.

Geoderma 99 2001 225243

www.elsevier.nlrlocatergeoderma

Description of sorption data with isotherm equations

Christoph Hinz)
Soil Science and Plant Nutrition, The Uniersity of Western Australia, Nedlands,WA 6907, AustraliaInstitute of Soil Science and Forest Nutrition, Uniersity of Gottingen, Busgenweg 2,

D-37077 Gottingen, Germany

Received 3 December 1999; received in revised form 25 May 2000; accepted 26 May 2000

Abstract Analysis of sorption data is important for characterizing retention of chemicals by soil. In this paper I review the most common isotherm equations used in soil science. The mathematical descriptions of these equations are classified into rational, power, and transcendental functions which are related to the isotherm classification. I use most well-known isotherm equation as special cases of a general equation. The meaning of the parameters of this equation is discussed in terms of the Giles classification. Guidelines are presented for choosing the correct type of isotherm equations to describe a set of sorption data. In particular, I show that plotting the distribution coefficient vs. the amount of solute sorbed to the solid phase on a loglog scale is the best way to identify the class and subgroup of isotherms based on the Giles classification. Examples of how to apply the guidelines to determine and modify isotherm equations are presented. q2001 Elsevier Science B.V. All rights reserved. Keywords: sorption; isotherms; equations; soils; solutes

1. Introduction Sorption isotherms are widely used to characterize retention of chemicals in soils. The importance of using isotherm equations is reflected by their incorpora-

Fax: q61-8-9380-1050.E-mail address: chinz@agric.uwa.edu.au C. Hinz . .

0016-7061r01r$ -see front matter q2001 Elsevier Science B.V. All rights reserved. . PII: S0016-7061 00 00071-9

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tion into chemical speciation programs, such as MINTEQA2 Allison et al., 1990.. Also, transport models for assessing the mobility of chemicals often require isotherm parameters as input. Simple equations, such as the Freundlich or Langmuir isotherms are commonly used to describe sorption data. Often these equations do not accurately describe the data. Consequently, more complicated expressions have to be used Kinniburgh, 1986. . Lack of an accurate description of sorption data may yield serious errors when applied to transport modeling Hinz et al., 1994. . Hence, it is crucial that sorption data are described adequately with appropriate equations. Regression methods are usually employed to determine the parameters of isotherm equations. Webster 1997. reviewed the use of regression in soil science. For determining functional relationships between two quantities, we need to employ structural analysis. One prerequisite is that we know in advance which isotherm equation may describe the data. An adequate description of sorption data therefore requires two steps. First, choose an equation that will describe the data with a given accuracy. Secondly, regression methods have to be employed to find an optimal parameter set. These two steps are of course not completely independent, because the goodness of fit criteria obtained from parameter estimation often suggests how well an equation describes the data. As yet, no inspectional analysis exists that allows researchers to easily determine the type of isotherm equation that best fits a specific data set. In this paper, I review isotherm equations which have proven to be useful for describing sorption data. These equations are classified, using the isotherm classification scheme suggested by Giles et al. 1974. . From a mathematical point of view, isotherm equations can be grouped into rational, power, and transcendental functions. I summarize a number of well-known isotherm equations into a general isotherm equation. A simple inspectional method is introduced to determine the types of isotherms and equations that are suitable to describe the data. Finally, I apply this method to two data sets and illustrate how isotherm equations can be modified to fit data over a wide range of concentrations.

2. Isotherm classification and mathematical description 2.1. Classification after Giles et al. (1974) Giles et al. 1974. classified sorption isotherms based on their initial slopes and curvatures. They distinguished between high affinity H. , Langmuir L. , constant partition C. , and sigmoidal-shaped S. isotherm classes Fig. 1. . To account for plateaus, points of inflection, and maxima, they further distinguished between subgroups in each class shown in rows 5 to 7 of Fig. 1. This phenomenological classification is based on pure observation and does not

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Fig. 1. Isotherm classification according to Giles et al. 1974. shown with differently transformed coordinates.

