adsorption data for the phenolic compounds onto granular activated carbon with the Fowler-Guggenheim isotherm and reported that the interaction energy () was positive which indicates that there is attraction between the adsorbed molecules [8].

3.3. Langmuir Isotherm

Langmuir adsorption which was primarily designed to describe gas-solid phase adsorption is also used to quantify and contrast the adsorptive capacity of various adsorbents [12]. Langmuir isotherm accounts for the surface coverage by balancing the relative rates of adsorption and desorption (dynamic equilibrium). Adsorption is proportional to the fraction of the surface of the adsorbent that is open while desorption is proportional to the fraction of the adsorbent surface that is covered [13].

The Langmuir equation can be written in the following linear form [14]:

where is concentration of adsorbate at equilibrium (mg g⁻¹).

is Langmuir constant related to adsorption capacity (mg g⁻¹), which can be correlated with the variation of the suitable area and porosity of the adsorbent which implies that large surface area and pore volume will result in higher adsorption capacity.

The essential characteristics of the Langmuir isotherm can be expressed by a dimensionless constant called the separation factor [15].

where is Langmuir constant (mg g⁻¹) and is initial concentration of adsorbate (mg g⁻¹).

values indicate the adsorption to be unfavourable when , linear when , favourable when , and irreversible when .

Da̧browski studied the adsorption of direct dye onto a Novel Green Adsorbate developed from Uncaria Gambir extract; their equilibrium data were well described by the Langmuir isotherm model [14].

3.4. Freundlich Isotherm

Freundlich isotherm is applicable to adsorption processes that occur on heterogonous surfaces [15]. This isotherm gives an expression which defines the surface heterogeneity and the exponential distribution of active sites and their energies [16].

The linear form of the Freundlich isotherm is as follows [17]:

where is adsorption capacity and is adsorption intensity; it also indicates the relative distribution of the energy and the heterogeneity of the adsorbate sites.

Boparai et al. investigate the adsorption of lead (II) ions [17] from aqueous solutions using coir dust and its modified extract resins. Although several isotherm models were applied, the equilibrium data was best represented by Freundlich and Flory-Huggins isotherms due to high correlation coefficients [18].

3.5. Dubinin-Radushkevich Isotherm

Dubinin-Radushkevich isotherm model [19] is an empirical adsorption model that is generally applied to express adsorption mechanism with Gaussian energy distribution onto heterogeneous surfaces [20].

This isotherm is only suitable for intermediate range of adsorbate concentrations because it exhibits unrealistic asymptotic behavior and does not predict Henry’s laws at low pressure [21].

The model is a semiempirical equation in which adsorption follows a pore filling mechanism [22]. It presumes a multilayer character involving Van Der Waal’s forces, applicable for physical adsorption processes, and is a fundamental equation that qualitatively describes the adsorption of gases and vapours on microporous sorbents [23].

It is usually applied to differentiate between physical and chemical adsorption of metal ions [22]. A distinguishing feature of the Dubinin-Radushkevich isotherm is the fact that it is temperature dependent; hence when adsorption data at different temperatures are plotted as a function of logarithm of amount adsorbed versus the square of potential energy, all suitable data can be obtained [13].

Dubinin-Radushkevich isotherm is expressed as follows [16]:

where ϵ is Polanyi potential, is Dubinin-Radushkevich constant, is gas constant (8.31 Jmol⁻¹ k⁻¹), is absolute temperature, and is mean adsorption energy.

Ayawei et al. and Vijayaraghavan et al. applied the Dubinin-Radushkevich isotherm in their investigation of Congo red adsorption behavior on Ni/Al-CO₃ and sorption behavior of cadmium on nanozero-valent iron particles, respectively [16, 22].

3.6. Temkin Isotherm

Temkin isotherm model takes into account the effects of indirect adsorbate/adsorbate interactions on the adsorption process; it is also assumed that the heat of adsorption of all molecules in the layer decreases linearly as a result of increase surface coverage [24]. The Temkin isotherm is valid only for an intermediate range of ion concentrations [25]. The linear form of Temkin isotherm model is given by the following [22]:

where is Temkin constant which is related to the heat of sorption and is Temkin isotherm constant [26].

Hutson and Yang applied Temkin isotherm model to confirm that the adsorption of cadmium ion onto nanozero-valent iron particles follows a chemisorption process. Similarly, Elmorsi et al. used the Temkin isotherm model in their investigation of the adsorption of methylene blue onto miswak leaves [18].

3.7. Flory-Huggins Isotherm

Flory-Huggins isotherm describes the degree of surface coverage characteristics of the adsorbate on the adsorbent [27].

The linear form of the Flory-Huggins equation is expressed as

where is degree of surface coverage, is number of adsorbates occupying adsorption sites, and is Flory-Huggins equilibrium constant .

This isotherm model can express the feasibility and spontaneity of an adsorption process.

The equilibrium constant is used to calculate spontaneity Gibbs free energy as shown in the following expression [28]:

where is standard free energy change, is universal gas constant 8.314 Jmol⁻¹ K⁻¹, and is absolute temperature.

Hamdaoui and Naffrechoux used the Flory-Huggins isotherm model in their study of the biosorption of Zinc from aqueous solution using coconut coir dust [29].

3.8. Hill Isotherm

The Hill isotherm equation describes the binding of different species onto homogeneous substrates. This model assumes that adsorption is a cooperative phenomenon with adsorbates at one site of the adsorbent influencing different binding sites on the same adsorbent [30].

The linear form of this isotherm is expressed as follows [29]:

where , , and are constants.

Hamdaoui and Naffrechoux investigated the equilibrium adsorption of aniline, benzaldehyde, and benzoic acid on granular activated carbon (GAC) using the Hill isotherm model; according to their report, the Hill model was very good in comparison with previous models with for all adsorbates [29].

