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- 1. Isotherms Adsorption is usually described through isotherms, that is, the amount of adsorbate on the adsorbent as a function of its pressure (if gas) or concentration (if liquid) at constant temperature. The quantity adsorbed is nearly always normalized by the mass of the adsorbent to allow comparison of different materials. Freundlich The first mathematical fit to an isotherm was published by Freundlich and Küster (1894) and is a purely empirical formula for gaseous adsorbates, where x is the quantity adsorbed, m is the mass of the adsorbent, P is the pressure of adsorbate and k and n are empirical constants for each adsorbent-adsorbate pair at a given temperature. The function has an asymptotic maximum as pressure increases without bound. As the temperature increases, the constants k and n change to reflect the empirical observation that the quantity adsorbed rises more slowly and higher pressures are required to saturate the surface. Langmuir In 1916, Irving Langmuir published a new model isotherm for gases adsorbed to solids, which retained his name. It is a semi-empirical isotherm derived from a proposed kinetic mechanism. It is based on four assumptions: 1. The surface of the adsorbent is uniform, that is, all the adsorption sites are equivalent. 2. Adsorbed molecules do not interact. 3. All adsorption occurs through the same mechanism. 4. At the maximum adsorption, only a monolayer is formed: molecules of adsorbate do not deposit on other, already adsorbed, molecules of adsorbate, only on the free surface of the adsorbent. These four assumptions are seldom all true: there are always imperfections on the surface, adsorbed molecules are not necessarily inert, and the mechanism is clearly not the same for the very first molecules to adsorb to a surface as for the last. The fourth condition is the most troublesome, as frequently more molecules will adsorb to the monolayer; this problem is addressed by the BET isotherm for relatively flat (non- microporous) surfaces. The Langmuir isotherm is nonetheless the first choice for most models of adsorption, and has many applications in surface kinetics (usually called Langmuir-Hinshelwood kinetics) and thermodynamics.
- 2. Langmuir suggested that adsorption takes place through this mechanism: , where A is a gas molecule and S is an adsorption site. The direct and inverse rate constants are k and k-1. If we define surface coverage, θ, as the fraction of the adsorption sites occupied, in the equilibrium we have or Where P is the partial pressure of the gas or the molar concentration of the solution. For very low pressures and for high pressures θ is difficult to measure experimentally; usually, the adsorbate is a gas and the quantity adsorbed is given in moles, grams, or gas volumes at standard temperature and pressure (STP) per gram of adsorbent. If we call vmon the STP volume of adsorbate required to form a monolayer on the adsorbent (per gram of adsorbent), and we obtain an expression for a straight line: Through its slope and y-intercept we can obtain vmon and K, which are constants for each adsorbent/adsorbate pair at a given temperature. vmon is related to the number of adsorption sites through the ideal gas law. If we assume that the number of sites is just the whole area of the solid divided into the cross section of the adsorbate molecules, we can easily calculate the surface area of the adsorbent. The surface area of an adsorbent depends on its structure; the more pores it has, the greater the area, which has a big influence on reactions on surfaces. If more than one gas adsorbs on the surface, we define θE as the fraction of empty sites and we have and
- 3. where i is each one of the gases that adsorb. BET Often molecules do form multilayers, that is, some are adsorbed on already adsorbed molecules and the Langmuir isotherm is not valid. In 1938 Stephen Brunauer, Paul Emmett, and Edward Teller developed a model isotherm that takes that possibility into account. Their theory is called BET theory, after the initials in their last names. They modified Langmuir's mechanism as follows: A(g) + S ⇌ AS A(g) + AS ⇌ A2S A(g) + A2S ⇌ A3S and so on Langmuir isotherm (red) and BET isotherm (green) The derivation of the formula is more complicated than Langmuir's (see links for complete derivation). We obtain: x is the pressure divided by the vapor pressure for the adsorbate at that temperature (usually denoted P / P0 ), v is the STP volume of adsorbed adsorbate, vmon is the STP volume of the amount of adsorbate required to form a monolayer and c is the equilibrium constant K we used in Langmuir isotherm multiplied by the vapor pressure of the adsorbate. The key assumption used in deriving the BET equation that the successive heats of adsorption for all layers except the first are equal to the heat of condensation of the adsorbate. The Langmuir isotherm is usually better for chemisorption and the BET isotherm works better for physisorption for non-microporous surfaces. Kisliuk