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Table 1 Compilation of isotherm equations, their properties at high and low concentrations, and their classification according to Giles et al. 1974. Name Rational functions Langmuir Two-site Langmuir Modified Langmuir BrunauerEmmettTeller FarleyDzombakMorel sT sT sT kc 1q kc f1 k1c 1q k 1 c k1c 1q k 1 c k1c f2 k2 c 1q k 2 c 1 1q k 2 c 1 sT k q sT sT sT na na na na na 1r k 3 1r k 2 L2 L2, L4 S2 L3 L3 Equation lim c

C. Hinz r Geoderma 99 (2001) 225243

0 dc

ds

lim c

` s

lim s

`c

Class

1q k 2 c sT k1c

/ / /
1y k 3 c

/ / /

sT f1 k1q f 2 k 2 . 0 k1 X y sT . k 2 q sT k1y k 2 r k 3

1q k 1 c X y sT k1 Xc q q 1q k 1 c 1q k 1 c k2 c k2 = y c 1y k 2 c k3

Power functions Freundlicha General Langmuir Freundlich General Freundlich RedlichPeterson Toth AranovichDonohue Transcendental functions Temkin FowlerGuggenheim

KFca sT sT sT sT

` 0.
a a a

` sT sT sT sT na

` na na na na

L1, H1 S1. L2, H2 L2, H2 L2 C. Hinz r Geoderma 99 (2001) 225243 L2

kc .

` ` sT k
a 1r a a

1q kc . kc 1q kc kc

/
a

1q kc . kc

sT k

1q kc . .

k1c 1q k 2 c

1 1y k 3 c

k1

1r k 3

L3

k 1 ln c q k 2 sr sT 1y s r s T s k 1 exp k 2 s r s T . c

` sT k

` sT

` na

L1, H1 S2

For a ) 1 Freundlich equation belongs to S1 and has zero slope at c s 0 listed in parenthesis..

229

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reveal the processes that lead to different isotherm shapes. On one hand, we need to know which classes of isotherms are most important for soils and, on the other hand, we need to take into account which processes lead to particular isotherm types. Generally, S isotherms have a concave shape at low concentrations. While both H and L isotherms have a convex shape, the slopes of H isotherms reach high values whereas slopes of L isotherms remain constant. This indicates that the sorption affinity of H isotherms increases with decreasing concentration. C isotherms are defined by a constant sorption affinity, expressed as a straight line in s vs. c plots. Subgroups are defined by sorption behavior at high concentrations. Subgroup 1 shows no plateau, whereas subgroup 2 is characterized by one plateau. Subgroup 3 has an inflection point due to a change from a plateau to a concave shape. Two plateaus are characteristic of subgroup 4 isotherms. Finally, subgroup max is defined by the existence of a maximum not shown in Fig. 1.. Giles et al. 1974. used classification to describe data rather than equations, and they used qualitative criteria lacking mathematical formalism. To apply this classification to isotherm equations, mathematical criteria must be used. I provide mathematical criteria which include curvature convex or concave given by d 2 srd c 2 evaluated at a point of interest., slope at low concentration lim c 0 d srd c ., asymptotic behavior at high solution concentration lim c ` s . or at high sorption concentration lim s ` c ., and the number of plateaus and inflection points. Fig. 1 summarizes these criteria and shows the plots of K d s src vs. s. The distribution coefficient K d is often used to transform sorption data to identify parameters for L-type isotherm equations. K d plots are useful for distinguishing between different classes and subgroups. This is especially true for low concentrations. Eq. 1. shows that K d values at c s 0 equal the slope of the isotherm at c s 0 by taking the limit using lHopitals rule: lim K d s lim
c

0 c

s lim
c

0 d c

ds

1.