3.9. Halsey Isotherm

The Halsey isotherm is used to evaluate multilayer adsorption at a relatively large distance from the surface [16]. The adsorption isotherm can be given as follows [31]:

where and are Halsey isotherm constant and they can be obtained from the slope and intercept of the plot of versus .

Fowler and Guggenheim reported the use of Halsey isotherm in their equilibrium studies of methyl orange sorption by pinecone derived activated carbon. The fitting of their experimental data to the Halsey isotherm model attests to the heteroporous nature of the adsorbent [31]. Similarly, Song et al. applied the Halsey isotherm for the study of coconut shell carbon prepared by KOH activation for the removal of ions from aqueous solutions. The Halsey isotherm fits the experimental data well due to high correlation coefficient , which may be attributed to the heterogeneous distribution of activate sites and multilayer adsorption on coconut shell carbons [16].

3.10. Harkin-Jura Isotherm

Harkin-Jura isotherm model assumes the possibility of multilayer adsorption on the surface of absorbents having heterogeneous pore distribution [32]. This model is expressed as follows:

where and are Harkin-Jura constants that can be obtained from plotting versus

Foo and Hameed reported that the Harkin-Jura isotherm model showed a better fit to the adsorption data than Freundlich, Halsey, and Temkin isotherm models in their investigation of the adsorptive removal of reactive black 5 from wastewater using Bentonite clay [32].

3.11. Jovanovic Isotherm

The Jovanovic model is predicated on the assumptions contained in the Langmuir model, but in addition the possibility of some mechanical contacts between the adsorbate and adsorbent [33].

The linear form of the Jovanovic isotherm is expressed as follows [34]:

where is amount of adsorbate in the adsorbent at equilibrium (mg g⁻¹), is maximum uptake of adsorbate obtained from the plot of versus , and is Jovanovic constant.

Kiseler reported the use of Jovanovic isotherm model while determining adsorption isotherms for L-Lysine imprinted polymer. Their report showed that the best prediction of retention capacity was obtained by applying the Jovanovic isotherm model [33].

3.12. Elovich Isotherm

The equation that defines this model is based on a kinetic principle which assumes that adsorption sites increase exponentially with adsorption; this implies a multilayer adsorption [35]. The equation was first developed to describe the kinetics of chemisorption of gas onto solids [36].

The linear forms of the Elovich model are expressed as follows [37]:

but the linear form is expressed as follows [8]:

Elovich maximum adsorption capacity and Elovich constant can be calculated from the slope and intercept of the plot of versus .

Rania et al. reported the use of Elovich isotherm model in their work titled “Equilibrium and Kinetic Studies of Adsorption of Copper (II) Ions on Natural Sorbent.” Their investigation showed that the value of the regression coefficient for the Elovich model was 0.808 which is higher than that of Langmuir; therefore the adsorption of copper (II) onto Chitin was best described by the Elovich isotherm.

3.13. Kiselev Isotherm

The Kiselev adsorption isotherm equation also known as localized monomolecular layer model [38] is only valid for surface coverage and its linearized expression is as follows:

where is Kiselev equilibrium constant (Lmg⁻¹) and is equilibrium constant of the formation of complex between adsorbed molecules.

Equilibrium data from adsorption processes can be modelled by plotting versus [8, 38–40].

4. Three-Parameter Isotherms

4.1. Redlich-Peterson Isotherm

The Redlich-Peterson isotherm is a mix of the Langmuir and Freundlich isotherms. The numerator is from the Langmuir isotherm and has the benefit of approaching the Henry region at infinite dilution [41].

This isotherm model is an empirical isotherm incorporating three parameters. It combines elements from both Langmuir and Freundlich equations; therefore the mechanism of adsorption is a mix and does not follow ideal monolayer adsorption [42].

This model is defined by the following expression:

where is Redlich-Peterson isotherm constant (Lg−1), is constant (Lmg⁻¹), is exponent that lies between 0 and 1, is equilibrium liquid-phase concentration of the adsorbent (mgl⁻¹), and is equilibrium adsorbate loading on the adsorbent (mg g⁻¹).

At high liquid-phase concentrations of the adsorbate, (16) reduces to the Freundlich equation:

where and of the Freundlich isotherm model.

When , (18) reduces to Langmuir equation with (Langmuir adsorption constant (Lmg⁻¹ which is related to the energy of adsorption.

where is Langmuir maximum adsorption capacity of the adsorbent (mg g⁻¹); when , (18) reduces to Henry’s equation with representing Henry’s constant.

The linear form of the Redlich-Peterson isotherm can be expressed as follows [34]:

A plot of versus enables the determination of Redlich-Peterson constants, where is slope and is intercept [30, 42–45].

This isotherm model has a linear dependence on concentration in the numerator and an exponential function in the denomination which altogether represent adsorption equilibrium over a wide range of concentration of adsorbate which is applicable in either homogenous or heterogeneous systems because of its versatility [46, 47].

4.2. Sips Isotherm

Sips isotherm is a combination of the Langmuir and Freundlich isotherms and it is given the following general expression [48]:

where is Sips isotherm model constant (Lg⁻¹), is Sips isotherm exponent, and is Sips isotherm model constant (Lg⁻¹). The linearized form is given as follows [12]:

This model is suitable for predicting adsorption on heterogeneous surfaces, thereby avoiding the limitation of increased adsorbate concentration normally associated with the Freundlich model [19]. Therefore at low adsorbate concentration this model reduces to the Freundlich model, but at high concentration of adsorbate, it predicts the Langmuir model (monolayer adsorption). The parameters of the Sips isotherm model are , temperature, and concentration dependent [12, 49] and isotherm constants differ by linearization and nonlinear regression [50].