- 4. Two adsorbate nitrogen molecules adsorbing onto a tungsten adsorbent from the precursor state around an island of previously adsorbed adsobate (left) and via random adsorption (right) In other instances, molecular interactions between gas molecules previously adsorbed on a solid surface form significant interactions with gas molecules in the gaseous phase. Hence, adsorption of gas molecules to the surface is more likely to occur around gas molecules that are already present on the solid surface, rendering the Langmuir adsorption isotherm ineffective for the purposes of modelling. This effect was studied in a system where nitrogen was the adsorbate and tungsten was the adsorbent by Paul Kisliuk (b. 1922-d. 2008) in 1957. To compensate for the increased probability of adsorption occurring around molecules present on the substrate surface, Kisliuk developed the precursor state theory, whereby molecules would enter a precursor state at the interface between the solid adsorbent and adsorbate in the gaseous phase. From here, adsorbate molecules would either adsorb to the adsorbent or desorb into the gaseous phase. The probability of adsorption occurring from the precursor state is dependent on the adsorbate’s proximity to other adsorbate molecules that have already been adsorbed. If the adsorbate molecule in the precursor state is in close proximity to an adsorbate molecule which has already formed on the surface, it has a sticking probability reflected by the size of the SE constant and will either be adsorbed from the precursor state at a rate of kEC or will desorb into the gaseous phase at a rate of kES. If an adsorbate molecule enters the precursor state at a location that is remote from any other previously adsorbed adsorbate molecules, the sticking probability is reflected by the size of the SD constant. These factors were included as part of a single constant termed a "sticking coefficient," kE, described below: As SD is dictated by factors that are taken into account by the Langmuir model, SD can be assumed to be the adsorption rate constant. However, the rate constant for the Kisliuk model (R’) is different to that of the Langmuir model, as R’ is used to represent the impact of diffusion on monolayer formation and is proportional to the square root of the system’s diffusion coefficient. The Kisliuk adsorption isotherm is written as follows, where Θ(t) is fractional coverage of the adsorbent with adsorbate, and t is immersion time: Solving for Θ(t) yields:
- 5. Henderson-Kisliuk The Henderson-Kisliuk adsorption equation prediction of normalised impedance as a function of adsorption time, where the first peak corresponds to the formation of an adsorbent surface that is saturated with MPA in its "lying down" structure. The curve then tends to an impedance value that is representative of an adsorbent saturated with "standing up" structure. This adsorption isotherm was developed for use with the new field of Self Assembling Monolayer (SAM) adsorption. SAM molecules adsorb to the surface of an adsorbent until the surface becomes saturated with the SAM molecules' hydrocarbon chains lying flat against the adsorbate. This is termed "lying down" structure (1st structure). Further adsorption then occurs, causing the hydrocarbon chains to be displaced by thiol groups present on the newly adsorbed SAM molecules. When this adsorption step takes place, electrostatic forces between the newly adsorbed SAM molecules and the ones previously adsorbed, causes a new structure to form, where all of the SAM molecules are occupying a "standing up" orientation (2nd structure). As further adsorption takes place, the entire adsorbent becomes saturated with SAM in a standing up orientation, and no further adsorption takes place. The SAM adsorbate is usually present in a liquid phase and the adsorbent is normally a solid. Hence, intermolecular interactions are significant and the Kisliuk adsorption isotherm applies. The sequential evolution of "lying down" and "standing up" mercaptopropionic acid (MPA) SAM structures on a gold adsorbent, from a liquid MPA- ethanol adsorbate phase, was studied by Andrew P. Henderson (b. 1982) et al. in 2009. Henderson et al. used electrochemical impedance spectroscopy to quantify adsorption and witnessed that the 1st structure had different impedance properties to the 2nd structure and that both structures evolved sequentially. This allowed four rules to be expressed: • That the amount of adsorbate on the adsorbent surface was equal to the sum of the adsorbate occupying 1st structure and 2nd structure. • The rate of 1st structure formation is dependent on the availability of potential adsorption sites and intermolecular interactions. • The amount of 1st structure is depleted as 2nd structure is formed.