The previous criteria for characterizing isotherm equations are included in Table 1. A different classification of sorption phenomena of gasrsolid systems is given by the International Union of Pure and Applied Chemistry Sing et al., 1985.. Sing et al. 1985. use a roman numbering from I to VI for their classification. Type I is characterised by a constant sorption maximum and a convex shape. It is therefore equivalent to the L2 and H2 isotherms of Giles et al. 1974.. Type II exhibits an inflection point at which the shape changes from convex to concave similar to the L3 and H3 isotherms. A concave isotherm is classified as type III and has its equivalent in the S1 isotherm of the Giles classification. Type IV is equivalent to the L4 and H4 isotherm since it has two

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plateaus. A concave isotherm with a sorption maximum is referred to as type V, which is the same as the S2 isotherm. Finally type VI isotherms belong to the L and H classes with multiple plateaus. This classification is based on physical adsorption of gases measured in porous or on dense solid materials. In addition to different shapes, it also takes into account different types of hysteresis loops that are caused by capillary condensation in pores. While the classification of Sing et al. 1985. is specifically tailored towards gasrsolid adsorption, the Giles et al. classification is more suitable for the general description of sorption isotherms especially when the retention processes are unknown. Sposito 1984. discussed the interpretation of this classification and its significance for sorption of chemicals to soils and presented examples for each group. An extensive list of isotherms of organic compounds in soil is provided by Weber and Miller 1989. . They classified isotherms according to Giles et al. 1974. and showed that C, L, and H isotherms are most common. Examples for subgroup 2 isotherms of inorganic solutes can be found in Kinniburgh 1986.. However, subgroup 3 and 4 isotherms are seldom observed. L4 isotherms were found for nickel sorption by soil from a B horizon Harter, 1983. . Also, sorption of phosphorus on aluminum oxide was described by L3 isotherms van Riemsdijk and Lyklema, 1980. . Furthermore, subgroup 3 and 4 isotherms that belong to either the L or S class are often observed for proton binding to humic and et al. 1995. and Scheidegger fulvic acids and to oxides as presented by Cernk et al. 1994.. 2.1.1. L-class isotherm Mathematical criteria to define L-class isotherms are based on the sorption behavior at low concentrations. The slope of L-isotherms should be constant when the concentration approaches zero: lim K d s lim
c

0 d c s const.

ds

2.

The Langmuir, two-site Langmuir, Toth, and RedlichPeterson isotherm equations can describe L-type data Table 1. . Generally, all rational functions with parameters greater than zero meet the above criteria. Functions involving power relations, such as the Toth and the RedlichPeterson isotherm equations, may satisfy the condition in Eq. 2.. 2.1.2. H-class isotherm Giles et al. 1974. characterized high affinity sorption isotherms H-class. according to how they behave at low concentrations. Mathematically, the slope at zero concentration is defined by: lim K d s lim
c

0 d c s `

ds

3.

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An affinity that approaches infinity when the concentration reaches zero does not make sense from a thermodynamic point of view Toth, 1995.. However, when a sorption data set can be described by an equation that satisfies Eq. 3. , H-class isotherm equations can be used for solely descriptive purposes. Examples of this type of isotherm equation are the Freundlich, the general LangmuirFreundlich, and the general Freundlich equations. All of these involve power functions which can be derived from continuous siteaffinity distributions Kinniburgh, 1986.. 2.1.3. S-class isotherm Isotherms of the S-class have two causes. First, solutesolute attractive forces at the surface may cause cooperative adsorption which leads to the S-shape Giles et al., 1974.. Second, the sorption of a solute may be inhibited by a competing reaction within the solution, such as a complexation reaction with a ligand. In many cases the total amount of a solute is measured and not the activity of the different species. For example, a heavy metal may form a stable complex with a chelate. Measuring metal concentration with atomic absorption spectroscopy will indiscriminately detect free and chelated species. The isotherm thus describes the total amount of metal in solution vs. the amount sorbed to the solid phase. S-class isotherms can be described by the Freundlich equation with a power greater than one and by the modified Langmuir equation. Also, the FowlerGuggenheim equation is a S2 isotherm. Compared to the L and H isotherms the S-class occurs less frequently. Proton binding to oxide surfaces may be described by S-class isotherms Scheidegger et al., 1994. . Cu sorption on a clay loam was attributed to the ligand effect Sposito, 1984. and is therefore a multicomponent effect. Methylene blue sorption on cristobalite was also described by an S isotherm Burgisser, 1994. and the adsorption of surfactants follows sigmoidal-shaped isotherms Rea and Parks, 1990. . 2.1.4. C-class isotherm C-class isotherms exhibit constant affinity for a wide range of concentrations, implying that K d is constant. At trace concentrations many solutesoil systems behave this way, especially when the Langmuir equation is an appropriate model for the sorption processes. Many organic substances follow a C1 isotherm. 2.2. Mathematical description First, I will show that the Giles classification and most of the isotherm equations listed in Table 1 are fully compatible with mathematical properties of rational functions. Most of the commonly used isotherm equations are indeed rational functions derived from the theory of adsorption processes. Furthermore, a second class of equations involving power laws can efficiently describe a wide range of isotherm types. Transcendental functions are also used and can describe