4.3. Toth Isotherm

The Toth isotherm is another empirical modification of the Langmuir equation with the aim of reducing the error between experimental data and predicted value of equilibrium data [51]. This model is most useful in describing heterogeneous adsorption systems which satisfy both low and high end boundary of adsorbate concentration [52]. The Toth isotherm model is expressed as follows [52]:

where is Toth isotherm constant (mg g⁻¹) and is Toth isotherm constant (mg g⁻¹).

It is clear that when , this equation reduces to Langmuir isotherm equation. Therefore the parameter characterizes the heterogeneity of the adsorption system [51] and if it deviates further away from unity (1), then the system is said to be heterogeneous. The Toth isotherm may be rearranged to give a linear form as follows:

The values of parameters of the Toth model can be evaluated by nonlinear curve fitting method using sigma plot software [53].

This isotherm model has been applied for the modelling of several multilayer and heterogeneous adsorption systems [53, 54].

4.4. Koble-Carrigan Isotherm

Koble-Carrigan isotherm model is a three-parameter equation which incorporates both Langmuir and Freundlich isotherms for representing equilibrium adsorption data [55]. The linear form of this module is represented by the following equation [56]:

where is Koble-Carrigan’s isotherm constant, is Koble-Carrigan’s isotherm constant, and is Koble-Carrigan’s isotherm constant.

All three Koble-Carrigan isotherm constants can be evaluated with the use of a solver add-in function of the Microsoft Excel [56]. At high adsorbate concentrations, this model reduces to Freundlich isotherm. It is only valid when the constant “” is greater than or equal to 1. When “” is less than unity (1), it signifies that the model is incapable of defining the experimental data despite high concentration coefficient or low error value [54].

4.5. Kahn Isotherm

The Kahn isotherm model is a general model for adsorption of biadsorbate from pure dilute equations solutions [57].

This isotherm model is expressed as follows [58]:

where is Kahn isotherm model exponent, is Khan isotherm model constant, and is Khan isotherm maximum adsorption capacity (mg g⁻¹).

Nonlinear methods have been applied by several researchers to obtain the Khan isotherm model parameters [59, 60].

4.6. Radke-Prausniiz Isotherm

The Radke-Prausnitz isotherm model has several important properties which makes it more preferred in most adsorption systems at low adsorbate concentration [61].

The isotherm is given by the following expression:

where is Radke-Prausnitz maximum adsorption capacity (mg g⁻¹), is Radke-Prausnitz equilibrium constant, and is Radke-Prausnitz model exponent.

At low adsorbate concentration, this isotherm model reduces to a linear isotherm, while at high adsorbate concentration it becomes the Freundlich isotherm and when , it becomes the Langmuir isotherm. Another important characteristic of this isotherm is that it gives a good fit over a wide range of adsorbate concentration. The Radke-Prausnitz model parameters are obtained by nonlinear statistical fit of experimental data [61, 62].

4.7. Langmuir-Freundlich Isotherm

Langmuir-Freundlich isotherm includes the knowledge of adsorption heterogeneous surfaces. It describes the distribution of adsorption energy onto heterogeneous surface of the adsorbent [54]. At low adsorbate concentration this model becomes the Freundlich isotherm model, while at high adsorbate concentration it becomes the Langmuir isotherm. Langmuir-Freundlich isotherm can be expressed as follows:

where is Langmuir-Freundlich maximum adsorption capacity (mg g⁻¹), is equilibrium constant for heterogeneous solid, and is heterogeneous parameter and it lies between 0 and 1. These parameters can be obtained by using the nonlinear regression techniques [63].

4.8. Jossens Isotherm

The Jossens isotherm model predicts a simple equation based on the energy distribution of adsorbate-adsorbent interactions at adsorption sites [64]. This model assumes that the adsorbent has heterogeneous surface with respect to the interactions it has with the adsorbate. The Jossen isotherm can be represented as follows:

where is Jossens isotherm constant (it corresponds to Henry’s constant), is Jossens isotherm constant and it is characteristic of the adsorbent irrespective of temperature and the nature of adsorbents, and is Jossens isotherm constant.

The equation reduces to Henry’s law at low capacities. However, upon rearranging (29) [65],

The values of and can be obtained from either a plot of versus or using a least square fitting procedure.

A good representation of equilibrium data using this equation was reported for phenolic compounds on activated carbon [66] and on amberlite XAD-4 and XAD-7 macroreticular resins [67].

5. Four-Parameter Isotherms

5.1. Fritz-Schlunder Isotherm

Fritz and Schlunder derived an empirical equation which can fit a wide range of experimental results because of the large number of coefficients in the isotherm [68].

This isotherm model has the following equation:

where is Fritz-Schlunder maximum adsorption capacity (mg g⁻¹), is Fritz-Schlunder equilibrium constant (mg g⁻¹), and is Fritz-Schlunder model exponent.

If , then the Fritz-Schlunder model becomes the Langmuir model, but, for high adsorbate concentrations, the model reduces to Freundlich model.

Fritz-Schlunder isotherm parameters can be determined by nonlinear regression analysis [69, 70].

5.2. Baudu Isotherm

Bauder observed that the estimation of the Langmuir coefficients, and , by measurement of tangents at different equilibrium concentrations shows that they are not constants in a broad range [71]; therefore the Langmuir isotherm has been reduced to the Bauder isotherm [62]:

where id Bauder maximum adsorption capacity (mg g⁻¹), is equilibrium constant, is Baudu parameter, and is Baudu parameter.

For lower surface coverage the Bauder isotherm model reduces to Freundlich model.

Due to the inherent bias resulting from linearization this isotherm parameters are determined by nonlinear regression analysis [72].

5.3. Weber-Van Vliet Isotherm

Weber and Van Vliet postulated an empirical relation with four parameters that provided excellent description of data patterns for a wide range of adsorption systems [73].