- 6. • The rate of second structure formation is dictated by the amount of adsorbate occupying 1st structure and intermolecular interactions at immersion time, t. From these statements, Henderson et al. used separate terms to describe rate of fractional adsorption for 1st structure [Θ1(t)] and 2nd structure [Θ2(t)] as a function of immersion time (t). Both of these terms were dictated by the Kisliuk adsorption isotherm, where variables with a subscript of 1 relate to 1st structure formation and a subscript of 2 relates to 2nd structure formation. These terms were combined in the Henderson adsorption isotherm, which determines the total normalised impedance detection signal strength caused by the adsorbate monolayer (z(t)) as a function of Θ1(t), Θ2(t), φ1 and φ2. Values of φ are weighting constants, which are normalized signal values that would result from an adsorbent covered entirely with either 1st structure or 2nd structure. This isotherm equation is shown below: Although the Henderson-Kisliuk adsorption isotherm was originally applied to SAM adsorption, Henderson et al. hypothesised that this adsorption isotherm is potentially applicable to many other cases of adsorption and that Θ1(t) and Θ2(t) can be calculated using other adsorption isotherms, in place of the Kisliuk model (such as the Langmuir adsorption isotherm equation). Adsorption enthalpy Adsorption constants are equilibrium constants, therefore they obey van 't Hoff's equation: As can be seen in the formula, the variation of K must be isosteric, that is, at constant coverage. If we start from the BET isotherm and assume that the entropy change is the same for liquefaction and adsorption we obtain ΔHads = ΔHliq − RTlnc, that is to say, adsorption is more exothermic than liquefaction.
- 7. • The rate of second structure formation is dictated by the amount of adsorbate occupying 1st structure and intermolecular interactions at immersion time, t. From these statements, Henderson et al. used separate terms to describe rate of fractional adsorption for 1st structure [Θ1(t)] and 2nd structure [Θ2(t)] as a function of immersion time (t). Both of these terms were dictated by the Kisliuk adsorption isotherm, where variables with a subscript of 1 relate to 1st structure formation and a subscript of 2 relates to 2nd structure formation. These terms were combined in the Henderson adsorption isotherm, which determines the total normalised impedance detection signal strength caused by the adsorbate monolayer (z(t)) as a function of Θ1(t), Θ2(t), φ1 and φ2. Values of φ are weighting constants, which are normalized signal values that would result from an adsorbent covered entirely with either 1st structure or 2nd structure. This isotherm equation is shown below: Although the Henderson-Kisliuk adsorption isotherm was originally applied to SAM adsorption, Henderson et al. hypothesised that this adsorption isotherm is potentially applicable to many other cases of adsorption and that Θ1(t) and Θ2(t) can be calculated using other adsorption isotherms, in place of the Kisliuk model (such as the Langmuir adsorption isotherm equation). Adsorption enthalpy Adsorption constants are equilibrium constants, therefore they obey van 't Hoff's equation: As can be seen in the formula, the variation of K must be isosteric, that is, at constant coverage. If we start from the BET isotherm and assume that the entropy change is the same for liquefaction and adsorption we obtain ΔHads = ΔHliq − RTlnc, that is to say, adsorption is more exothermic than liquefaction.

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