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some of the sorption phenomena in soil, although, they are seldom used. An equation describing all classes requires a flexible expression of the following form:
n mi

s s sT fi

is 1 js 1

qi j c a i j 1 q pi j c b i j

gi j

4.

where s denotes the amount of solute sorbed to the solid phase mol kgy1 soil. and c is the solute concentration in aqueous solution mol ly1 .. s T is a parameter indicating asymptotic sorption at high concentrations mol kgy1 soil. , and f i is the fraction of site i with n is 1 f i s 1. The parameters pi j and q i j are empirical coefficients moly1 l. and the exponents a i j , bi j , and g i j are dimensionless empirical parameters. The total number of sites is denoted by n and m i gives the number of interaction terms, which relate the mathematical structure of Eq. 4. to the Giles classification. In this paper sites are defined as different types of reactive surfaces that may be described with their own sorption relationship. To better understand Eq. 4., we first need to discuss the relationships between the parameters and characteristics of the isotherm and the possible meaning of the parameters. It should be emphasized that the parameters are empirical coefficients when Eq. 4. is used for pure descriptive purposes. Only for very well-defined systems can parameters be interpreted as meaningful system properties. I will first consider the equation where all powers are equal to one, which is essentially a rational function. In order to relate well-known isotherms to Eq. 4. , I have written all isotherm equations in Table 1 as sums and products of simple Langmuir type expressions. summarizes how parameters of Eq. 4. need to be adjusted to obtain isotherm equations of Table 1. 2.2.1. Rational functions Rational functions are quotients of polynomials. Unlike simple polynomials, rational functions can describe asymptotic behavior at high concentrations. If, for example, sorption data approach an asymptotic sorption maximum, a polynomial is not able to describe the maximum without introducing fluctuations around this asymptotic value. It is not by chance that most isotherm equations listed in Table 1 are rational functions. Rational functions are known to be superior over polynomials for interpolation or extrapolation Press et al., 1992. . Eq. 4. can be viewed as a rational function if a common denominator can be found and the powers a i j , bi j , and g i j are equal to one. Sums of Langmuir equations can be written as rational functions. This implies that discrete siteaffinity distributions of Langmuir affinity parameters can always be written as rational functions. In particular, the number of sites n is also the highest power of polynomials in the nominator and denominator of the rational function. Also, all coefficients of rational functions are greater then zero.

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Table 2 Parameter adjustment of Eq. 4. to obtain well known isotherm equations Rational functions with bi j sg i j s 1 Name a n i sT Langmuir TSL ML BET FDM 1 2 1 1 4 1 1 2 1 1 1 2 3 4 Power functions with qi j s pi j ) 0 Name a n i sT FRD GLF GF Toth RP AD c
a b