The isotherm developed by weber and Van Vliet has the following form:

where is equilibrium concentration of the adsorbate (mg g⁻¹), is adsorption capacity mg g⁻¹, , , , and are Weber-Van Vliet isotherm parameters

The isotherm parameters (, , , and ) can be defined by multiple nonlinear curve fitting techniques which is predicated on the minimization of sum of square of residual [72–74].

5.4. Marczewski-Jaroniec Isotherm

The Marczewski-Jaroniec isotherm is also known as the four-parameter general Langmuir equation [75]. It is recommended on the basis of the supposition of local Langmuir isotherm and adsorption energies distribution in the active sites on adsorbent [76].

The isotherm equation is expressed as follows:

where and are parameters that characterize the heterogeneity of the adsorbent surface, describes the spreading of distribution in the path of higher adsorption energy, and describes the spreading in the path of lesser adsorption energies.

The isotherm reduces to Langmuir isotherm when and , when ; it reduces to Langmuir-Freundlich model.

6. Five-Parameter Isotherms

Fritz and Schlunder developed a five-parameter empirical model that is capable of simulating the model variations more precisely for application over a wide range of equilibrium data [74].

The isotherm equation is

where is Fritz-Schlunder maximum adsorption capacity (mg g⁻¹) and , , , and are Fritz-Schlunder parameters.

This isotherm is valid only in the range of value less than or equal to 1.

This model approaches Langmuir model while the value of both exponents and equals 1 and for higher adsorbate concentrations it reduces to Freundlich model.

7. Error Analysis

In recent times linear regression analysis has been among the most pronounced and viable tools frequently applied for analysis of experimental data obtained from adsorption process. It has been used to define the best fitting relationship that quantify the distribution of adsorbates and also in the verification of the consistency of adsorption models and the theoretical assumptions of adsorption models [77, 78].

Studies have shown that the error structure of experimental data is usually changed during the transformation of adsorption isotherms into their linearized forms [79]. It is against this backdrop that nonlinearized regression analysis became inevitable, since it provides a mathematically rigorous method for determining adsorption parameters using original form of isotherm equations [80, 81].

Unlike linear regression, nonlinear regression usually involved the minimization of error distribution between the experimental data and the predicted isotherm based on its convergence criteria [82]. This operation is no longer computationally difficult because of availability of computer algorithms [21].

7.1. The Sum Square of Errors (ERRSQ)

The sum of square of errors (ERRSQ) is said to be the most widely used error function [83]. This method can be represented by the following expression [45]:

where is the theoretical concentration of adsorbate on the adsorbent, which have been calculated from one of the isotherm models.

is the experimentally measured adsorbed solid phase concentration of the adsorbate adsorbed on the adsorbent.

One major disadvantage of this error function is that at higher end of liquid-phase adsorbate concentration ranges the isotherm parameters derived using this error function will provide a better fit as the magnitude of the errors and therefore the square of errors tend to increase illustrating a better fit for experimental data obtained at the high end of concentration range [45, 84].

7.2. Hybrid Fractional Error Function (HYBRID)

The hybrid fractional error function (HYBRID) was developed by Kapoor and Yang, to improve the fit of the sum square of errors (ERRSQ) [85] at low concentrations by dividing it by the measured value. This function includes the number of data points (), minus the number of parameters () or isotherm equation as a divisor [85].

The equation for this error function is

7.3. Average Relative Error (ARE)

The average relative error was developed by Marquardt [86] with the aim of minimizing the fractional error distribution across the entire concentration range. It is given by the following expression:

7.4. Marquardt’s Percent Standard Deviation (MPSD)

The Marquardt’s percent standard deviation error function is similar to a geometric mean error distribution modified according to the degree of freedom of the system [87]. It is given by the following expression:

7.5. Sum of Absolute Errors (EABS)

This model is similar to the sum square error (ERRSQ) function. In this case isotherm parameters determined using this error function would provide a better fit as the forward high concentration data [88]. It is represented by the following equation:

7.6. Sum of Normalized Errors (SNE)

Since each of the error criteria is likely to produce a different set of parameters of the isotherm, a standard procedure known as sum of the normalized errors is adopted to normalize and to combine the error in order to make a move meaningful comparison between the parameters sets. It has been used by several researchers to determine the best fitting isotherm model [88–91].

Calculation procedure is as follows:

(i)Selection of an isotherm model and error function and determination of the adjustable parameters which minimized the error function(ii)Determination of all other error functions by referring to the parameters set(iii)Computation of other parameter sets associated with their error function values(iv)Normalization and selection of maximum parameters sets with respect to the largest error measurement(v)Summation of all these normalized errors for each parameter set

7.7. Coefficient of Determination (²) Spearman’s Correlation Coefficient () and Standard Deviation of Relative Errors (RE)

The coefficient of determination represents the variance about the mean; it is used to analyze the fitting degrees of isotherms and kinetic models with experimental data [12, 92]. The coefficient of determination () is defined by the following equation [93]:

where is amount of adsorbate adsorbed by adsorbent during the experiment (mg g⁻¹), is amount of adsorbate obtained by kinetic isotherm models (mg g⁻¹), and is average of (mg g⁻¹).

7.8. Nonlinear Chi-Square Test ()

This function is very important in the determination of the best fit of an adsorption system. It can be obtained by judging the sum square difference between experimental and calculated data, with each square difference divided by its corresponding values [90]. The value of this function can be obtained from the following equation:

7.9. Coefficient of Nondetermination

This function is very valuable tool for describing the extent of relationship between the transformed experimental data and the predicted isotherms and minimization of error distribution [93].

where is coefficient of determination.

8. Conclusion

The level of accuracy obtained from adsorption processes is greatly dependent on the successful modelling and interpretation of adsorption isotherms.

