Linearised and non-linearised isotherm models optimization analysis by error functions and statistical means
© Subramanyam and Das; licensee BioMed Central Ltd. 2014
Received: 31 July 2012
Accepted: 31 May 2014
Published: 10 June 2014
In adsorption study, to describe sorption process and evaluation of best-fitting isotherm model is a key analysis to investigate the theoretical hypothesis. Hence, numerous statistically analysis have been extensively used to estimate validity of the experimental equilibrium adsorption values with the predicted equilibrium values. Several statistical error analysis were carried out. In the present study, the following statistical analysis were carried out to evaluate the adsorption isotherm model fitness, like the Pearson correlation, the coefficient of determination and the Chi-square test, have been used. The ANOVA test was carried out for evaluating significance of various error functions and also coefficient of dispersion were evaluated for linearised and non-linearised models. The adsorption of phenol onto natural soil (Local name Kalathur soil) was carried out, in batch mode at 30 ± 20 C. For estimating the isotherm parameters, to get a holistic view of the analysis the models were compared between linear and non-linear isotherm models. The result reveled that, among above mentioned error functions and statistical functions were designed to determine the best fitting isotherm.
Phenols are primarily present in oil refinery, coal, paper, textile, synthetic rubber and pharmaceutical wastewaters and are an problem of a serious environmental due to their high toxicity and potential accretion in the environment. There are numerous methods for removing phenols from the wastewaters, such as reverse osmosis, adsorption, bio-degradation, chemical oxidation and solvent extraction. Adsorption is an efficient treatment system for removing phenols from wastewaters.
Adsorption isotherms experimental data is necessary for the design of sorbate-sorbent. To remove phenols from wastewaters a definite sorbate-sorbent system has required to optimize the design and also experimental equilibrium data is important to establish the most appropriate correlation. Kumar and Sivanesan has been studied comparison of linear and non-linear methods for removal of safranin onto rice husk. Subramanyam and Das has been studied comparison of linear and non-linear isotherm models, adsorption of phenol onto natural soil (Kalathur soil). The various adsorption isotherm equation to remove pollutants from wastewaters as have been used to study the nature of adsorption, with the fundamental idea of optimization of the design parameters. Many most commonly used isotherms models appearing in the adsorption literature including, Langmuir, Freundlich and Redlich–Peterson isotherm models [1, 2]. All these isotherm models derived based on the theoretical assumption, to measure the goodness of fit in the literature there are number of statistical error deviation functions such as the Marquardt’s percent standard error deviation (MPSED), the correlation coefficient (r2), the sum of the squares of the errors (SSE), the hybrid fractional error function (HYBRID), the average relative error deviation (ARED) and the residual analysis (RESID) . However, the very approach of linearization of the nonlinear models necessarily yields rationalization of specific variables, which may have significant bearings on the adsorption process itself.
The main objective of this study was to explore, the applicability of the statistical methods in determining the best fitting isotherm models. The statistical tools used in the present study were Pearson correlation coefficient (r), the coefficient of determination (r2), the Chi square test (χ2) and ANOVA test. The single component sorption study was carried out based on experiment and computed phenol-sorption by the soil selected (namely, Kalathur soil) on phenol from its aqueous solution to estimate the effect of linearization on the accuracy of the model (on comparison with experimental values).
Material and methods
The soil (namely Kalathur soil) sample was collected from Thanjavur districts, Tamil Nadu (India). The samples, thus obtained, was washed thoroughly with distilled water and dried for 2 hours, at 105°C in an electric oven, followed by crushing and sieving (100–635 SIEVE NO ASTM E11-87), to obtain the uniform size of particles. The final sample, after passing through the sieve, was dried, desiccated and preserved in air-tight chamber for subsequent analysis and experiments. Soil texture analysis was carried out to find the percentage of sand (25%), silt (20%) and clay (55%) present in the soil. According to United States Department of Agriculture (USDA) texture triangle Kalathur soil (Kr) was classified as clayey soil.
Phenol (C6H5OH) of analytical reagent (AR) grade supplied by Ranbaxi Laboratories Ltd., India, was used for the preparation of synthetic adsorbate of concentration 100 mg/l. The required quantity of phenol was accurately weighed and dissolved in distilled water and make up to one liter. Fresh stock solution was prepared every day and stored in a brown color glass bottles to prevent photo-oxidation.