mi 1 1 1 2 2 1 2 2 1

j 1 1 1 1 2 1 2 1 1 2 1 2 1

qi j )0 )0 )0 )0 1 )0 1 )0 /0 )0 )0 )0 )0

pi j q11 q11 q11 q11 )0 q11 -0 q11 )0 -0 )0 -0 0

ai j
1 1 1 1 0 1 0 1 1 0 1 0 0

)0 )0 )0 )0 )0

mi 1 1 1 1 1 2

j 1 1 1 1 1 1 2

ai j
)0 0 - a -1 1 0 - a -1 1 1 0

bi j
1 a 1 a )0 1 1

gi j
1 1 0 -g - 1 1r a 1 1 )0

1 1 1 1 1 1

1 1 1 1 1 1

1 )0 )0 )0 )0 )0

TSL, two-site Langmuir; ML, modified Langmuir; BET, BrunauerEmmettTeller; FDM, FarleyDzombakMorel; FRD, Freundlich; GLF, general LangmuirFreundlich; GF, general Freundlich; RP, RedlichPeterson; AD, AranovichDonohue. b p 11 s 0 required for FRD equation. c p 12 - 0 and q12 s 1 required for AD equation.

Apart from their utility for interpolating mathematical functions, rational functions also have statistical properties that makes them suitable for efficient parameter estimation. Ratkowsky 1987. showed that rational functions can describe a wide variety of ascending and descending curves. Least-squares estimators of model parameters are unbiased and normally distributed when the model is linear and the error is unbiased and identically normally distributed. These properties are only asymptotically approached for least-squares estimators of nonlinear models Ratkowsky, 1987. . This means that in general a large number of data points is required to apply nonlinear least-squares techniques. However, Ratkowsky 1987. showed that rational function models exhibit Aclose-to-linearB behavior meaning that the asymptotic behavior is reached with

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235

a small number of data points. This ensures that least-squares techniques, such as the GaussNewton method, will converge rapidly to an optimal set of parameters. I have written Eq. 4. in terms of sums and products because this is the easiest way to make it compatible with the Giles et al. classification of isotherms. In particular, the parameter s T equals the plateau for isotherms of subgroup 2 of H and L isotherms. When isotherm equations are derived from surface reactions s T relates to the surface area. This interpretation of s T is only valid for very well defined sorbents and sorbates. The parameters qi j s pi j are positive real numbers. With increasing qi j , the slope becomes steep and the solution concentration rapidly approaches the plateau of L2 and H2 isotherms. It can also be viewed as a measure of the affinity of a solute to sorb to a surface. The affinity coefficient qi j is related to an equilibrium constant for adsorption to well defined surfaces. For multisite isotherms n ) 1., f i can be viewed as the fraction of total surface area which each site i constitutes. For sums of simple isotherms, such as multisite Langmuir equations, we have n is 1 f i s 1. Also, isotherms of subgroup 4 with more than one plateau require n ) 1, where the plateau concentration of site i is equal to f i s T . Isotherms which are concave at high or low solution concentrations require that m i ) 0, which means that two hyperbolic functions are multiplied. We can therefore describe isotherms of the S class and subgroup 3 of the L and H classes. In fact, with pi j ) 0 and qi j ) 0, Eq. 4. describes a class S isotherm, such as a modified Langmuir isotherm Schmidt and Sticher, 1986, Table 1. . For pi j ) 0 and qi j - 0, the equation describes isotherms belonging to subgroup 3 where lim s ` c s 1rqi j . The BrunauerEmmettTeller BET. and Farley DzombakMorel FDM. isotherms are examples of L3 class isotherms Brunauer et al., 1938; Farley et al., 1985. . The asymptotic behavior at high s values can be interpreted as the concentration of 1rqi j at which either surface condensation BET. or precipitation FDM. takes place Table 1. . 2.2.2. Power functions Isotherm equations that involve power functions are often based on the Langmuir equation. In particular, the exponents a i j , bi j , and g i j are derived from averaging local-affinity coefficients that are continuously distributed at the microscopic scale Sips, 1950; Sposito, 1984; Nederlof et al., 1990. . In this context, exponents may be viewed as heterogeneity factors which normally vary between 0 and 1. With a decreasing value of the exponent, the distribution of the local affinity coefficients becomes wider. Special cases of isotherm equations with m i s 0 are the general LangmuirFreundlich, general Freundlich isotherm, and Toth isotherms Table 1.. The Freundlich isotherm with a ) 1 can be derived from the general LangmuirFreundlich isotherm for low concentrations Sposito, 1984.. The exponent g i may be greater than 1 if m i ) 0 and qi j s pi j . In addition to isotherms that are based on continuous site affinity distributions,