While linear regression analysis has been frequently used in accessing the quality of fits and adsorption performance because of its wide applicability in a variety of adsorption data, nonlinear regression analysis has also been widely used by a number of researchers in a bid to close the gap between predicted and experimental data. Therefore, there is the need to identify and clarify the usefulness of both linear and nonlinear regression analysis in various adsorption systems.

Conflicts of Interest

The authors (Ayawei Nimibofa, Ebelegi Newton Augustus, and Wankasi Donbebe) declare that there are no conflicts of interest regarding the publication of this paper.

References

N. Ayawei, M. Horsfall Jnr, and I. Spiff, “Rhizophora mangle waste as adsorbent for metal ions removal from aqueous solution,” European Journal of Scientic Research, vol. 9, no. 1, p. 21, 2005.

N. D. Shooto, N. Ayawei, D. Wankasi, L. Sikhwivhilu, and E. D. Dikio, “Study on cobalt metal organic framework material as adsorbent for lead ions removal in aqueous solution,” Asian Journal of Chemistry, vol. 28, no. 2, pp. 277–281, 2016.

M. I. El-Khaiary, “Least-squares regression of adsorption equilibrium data: comparing the options,” Journal of Hazardous Materials, vol. 158, no. 1, pp. 73–87, 2008.

S. D. Fost and M. O. Aly, Adsorption Processes for Water Treatment, Betterworth Publications, Stoneharm, Massachusetts, Mass, USA, 1981.

D. M. Ruthven, Principle of Adsorption and Adsorption Processes, John Willey and Sons, New Jersey, NJ, USA, 1984.

T. L. Hill, “Statistical mechanics of multimolecular adsorption II. Localized and mobile adsorption and absorption,” The Journal of Chemical Physics, vol. 14, no. 7, pp. 441–453, 1946.

J. H. De Boer, The Dynamical Character of Adsorption, Oxford University Press, Oxford, England, 1953.

P. S. Kumara, S. Ramalingamb, S. D. Kiruphac, A. Murugesanc, and S. Vidhyarevicsivanesam, “Adsorption behaviour of Nickel (II) onto cashew nut shell,” in Equilibrium, Thermodynamics, Kinetics, Mechanism and Process design. Chemical Engineering Journal, vol. 1169, pp. 122–131, Adsorption behaviour of Nickel (II) onto cashew nut shell, Equilibrium, 2010.

M. A. Hubbe, J. Park, and S. Park, “Cellulosic substrates for removal of pollutants from aqueous systems: A review. Part 4. Dissolved petrochemical compounds,” BioResources, vol. 9, no. 4, pp. 7782–7925, 2014.

O. Redlich and D. L. Peterson, “A useful adsorption isotherm,” The Journal of Physical Chemistry, vol. 63, no. 6, p. 1024, 1959.

P. Sampranpiboon, P. Charnkeitkong, and X. Feng, “Equilibrium isotherm models for adsorption of zinc (II) ion from aqueous solution on pulp waste,” WSEAS Transactions on Environment and Development, vol. 10, pp. 35–47, 2014.

T. M. Elmorsi, “Equilibrium isotherms and kinetic studies of removal of methylene blue dye by adsorption onto miswak leaves as a natural adsorbent,” Journal of Environmental Protection, vol. 2, no. 6, pp. 817–827, 2011.

A. Günay, E. Arslankaya, and I. Tosun, “Lead removal from aqueous solution by natural and pretreated clinoptilolite: adsorption equilibrium and kinetics,” Journal of Hazardous Materials, vol. 146, no. 1-2, pp. 362–371, 2007.

A. Da̧browski, “Adsorption—from theory to practice,” Advances in Colloid and Interface Science, vol. 93, no. 1–3, pp. 135–224, 2001.

N. Ayawei, S. S. Angaye, D. Wankasi, and E. D. Dikio, “Synthesis, characterization and application of Mg/Al layered double hydroxide for the degradation of congo red in aqueous solution,” Open Journal of Physical Chemistry, vol. 5, no. 03, pp. 56–70, 2015.

N. Ayawei, A. T. Ekubo, D. Wankasi, and E. D. Dikio, “Adsorption of congo red by Ni/Al-CO₃: equilibrium, thermodynamic and kinetic studies,” Oriental Journal of Chemistry, vol. 31, no. 30, pp. 1307–1318, 2015.

H. K. Boparai, M. Joseph, and D. M. O'Carroll, “Kinetics and thermodynamics of cadmium ion removal by adsorption onto nano zerovalent iron particles,” Journal of Hazardous Materials, vol. 186, no. 1, pp. 458–465, 2011.

N. D. Hutson and R. T. Yang, “Theoretical basis for the Dubinin-Radushkevitch (D-R) adsorption isotherm equation,” Adsorption, vol. 3, no. 3, pp. 189–195, 1997.

C. C. Travis and E. L. Etnier, “A survey of sorption relationships for reactive solutes in soil,” Journal of Environmental Quality, vol. 10, no. 1, pp. 8–17, 1981.

O. Çelebi, Ç. Üzüm, T. Shahwan, and H. N. Erten, “A radiotracer study of the adsorption behavior of aqueous Ba²⁺ ions on nanoparticles of zero-valent iron,” Journal of Hazardous Materials, vol. 148, no. 3, pp. 761–767, 2007.

C. Theivarasu and S. Mylsamy, “Removal of malachite green from aqueous solution by activated carbon developed from cocoa (Theobroma Cacao) shell—A kinetic and equilibrium studies,” E-Journal of Chemistry, vol. 8, no. 1, pp. S363–S371, 2011.

K. Vijayaraghavan, T. V. N. Padmesh, K. Palanivelu, and M. Velan, “Biosorption of nickel(II) ions onto Sargassum wightii: application of two-parameter and three-parameter isotherm models,” Journal of Hazardous Materials, vol. 133, no. 1–3, pp. 304–308, 2006.

