The surface excess

The presence of an interface influences generally all thermodynamic parameters of a system. To consider the thermodynamics of a system with an interface, we divide that system into three parts The two bulk phases with volumes Va and V13, and the interface a. 

In the Gibbs model the interface is ideally thin (Va = 0) and the total volume is 

1 Josiah Willard Gibbs, 1839-1903. American mathematician and physicist, Yale College. 

All other extensive quantities can be written as a sum of three components one of bulk phase a, one of bulk phase / , and one of the interfacial region a. Examples are the internal energy U, the number of molecules of the th substance Nu and the entropy S  

The contributions of the two phases and of the interface are derived as follows. Let ua and vP be the internal energies per unit volume of the two phases. The internal energies ua and vP are determined from the homogeneous bulk regions of the two phases. Close to the interface they might be different. Still, we take the contribution of the volume phases to the total energy of the system as uaVa + vPV. The internal energy of the interface is 

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The type of behavior shown by the ethanol-water system reaches an extreme in the case of higher-molecular-weight solutes of the polar-nonpolar type, such as, soaps and detergents [91]. As illustrated in Fig. Ul-9e, the decrease in surface tension now takes place at very low concentrations sometimes showing a point of abrupt change in slope in a y/C plot [92]. The surface tension becomes essentially constant beyond a certain concentration identified with micelle formation (see Section XIII-5). The lines in Fig. III-9e are fits to Eq. III-57. The authors combined this analysis with the Gibbs equation (Section III-SB) to obtain the surface excess of surfactant and an alcohol cosurfactant. 

A schematic picture of how concentrations might vary across a liquid-vapor interface is given in Fig. III-ll. The convention indicated by superscript 1, that is, the F = 0 is illustrated. The dividing line is drawn so that the two areas shaded in full strokes are equal, and the surface excess of the solvent is thus zero. The area shaded with dashed strokes, which lies to the right of the dividing... 

It was noted in connection with Eq. III-56 that molecular dynamics calculations can be made for a liquid mixture of rare gas-like atoms to obtain surface tension versus composition. The same calculation also gives the variation of density for each species across the interface [88], as illustrated in Fig. Ill-13b. The density profiles allow a calculation, of course, of the surface excess quantities. 

It has been pointed out [138] that algebraically equivalent expressions can be derived without invoking a surface solution model. Instead, surface excess as defined by the procedure of Gibbs is used, the dividing surface always being located so that the sum of the surface excess quantities equals a given constant value. This last is conveniently taken to be the maximum value of F. A somewhat related treatment was made by Handa and Mukeijee for the surface tension of mixtures of fluorocarbons and hydrocarbons [139]. 

Tajima and co-workers [108] determined the surface excess of sodium dode-cyl sulfate by means of the radioactivity method, using tritiated surfactant of specific activity 9.16 Ci/mol. The area of solution exposed to the detector was 37.50 cm. In a particular experiment, it was found that with 1.0 x 10" Af surfactant the surface count rate was 17.0 x 10 counts per minute. Separate calibration showed that of this count was 14.5 X 10 came from underlying solution, the rest being surface excess. It was also determined that the counting efficiency for surface material was 1.1%. Calculate F for this solution. 

McBain reports the following microtome data for a phenol solution. A solution of 5 g of phenol in 1000 g of water was skimmed the area skimmed was 310 cm and a 3.2-g sample was obtained. An interferometer measurement showed a difference of 1.2 divisions between the bulk and the scooped-up solution, where one division corresponded to 2.1 X 10 g phenol per gram of water concentration difference. Also, for 0.05, 0.127, and 0.268M solutions of phenol at 20°C, the respective surface tensions were 67.7, 60.1, and 51.6 dyn/cm. Calculate the surface excess Fj from (a) the microtome data, (b) for the same concentration but using the surface tension data, and (c) for a horizontally oriented monolayer of phenol (making a reasonable assumption as to its cross-sectional area). 

The treatments that are concerned in more detail with the nature of the adsorbed layer make use of the general thermodynamic framework of the derivation of the Gibbs equation (Section III-5B) but differ in the handling of the electrochemical potential and the surface excess of the ionic species [114-117]. The derivation given here is after that of Grahame and Whitney [117]. Equation III-76 gives the combined first- and second-law statements for the surface excess quantities... 

The surface excess per square centimeter F is just n/E, where n is the moles adsorbed per gram and E is the specific surface area. By means of the Gibbs equation (111-80), one can write the relationship... 

We suppose that the Gibbs dividing surface (see Section III-5) is located at the surface of the solid (with the implication that the solid itself is not soluble). It follows that the surface excess F, according to this definition, is given by (see Problem XI-9)... 