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the RedlichPeterson isotherm has a fractional power based on interactions of adsorption sites. High affinity sorption isotherms H. require exponents so that the slope will approach infinity when c approaches zero. The general Freundlich and general LangmuirFreundlich isotherms belong to the H class Table 1. . Furthermore, one can describe isotherms of subgroup 3 and 4 with exponents greater than one. Although isotherms of subgroup max seem to be rare for natural soils, one can still obtain a maximum, if bi ) a i . 2.2.3. Transcendental functions Transcendental function can also be used to describe sorption data see also Table 1.. In particular, the Temkin isotherm can be used to describe binding-site heterogeneity Stumm and Morgan, 1981. . The FowlerGuggenheim equation describes adsorption where interactions between adsorbed solutes occur so as to form S2 isotherms Adamson, 1990. . Nonetheless, they are of little importance for describing sorption data in soil. Another transcendental function is the DubininRadushkevich equation that was used and modified by Kinniburgh 1986.. He showed that a modified version of this equation has similar properties to the Toth isotherm.

3. Identifying sorption isotherm equations 3.1. A qualitatie approach to determining sorption equations To determine which equation best describes any given sorption data, it is useful to first assign the class and subgroup of the classification of Giles et al. 1974. to the data. This can be done by plotting the data in different ways. Once the class and subgroup are determined, one can use an isotherm equation from Table 1. Plots of sorption data on a linear scale will show a concentration range within two orders of magnitude. Data within this range can therefore be plotted as s vs. c on a linear scale. This plot reveals the type of isotherm, as shown in Fig. 1, which is similar to the presentation of Giles et al. 1974. . Because sorption data are often determined for concentrations ranging over several orders of magnitude, loglog plots of s vs. c, sometimes referred to as Freundlich plots, are employed. However, loglog plots are not suitable to identify class and subgroup of isotherms by inspection. Instead, I suggest that K d be plotted vs. s or c. Because K d is defined as src, it is a measure of sorption affinity. In fact, since s is dependent on c, plots of K d vs. s or c amplify variations of s c .. This yields a larger scatter of data points in K d vs. s or c plots. Outliers which may cause problems during parameter estimation can easily be detected by plotting data this way.

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237

On a linear scale, K d vs. s plots are referred to as Scatchard plots and they transform the Langmuir isotherm into a straight line Sposito, 1984. : K d s ks T q ks

5.

As pointed out by Veith and Sposito 1977. , this plot is more sensitive at low concentrations than other linearizations. Also, this plot is especially useful to determine whether or not a two-site Langmuir equation is suitable to describe the data. Sposito 1982. showed that a two-site Langmuir can fit any convex sorption data that tends to a maximum asymptotically. A simple inspection of the trend of K d vs. s reveals this behaviour. In fact, parameters of the two-site Langmuir equation can be determined from the slopes of the data points at high values of K d and from the slope at low values of K d Sposito, 1982. . A detailed description of how to determine parameters of the two-site Langmuir equation is given by Sposito 1982.. Plotting K d vs. s on a loglog scale will yield a straight line for Freundlich isotherms. This linearization of the Freundlich isotherm, which is not commonly used, is given by log K d s 1 log K F q

a y 1.
a

log s

6.

This linearization reveals when sorption data deviate from the Freundlich equation at low concentrations and hence aid in choosing the correct isotherm equation to describe the data. While this linearization provides insight in the choice of the correct isotherm equation, parameter estimation should be carried out with untransformed data. From Fig. 1, it is also evident how the parameters in Eq. 4. have to be adjusted to account for certain phenomena in the log K d vs. log s plots. At low sorption concentrations, Langmuir-type isotherms exhibit constant K d which appears as a horizontal line in logarithmic Scatchard plots. H-isotherms have negative slopes whereas S-isotherms have positive ones at low concentrations. Classification of isotherms into subgroups depends on isotherm behavior at high concentrations. Accordingly, a sorption maximum for subgroup 2 isotherms appears as asymptotic behavior at low K d values. Subgroup 3 isotherms show a minimum at high s values. To systematically determine isotherm class and subgroups, I have developed a scheme which classifies a given data set Table 3. . This scheme should be viewed as a qualitative tool in finding an appropriate equation. It is especially useful for determining whether or not a Freundlich or Langmuir isotherm is suitable to describe sorption data. If both equations are inadequate for data description, other isotherm equations as listed in Table 1 should be used. Furthermore, this scheme helps to determine whether an initial amount of solute is sorbed to the soil as shown by a maximum in log K d vs. log s plot item 5... Kinniburgh 1986. demonstrated how one can analyze sorption data with