U. Israel and U. M. Eduok, “Biosorption of zinc from aqueous solution using coconut (Cocos nuciferaL) coirdust,” Archives of Applied Science Research, vol. 4, pp. 809–819, 2012.

D. Ringot, B. Lerzy, K. Chaplain, J.-P. Bonhoure, E. Auclair, and Y. Larondelle, “In vitro biosorption of ochratoxin A on the yeast industry by-products: comparison of isotherm models,” Bioresource Technology, vol. 98, no. 9, pp. 1812–1821, 2007.

H. Shahbeig, N. Bagheri, S. A. Ghorbanian, A. Hallajisani, and S. Poorkarimi, “A new adsorption isotherm model of aqueous solutions on granular activated carbon,” World Journal of Modelling and Simulation, vol. 9, no. 4, pp. 243–254, 2013.

M. R. Samarghandi, M. Hadi, S. Moayedi, and F. B. Askari, “Two-parameter isotherms of methyl orange sorption by pinecone derived activated carbon,” Iranian Journal of Environmental Health Science and Engineering, vol. 6, no. 4, pp. 285–294, 2009.

M. T. Amin, A. A. Alazba, and M. Shafiq, “Adsorptive removal of reactive black 5 from wastewater using bentonite clay: isotherms, kinetics and thermodynamics,” Sustainability, vol. 7, no. 11, pp. 15302–15318, 2015.

N. A. Ebelegi, S. S. Angaye, N. Ayawei, and D. Wankasi, “Removal of congo red from aqueous solutions using fly ash modified with hydrochloric acid,” British Journal of Applied Science and Technology, vol. 20, no. 4, pp. 1–7, 2017.

O. Hamdaoui and E. Naffrechoux, “Modeling of adsorption isotherms of phenol and chlorophenols onto granular activated carbon. Part I. Two-parameter models and equations allowing determination of thermodynamic parameters,” Journal of Hazardous Materials, vol. 147, no. 1-2, pp. 381–394, 2007.

F. Rania and N. S. Yousef, “Equilibrium and Kinetics studies of adsorption of copper (II) on natural Biosorbent,” International Journal of Chemical/Engineering and Applications, vol. 6, no. 5, 2015.

R. H. Fowler and E. A. Guggenheim, Statistical Thermodynamics, Cambridge University Press, London, England, 1939.

K. Y. Foo and B. H. Hameed, “Insights into the modeling of adsorption isotherm systems,” Chemical Engineering Journal, vol. 156, no. 1, pp. 2–10, 2010.

S. K. Knaebel, “Adsorbent selection,” International Journal of Trend in Research and Development, Adsorption Research, Incorporated Dublin, Ohio. 43016, 2004.

A. V. C. Kiseler, “vapour adsorption in the formation of adsorbate Mollecule Complexes on the surface,” Kolloid Zhur, vol. 20, pp. 338–348, 1958.

M. Gubernak, W. Zapała, and K. Kaczmarski, “Analysis of amylbenzene adsorption equilibria on an RP-18e chromatographic column,” Acta Chromatographica, no. 13, pp. 38–59, 2003.

O. Hamdaoui and E. Naffrechoux, “Modeling of adsorption isotherms of phenol and chlorophenols onto granular activated carbon. Part II. Models with more than two parameters,” Journal of Hazardous Materials, vol. 147, no. 1-2, pp. 401–411, 2007.

A. Achmad, J. Kassim, T. K. Suan, R. C. Amat, and T. L. Seey, “Equilibrium, kinetic and thermodynamic studies on the adsorption of direct dye onto a novel green adsorbent developed from Uncaria gambir extract,” Journal of Physical Science, vol. 23, no. 1, pp. 1–13, 2012.

T. W. Weber and R. K. Chakravorti, “Pore and solid diffusion models for fixed-bed adsorbers,” Journal of American Institute of Chemical Engineers, vol. 20, no. 2, pp. 228–238, 1974.

C. Song, S. Wu, M. Cheng, P. Tao, M. Shao, and G. Gao, “Adsorption studies of coconut shell carbons prepared by KOH activation for removal of lead(ii) from aqueous solutions,” Sustainability (Switzerland), vol. 6, no. 1, pp. 86–98, 2014.

A. A. Israel, O. Okon, S. Umoren, and U. Eduok, “Kinetic and equilibrium studies of adsorption of lead (II) Ions from aqueous solution using coir dust (Cocos nucifera L) and it's modified extract resins,” The Holistic Approach to Environment, 2013.

M. Davoundinejad and S. A. Gharbanian, “Modelling of adsorption isotherm of benzoic compounds onto GAC and introducing three neww isotherm models using new concept of adsorption effective surface (AEC),” Academic Journals, vol. 18, no. 46, pp. 2263–2275, 2013.

F. Brouers and T. J. Al-Musawi, “On the optimal use of isotherm models for the characterization of biosorption of lead onto algae,” Journal of Molecular Liquids, vol. 212, pp. 46–51, 2015.

F.-C. Wu, B.-L. Liu, K.-T. Wu, and R.-L. Tseng, “A new linear form analysis of Redlich-Peterson isotherm equation for the adsorptions of dyes,” Chemical Engineering Journal, vol. 162, no. 1, pp. 21–27, 2010.

L. S. Chan, W. H. Cheung, S. J. Allen, and G. McKay, “Error analysis of adsorption isotherm models for acid dyes onto bamboo derived activated carbon,” Chinese Journal of Chemical Engineering, vol. 20, no. 3, pp. 535–542, 2012.

J. C. Y. Ng, W. H. Cheung, and G. McKay, “Equilibrium studies of the sorption of Cu(II) ions onto chitosan,” Journal of Colloid and Interface Science, vol. 255, no. 1, pp. 64–74, 2002.