To study the equilibrium, batch experiments were conducted at room temperature (30 ± 2°C) for an adsorption period of 24 hours. The effect of adsorbent dosage on the uptake of phenol on to the soil (namely Kalathur soil) was studied at different adsorbent doses (50 to 1000 mg/100 ml) for the concentration of 100 mg/l. The percentage phenol removal and equilibrium adsorption uptake, qe (mg/g), was computed by making use of the equation as given below:
Where C0 is the initial phenol concentration (mg/l), Ce the equilibrium phenol concentration (mg/l), V the volume of phenol solution (l) and w is the soil mass of the adsorbent (g).
Estimation of best-fitting isotherm model
Where SXY is the sum of squares of X and Y, SXX is the sum of squares of X and SYY is the sum of squares of Y. In addition to above mentioned error and statistical functions Chi-square test, was also examined to predict best-fitting isotherm models.
The ANOVA test (two factors without replication) was carried out for evaluating significance of various error-functions and four coefficients of dispersion (namely, Coefficient of Range, Coefficient of Quartile Deviation, Coefficient of Mean Deviation, Coefficient of Variation) were evaluated, separately for linearised and non-linearised models. In case of linearised models, only one type of Langmuir distribution (i.e., type-1) was considered because of low mean and lowest variance. A paired t-test was also carried out between the dispersion coefficients of linearised and non-linearised models to evaluate the t-statistics.
Results and discussion
Linear and non-linear isotherm equation
Linearised isotherm parameters
Non-linearised isotherm parameters
Variation of mean & dispersion coefficients between linearised and Non-linear models
Errors-- > statistics
Coefficient of Range
Coefficient of Quartile Deviation
Coefficient of Mean Deviation
Coefficient of Variation
Coefficient of Range
Coefficient of Quartile Deviation
Coefficient of Mean Deviation
Coefficient of Variation
Source of variation
Sum of squares
Mean sum of square
Between error Functions
The linearized four forms of Langmuir isotherm model were presented in Table 1 and the Langmuir coefficients for four linearized Langmuir equation were obtained by plotting graphs between Ce/qe versus Ce (Type- I linearized equation), 1/qe versus 1/Ce (Type- II linearized equation), qe versus qe/Ce (Type- III linearized equation), and qe/Ce versus qe (Type- IV linearized equation). Table 2 shows the calculated parameters of the four linearized Langmuir isotherm model. A graph was drawn between experimental and observed data as shown in Figure 2. From Table 2, it can be inferred that, different linear Langmuir equations show different Langmuir constants, as indicated by variation in errors, specific to the corresponding mode of linearization . In the case of Kalathur soil, on comparison of the four linearized Langmuir equations, it is observed that the Type- I linearized Langmuir equation showed higher value of correlation coefficient (r2 = 0.994) than that of the other three linearized equations (Type- II to IV) as shown in Table 2. The adsorption capacity of Kalathur soil was found to be 52.63 mg/g for Type –I linearized Langmuir and that of Type- II, III and IV are 41.67 mg/g, 46.52 mg/g and 49.37 mg/g, respectively. Thus, during linearization, errors in the computation of parameters may be responsible for the variation in adsorption capacity ‘qm’ and adsorption constant ‘b’ (from Type-I linearized isotherm form to Type-IV linearized isotherm). In other words, the transformation of non-linear isotherm model to linear isotherm models seems to implicitly alter the error functions as well as the error variance and normality assumptions of the least-squares methods [4, 6, 7]. As suggested in the lower correlation coefficient values, it will be inappropriate to use this type of linearization.
Error function type/isotherm model
Statistical function type/isotherm model
Pearson correlation coefficient
In the present study, for studying non-linear isotherm models, Graph Pad Prism versions 5.0 have been used for determining the non-linear coefficients. The determined coefficients were shown in Table 3. Correspondingly, a plot was drawn between Ce versus qe (Figure 2) using the experimental and predicted value by non-linear models. From Tables 6 and 7, it was observed that the correlation coefficient value is high (r 2 = 0.9953) and the low ARED, HYBRID and EABS values, thus it indicates that the models are able describe equilibrium data perfectly. Therefore, as far as the non-linear isotherm model is concerned the error remains constant. Hence, to use the correlation coefficient values for comparing the best-fitting non-linear isotherm models is befitting.
Table 3 shows a non-linear Langmuir, Freundlich and Redlich-Peterson model parameter values and Figure 2 shows a plot between Ce versus qe . The correlation coefficient value higher than that of linearized isotherm model. Table 6, shows error function value. But, the error values show the improved up on linearized isotherm.
In the case of Langmuir and Redlich-Peterson model, the model shows high correlation coefficients value. The error functions ARED, HYBRID and EABS was found to be good for Langmuir isotherm model and error functions MPSED and SSE was found to be good for Redlich-Peterson isotherm models. It is clear from above results the Langmuir isotherm and Redlich-Peterson model were for better than Freundlich isotherm model. The models were able describe experimental data perfectly. Hence, it can be understood that, the Redlich–Peterson and Langmuir isotherms were the most suitable models for sorbate-sorbent system. A close correspondence was found to exist between Langmuir and Redlich-Peterson isotherm models. Similar findings have also been reported by other researchers as well [3, 4, 8, 9].