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Table 3 Qualitative approach to identify isotherm class and subgroup and sorption model Data range A. c - 2 orders of magnitude Plot s vs. c Curve 1. curvature at low c Properties 1. straight line 2. concave line 3. convex line linear at low c. 4. convex line convex at low c. 1. straight line with negative slope 1. negative slope 2. positive slope 4. slope at low s 1. positive 2. zero 3. negative 1. s0. s 0 2. s0. - 0 1. asymptote 2. minimum Isotherm C class S class L class H class Langmuir isotherm Freundlich isotherm a - 1. Freundlich isotherm a ) 1. S class L class H class S2 type isotherm any class with constant term Subgroup 2 Subgroup 3

K d vs. s A) . c ) 2 orders of magnitude log K d vs. log s

2. curve over the whole data range 3. straight line

5. maximum at low s 6. behavior at high s

an initial sorption by subtracting an adjustable parameter from the isotherm equation. 3.2. Examples To show how Table 3 helps to determine an appropriate isotherm equation, I present two examples. Sorption of 1,3-dinitrobenzene on montmorillonite was investigated at concentrations ranging from 0.14 to 413 mg ly3, equivalent to three orders of magnitude Table 4. . Fig. 2a shows the data s vs. c plotted on a linear scale. The convex shape is clear, but low concentrations are not shown at a resolution that makes it possible to recognize the class of isotherm. We need therefore to plot the data on a loglog scale as indicated by criteria A and A) in Table 3. Fig. 2b shows the same data on a loglog scale. The curvature indicates that the Freundlich isotherm is not appropriate to describe the data. To determine whether the Langmuir equation is appropriate, K d is plotted vs. s in Fig. 2c. Since the data points do not follow a straight line, an equation with more than two parameters needs to be employed to describe the data. Plots of K d vs. s on a linear and loglog scale exhibit a maximum at low s values. Following Table 3 A) item 5. this isotherm belongs to the S class or the soil

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Table 4 Results of parameter estimation of the best fit of the original and modified general Langmuir Freundlich equation for 1,3-dinitrobenzene and the regular and modified AranovichDonohue equations for benzene sorption on dry Kettleman loam Example Equationa sT mmol kgy1 . 2600 2316 s0 mmol kgy 1 . y44.1 k1 mmoly a la . 0.0076 0.013 38.3 69.9 k2 mmoly a la . 3.33 7.51

a1

a2

1,3-Dinitrobenzene 1,3-Dinitrobenzene Benzene Benzene

a

mGLF GLF mAD AD

0.55 0.62 0.81

0.36 0.39

Parameters are from unmodified and modified general LangmuirFreundlich equations GLF and mGLF, Eq. 7.. and unmodified and modified AranovichDonohue equations AD and mAD, Eq. 8...

contained an initial amount of 1,3-dinitrobenzene. At high concentrations the data seem to reach a sorption maximum indicating a subgroup 2 isotherm. The general LangmuirFreundlich equation was used in a first attempt to describe the data. The dashed line in Fig. 2 shows the best fit. It systematically overestimates data points at low concentrations suggesting that the model is not

Fig. 2. Adsorption of 1,3-dinitrobenzene on montmorillonite saturated with KCl. General LangmuirFreundlich equation was fitted to the data with dashed line. and without a constant solid line.. Data are plotted s vs. c on a linear a. and a logarithmic b. scale and K d vs. s on a linear c. and a logarithmic scale d. data are from Fesch, 1997, Apersonal communicationB.