F. Gimbert, N. Morin-Crini, F. Renault, P.-M. Badot, and G. Crini, “Adsorption isotherm models for dye removal by cationized starch-based material in a single component system: error analysis,” Journal of Hazardous Materials, vol. 157, no. 1, pp. 34–46, 2008.

R. Sips, “On the structure of a catalyst surface,” The Journal of Chemical Physics, vol. 16, no. 5, pp. 490–495, 1948.

G. P. Jeppu and T. P. Clement, “A modified Langmuir-Freundlich isotherm model for simulating pH-dependent adsorption effects,” Journal of Contaminant Hydrology, vol. 129-130, pp. 46–53, 2012.

C. Chen, “Evaluation of equilibrium sorption isotherm equations,” Open Chemical Engineering Journal, vol. 7, no. 1, pp. 24–44, 2012.

J. Toth, “State equation of the solid gas interface layer,” Acta Chimica (Academiae Scientiarum) Hungaricae, vol. 69, pp. 311–317, 1971.

T. Jafari Behbahani and Z. Jafari Behbahani, “A new study on asphaltene adsorption in porous media,” Petroleum and Coal, vol. 56, no. 5, pp. 459–466, 2014.

M. S. Padder and C. B. C. Majunder, Studies on Removal of As(II) and S(V) onto GAC/MnFe, 804 Composite: Isotherm Studies and Error Analysis, 2012.

T. Benzaoui, A. Selatnia, and D. Djabali, “Adsorption of copper (II) ions from aqueous solution using bottom ash of expired drugs incineration,” Adsorption Science and Technology, pp. 1–16, 2017.

R. A. Koble and T. E. Corrigan, “Adsorption isotherms for pure hydrocarbons,” Industrial and Engineering Chemistry, vol. 44, no. 2, pp. 383–387, 1952.

S. Alahmadi, S. Mohamad, and M. J. Maah, “Comparative study of tributyltin adsorption onto mesoporous silica functionalized with calix(4) arene, p-tert-butylcalix(4) arene and p-sulfonatocalix(4) arene,” Molecules, vol. 19, no. 4, pp. 4524–4547, 2014.

A. R. Khan, R. Ataullah, and A. Al-Haddad, “Equilibrium adsorption studies of some aromatic pollutants from dilute aqueous solutions on activated carbon at different temperatures,” Journal of Colloid and Interface Science, vol. 194, no. 1, pp. 154–165, 1997.

O. Amrhar and M. S. NassaliElyoubi, “Two and three-parameter isothermal modeling for adsorption of Crystal Violet dye onto Natural Illitic Clay: nonlinear regression analysis,” Journal of Chemical and Pharmaceutical Research, vol. 7, no. 9, pp. 892–903, 2015.

O. Amrhar, H. Nassai, and M. S. Elyoubi, “Application of nonlinear regression analysis to select the optimum absorption isotherm for Methylene Blue adsorption onto Natural Illitic Clay,” Bulletia de la societe Royale des Science de Kiege, vol. 84, pp. 116–130, 2015.

G. Varank, A. Demir, K. YetiImezsoy, S. Top, E. Sekman, and M. S. Bilgili, “Removal of 4-nitrophenol from aqueous solution by natural low cost adsorbents,” Indian Journal of Chemical Technology, vol. 19, pp. 7–25, 2011.

F. B. Aarden, “Adsorption onto Heterogeneous porous materials,” Equilibria and Kinetics Eindorea, Technische Universiteit Eindoven, 2001.

B. Subramanyam and D. Ashutosh, “Adsorption isotherm modeling of phenol onto natural soils—applicability of various isotherm models,” International Journal of Environmental Research, vol. 6, no. 1, pp. 265–276, 2012.

S. A. Al-Jlil and M. S. Latif, “Evaluation of Equilibrium isotherms models for the adsorption of Cu and Ni from wastewater on Benronite clay,” Material and Technology, vol. 47, no. 4, pp. 481–486, 2013.

L. Jossens, J. M. Prausnitz, W. Fritz, E. U. Schlünder, and A. L. Myers, “Thermodynamics of multi-solute adsorption from dilute aqueous solutions,” Chemical Engineering Science, vol. 33, no. 8, pp. 1097–1106, 1978.

M. F. Dilekoglu, “Use of generic algorithm optimzation Techniques in the adsorption of phenol on Banana and grapetruit peels,” Journal of the Chemical Society of Pakistan, vol. 38, no. 6, 2016.

R. Juang, F. Wu, and R. Tseng, “Adsorption isotherms of phenolic compounds from aqueous solutions onto activated carbon fibers,” Journal of Chemical and Engineering Data, vol. 41, no. 3, pp. 487–492, 1996.

A. Etaya, N. Koto, and J. Yamanato, “Liquid phase adsorption equilibrium of rhenol and it's derivatives on macroreticular adsorbents,” J. Chem. Eng. JPN, vol. 17, p. 389, 1984.

W. Fritz and E.-U. Schluender, “Simultaneous adsorption equilibria of organic solutes in dilute aqueous solutions on activated carbon,” Chemical Engineering Science, vol. 29, no. 5, pp. 1279–1282, 1974.

Z. L. Yaneva, B. K. Koumanova, and N. V. Georgieva, “Linear regression and nonlinear regression methods for equilibrium modelling of p-nitrophenol biosorption by Rhyzopus oryzen: comparison of error analysic criteria,” Journal of Chemistry, vol. 2013, Article ID 517631, 10 pages, 2013.

N. Singh and C. Balomajumder, “Removal of cyanide from aqueous media by adsorption using Al-activated carbon: parametric experiments equilibrium, kinetics and thermodynamic analysis,” in Proceedings of the 2nd International Conference on Science, Technology and Management, University of Delhi, New Delhi, India, 2015.