As can be seen from Table 7, best fitting isotherm model was determined more appropriately by the Chi-square test. However, among the three isotherm models studied in this work, the phenol adsorption onto soil system was appropriately explained by Redlich-Peterson isotherm model only. Indeed the transformation of non-linear to linear models misrepresents the experimental error, which limits the validity of the error function and statistical tools. To avoid the errors discussed above, non-linear regression method can be more appropriately used.
As per the ANOVA table, although the p-values for isotherms is higher in case of linearised model than in case of non-linear models, indicating the relatively higher significance level associated with non-linearised case than the linearised case, yet at 0.05 significant level the variation is less than the table values for F-distributions. In fact, the variability between error functions is even less significant. These indicate that the selection of error functions and the isotherm models are fairly unbiased estimators for linearised and nonlinear models (Tables 4 and 5).
The overall mean of the errors of the linearised models is 93.5% higher than that of the non-linear models. To evaluate dispersion from the mean value, four coefficients of dispersion were studied, which indicated that 87.5% time the linearised models show higher dispersion coefficient. In fact, paired t-test results show that the confidence level for the non-linear models (as higher than linearised models) is more than 84%.
Thus based on the statistical studies it was found that variability in both linearised and non-linear cases are not significant at 0.05 significant level (both among isotherms and among error functions) confirming the error-estimators & isotherm models used as fairly unbiased (yet non-linear models do have relatively higher significance compared to linearised models, though). The overall mean of the error functions of linearised models is significantly higher (and so also most of the dispersion coefficients), compared to their non-linear counterparts, indicating non-linear modeling to be much better representation of experimental results than the linearised ones.
The author(s) thank the anonymous reviewers for helping us to present this research in a more effective manner. Authors also gratefully acknowledge the support received from SASTRA University.
- Srivastava VC, Swamy MM, Mall ID, Prasad B, Mishra IM: Adsorptive removal of phenol by bagasse fly ash and activated carbon: Equilibrium, kinetics and thermodynamics. Colloids Surf A: Physicochemical and Engineering Aspects 2006, 272: 89–104. 10.1016/j.colsurfa.2005.07.016View ArticleGoogle Scholar
- Porter JF, Mckay G, Choy KH: The prediction of sorption from a binary mixture of acidic dyes using single- and mixed-isotherm variants of the ideal adsorbed solute theory. Chem. Eng. Sci 1999, 54: 5863–5885. 10.1016/S0009-2509(99)00178-5View ArticleGoogle Scholar
- Ncibi MC: Applicability of some statistical tools to predict optimum adsorption isotherm after linear and non-linear regression analysis. J Hazard Mater 2007, 2008(153):207–212.Google Scholar
- Subramanyam B, Das A: Comparison of linearized and non-linearized isotherm models for adsorption of aqueous phenol by two soils. Int J Environ Sci Tech 2009, 6: 633–640. 10.1007/BF03326104View ArticleGoogle Scholar
- Vasanth Kumar K, Sivanesan S: Comparison of linear and non-linear method in estimating the sorption isotherm parameters for safranina onto activated carbon. J Hazard Mater 2005, 123: 288–292. 10.1016/j.jhazmat.2005.03.040View ArticleGoogle Scholar
- Kinniburgh DG: General purpose adsorption isotherms. Environ. Sci. Technol 1986, 20: 895–904. 10.1021/es00151a008View ArticleGoogle Scholar
- Ho YS, Wang CC: Pseudo-isotherms for the sorption of cadmium ion onto tree fern. Process Biochem 2004, 39: 759–763.Google Scholar
- Vasanth Kumar K, Sivanesan S: Isotherms for Malachite Green onto rubber Wood (Hevea brasiliensis) sawdust: Comparison of linear and non-linear methods. Dyes Pigments 2007, 72: 124–129. 10.1016/j.dyepig.2005.07.021View ArticleGoogle Scholar
- Vasanth Kumar K, Sivanesan S: Sorption isotherm for safranin onto rice husk: Comparison of linear and non-linear methods. Dyes Pigments 2007, 72: 130–133. 10.1016/j.dyepig.2005.07.020View ArticleGoogle Scholar
This article is published under license to BioMed Central Ltd. This is an Open Access article distributed under the terms of the Creative Commons Attribution License (http://creativecommons.org/licenses/by/2.0), which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly credited.