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adequate at these concentrations. We know that a maximum in a K d vs. s plot can be described by adding a constant to the isotherm equation. The general LangmuirFreundlich equation is then written as s s sT k 1 c a1 1 q k1c a1 q s0

7.

where s0 denotes a constant mmol kgy1 . . The solid line shows the best fit which describes the isotherm over the whole range of concentrations equally well. The second example is taken from Shonnard et al. 1993. . They measured sorption of benzene on dry Kettleman soil. Data points lie within a range of two orders of magnitude. Fig. 3a and b show s vs. c plots on linear and loglog scales. After an initial convex shape the isotherm becomes concave and seems to approach an asymptotic value on the c axis implying that this isotherm falls into either the L or H class and subgroup 3. The AranovichDonohue AD. equation describes an L3 isotherm Aranovich and Donohue, 1995. . The solid line in Fig. 3 shows the best fit which systematically underestimates the data at low concentrations. This is even more pronounced in Fig. 3c and d where K d vs. s is plotted on linear and loglog scales. It shows that data points of K d increase with decreasing s and therefore that K d is not constant at low concentrations.

Fig. 3. Adsorption of benzene on Kettleman soil Shonnard et al., 1993.. A modified dashed line. and the original solid line. AranovichDonohue equation was fitted to the data. Data are plotted s vs. c on a linear a. and a logarithmic b. scale and K d vs. s on a linear c. and a logarithmic scale d.. c r denotes normalized concentration with respect to the condensation concentration.

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To account for this behavior I modified the AranovichDonohue equation by introducing a power function as follows: ss

k 1 c a1 1 q k 2 c a1

1 1 y k3c

a2

8.

where a 1 is an additional parameter which makes the first part of this equation identical to the general LangmuirFreundlich equation. The difference between the original AD equation and the modified AD equation is that at low concentrations the modified equation belongs to the H instead of the L class. The best fit is shown as dashed lines in Fig. 3. The description of the data at low concentrations has improved considerably without systematic deviations.

4. Conclusions and outlook Parameter estimation of isotherm equations has been addressed by several authors Veith and Sposito, 1977; Harter, 1984; Harter and Baker, 1977, 1978; Holford, 1978; Kinniburgh, 1986; Persoff and Thomas, 1988; Schulthess and Dey, 1996.. They addressed the suitability of specific isotherm equations for describing sorption phenomena and statistical issues of curve fitting. The problem of describing sorption data when both Freundlich and Langmuir equations fail to describe data was not resolved. In this paper I have demonstrated that the appearance of sorption data can be related to the mathematical form of isotherm equations by using the Giles et al. classification. Eq. 4. reveals the structure of the mathematical expressions in isotherm equations. Mathematical expressions can be grouped into rational, power, and transcendental functions. The first two functions are most useful. The asymptotic behavior at low and high concentrations of these equations is most useful for determining the class and subgroup of isotherms. An inspectional analysis of sorption data using this classification and graphical representations of the data has been shown to be a useful tool in identifying isotherm class and subgroup. Knowledge of the relations between the isotherm equation and data appearance reveals which group of isotherm equations of Table 1 should be used. Two examples have been presented to show how inspectional analysis can be used to modify isotherm equations. I used an unweighted nonlinear least-squares technique to obtain an optimal set of parameters. Statistical issues of how over-parameterized equations can be used to describe sorption data have been et al. 1995. in the context of discrete and continuous addressed by Cernk siteaffinity distributions. Regularization techniques were used to determine affinity spectra. One purpose of using regularization is to incorporate a priori knowledge into parameter optimization routines. Inspectional analysis presented

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in this chapter provides qualitative a priori knowledge on the mathematical description of data. Further research should employ methods that can make use of the rules given in Table 3.

Acknowledgements I thank Bernhard Buchter for valuable discussions, Hannes Fluhler, Edzo Veldkamp, and Ruben Kretzschmar for their comments on the manuscript and Claudia Fesch and Stefan Haderlein for providing the 1,3-dinitrobenzene data.

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