M. S. Podder and C. B. Majumder, Simultaneous Biosorption and Bioaccumulation: A Novel Technique for the Efficient Removal of Arsenic, Department of Chemical Engineering, Institute of Technology, Roorkee, India, 2017.

G. McKay, A. Mesdaghinia, S. Nasseri, M. Hadi, and M. Solaimany Aminabad, “Optimum isotherms of dyes sorption by activated carbon: fractional theoretical capacity and error analysis,” Chemical Engineering Journal, vol. 251, pp. 236–247, 2014.

B. M. van Vliet, W. J. Weber Jr., and H. Hozumi, “Modeling and prediction of specific compound adsorption by activated carbon and synthetic adsorbents,” Water Research, vol. 14, no. 12, pp. 1719–1728, 1980.

K. Vijayaraghavan, “Biosorption of Lan thamide (preseodymium) using ulva lactuca: mechanistic study and application of two, three, four and five parameter isotherm models,” Journal of Environment and Biotechnology Research, vol. 1, no. 1, pp. 1–8, 2015.

G. R. Parker Jr., “Optimum isotherm equation and thermodynamic interpretation for aqueous 1,1,2-trichloroethene adsorption isotherms on three adsorbents,” Adsorption, vol. 1, no. 2, pp. 113–132, 1995.

N. Sivarajasekar and R. Baskar, “Adsoprtion of basic red onto activated carbon derived from immature cotton seeds: Isotherm studies and ether analysis,” Desalination and Water Treatment, vol. 52, pp. 1–23, 2014.

C. Chen, “Evaluation of equilibrium sorption isotherm equations,” Open Chemical Engineering Journal, vol. 7, pp. 24–44, 2003.

T. F. Edgar and D. M. Himmelblau, Optimization of Chemical Processes, 1989.

O. T. Hanna and O. C. Sandall, Computerization Methods in Chemical Engineering, Printice-Hall International, New Jessey, NH, USA, 1995.

K. V. Kumar, “Comparative analysis of linear and non-linear method of estimating the sorption isotherm parameters for malachite green onto activated carbon,” Journal of Hazardous Materials, vol. 136, no. 2, pp. 197–202, 2006.

D. H. Lataye, I. M. Mishra, and I. D. Mall, “Adsorption of 2-picoline onto bagasse fly ash from aqueous solution,” Chemical Engineering Journal, vol. 138, no. 1–3, pp. 35–46, 2008.

K. V. Kumar, K. Porkodi, and F. Rocha, “Isotherms and thermodynamics by linear and non-linear regression analysis for the sorption of methylene blue onto activated carbon: Comparison of various error functions,” Journal of Hazardous Materials, vol. 151, no. 2-3, pp. 794–804, 2008.

K. V. Kumar and S. Sivanesan, “Pseudo second order kinetics and pseudo isotherms for malachite green onto activated carbon: comparison of linear and non-linear regression methods,” Journal of Hazardous Materials, vol. 136, no. 3, pp. 721–726, 2006.

V. S. Mane, I. Deo Mall, and V. Chandra Srivastava, “Kinetic and equilibrium isotherm studies for the adsorptive removal of Brilliant Green dye from aqueous solution by rice husk ash,” Journal of Environmental Management, vol. 84, no. 4, pp. 390–400, 2007.

J. F. Porter, G. McKay, and K. H. Choy, “The prediction of sorption from a binary mixture of acidic dyes using single- and mixed-isotherm variants of the ideal adsorbed solute theory,” Chemical Engineering Science, vol. 54, no. 24, pp. 5863–5885, 1999.

A. Kapoor and R. T. Yang, “Correlation of equilibrium adsorption data of condensible vapours on porous adsorbents,” Gas Separation and Purification, vol. 3, no. 4, pp. 187–192, 1989.

D. Marquardt, “An algorithm for least-squares estimation of nonlinear parameters,” SIAM Journal on Applied Mathematics, vol. 11, no. 2, pp. 431–441, 1963.

J. Ng, W. H. Cheung, and G. McKay, “Equilibrium studies for the sorption of lead from effluents using chitosan,” Chemosphere, vol. 52, no. 6, pp. 1021–1030, 2003.

S. Kundu and A. K. Gupta, “Arsenic adsorption onto iron oxide-coated cement (IOCC): regression analysis of equilibrium data with several isotherm models and their optimization,” Chemical Engineering Journal, vol. 122, no. 1-2, pp. 93–106, 2006.

B. Boulinguiez, P. Le Cloirec, and D. Wolbert, “Revisiting the determination of langmuir parameters-application to tetrahydrothiophene adsorption onto activated carbon,” Langmuir, vol. 24, no. 13, pp. 6420–6424, 2008.

F. J. Rivas, F. J. Beltrán, O. Gimeno, J. Frades, and F. Carvalho, “Adsorption of landfill leachates onto activated carbon. Equilibrium and kinetics,” Journal of Hazardous Materials, vol. 131, no. 1-3, pp. 170–178, 2006.

D. Karadag, Y. Koc, M. Turan, and M. Ozturk, “A comparative study of linear and non-linear regression analysis for ammonium exchange by clinoptilolite zeolite,” Journal of Hazardous Materials, vol. 144, no. 1-2, pp. 432–437, 2007.

Y. S. Ho, “Second-order kinetic model for the sorption of cadmium onto tree fern: a comparison of linear and non-linear methods,” Water Research, vol. 40, no. 1, pp. 119–125, 2006.

K. V. Kumar, K. Porkodi, and F. Rocha, “Comparison of various error functions in predicting the optimum isotherm by linear and non-linear regression analysis for the sorption of basic red 9 by activated carbon,” Journal of Hazardous Materials, vol. 150, no. 1, pp. 158–165, 2008.