Equation 9 states that the surface excess of solute, F, is proportional to the concentration of solute, C, multipHed by the rate of change of surface tension, with respect to solute concentration, d /dC. The concentration of a surfactant ia a G—L iaterface can be calculated from the linear segment of a plot of surface tension versus concentration and similarly for the concentration ia an L—L iaterface from a plot of iaterfacial teasioa. la typical appHcatioas, the approximate form of the Gibbs equatioa was employed to calculate the area occupied by a series of sulfosucciaic ester molecules at the air—water iaterface (8) and the energies of adsorption at the air-water iaterface for a series of commercial aonionic surfactants (9). 

Surface Excess With a Gibbs dividing surface placed at the surface of the solid, the surface excess of component i, F (moVm"), is the amount per unit area of solid contained in the region near the surface, above that contained at the fluid-phase concentration far from the surface. This is depicted in two ways in Fig. 16-4. The quantity adsorbed per unit mass of adsorbent is... 

Tj is the surface excess (Davies and Rideal, Jnteifacial Phenomena, 2d ed.. Academic, New York, 1963). For most purposes, it is sufficient to view Vj as the concentration of adsorbed component i at the surface in units of, say (g mol)/cm . R is the gas constant, T is the absolute temperature, Y is the surface tension, and a is the activity of component i. The minus sign shows that material which concentrates at the surface generally lowers the surface tension, and vice versa. This can sometimes be a guide in determining preliminarily what materials can be separated. 

K is K, just below the collectors critical micelle concentration, C,. Ko is Ki at some higher cohector concentration, C,. E is the relative effectiveness, in adsorbing cohigend, of surface cohector versus micehar collector. Generally, E > 1. F, is the surface excess of collector. More about each K is avahable [Lemhch, Adsubble Methods, in Li (ed.). Recent Developments in Separation Science, vol. 1, CRC Press, Cleveland, 1972, pp. 113-127 Jashnani and Lemlich, Ind. Eng. Chem. Process Des. Dev., 12, 312 (1973)]. 

Cf, C y, and Cq are the concentrations of the substance in question (which may be a colligend or a surfactant) in the feed stream, bottoms stream, and foamate (collapsed foam) respectively. G, F, and Q are the volumetric flow rates of gas, feed, and foamate respectively, is the surface excess in equilibrium with C y. S is the surface-to-volume ratio for a bubble. For a spherical bubble, S = 6/d, where d is the bubble diameter. For variation in bubble sizes, d should be taken as YLnid fLnidj, where n is the number of bubbles with diameter dj in a representative region of foam. 

Finding F Either Eq. (22-45) or Eq. (22-46) can be used to find the surface excess indirectly from experimental measurements. To assure a close approach to operation as a single theoretical stage, coalescence in the rising foam should be minimized by maintaining a proper gas rate and a low foam height [Brunner and Lemhch, Ind. Eng. Chem. Fundam. 2, 297 (1963)]. These precautions apply particularly with Eq. (22-45). 

The excess energy associated with an interface is formally defined in terms of a surface energy. This may be expressed in terms either of Gibbs, G, or Helmholtz, A, free energies. In order to circumvent difficulties associated with the unavoidably arbitrary position of the surface plane, the surface energy is defined as the surface excess [7,8], i.e the excess (per unit area) of the property concerned consequent upon the presence of the surface. Thus Gibbs surface free energy is defined by... 

It follows that the surface excess F of an anion / (e.g. the Cl ion) can be evaluated from the electrocapillary curves of a given electrolyte (e.g. HCl) by plotting surface tension against the logarithm of the activity of the electrolyte (evaluated at various constant potentials) and determining the slope of the curve dy/d log and introducing it into equation 20.7. 

We thus obtain an equation for the surface excess, F = substance per unit surface area ... 

This equation for the surface excesses is the analog of the Gibbs-Duhem equation for bulk phases. 

In this example, we have focused on the surface excess charge term in (5.18) and (5.19) the next example wUl show that the potential is able to modify not only the electrode structure, but also its composition. 

The meaning of the surface excess is illustrated in Fig. 1, in which the solid line represents the actual concentration profile of an adsorbate i, when the bulk concentration of i in the phase a (a = O or W) is c . The hatched area corresponds to be the surface excess of i, T,. This quantity depends on the location of the dividing surface. On the other hand, the experimentally accessible quantity should not depend on the location of the artificially introduced dividing surface. The relative surface excess, which is independent of the location of the dividing surface, is defined by relativizing it with respect to those of certain reference components. In oil water interfaces, the mutual solubility of solvents can be significant. The relative surface excess in Eq. (3) is then related to the surface excesses through... 

When a component of interest is considerably surface active, its adsorbed amount is high even when its bulk concentration is low. The second terms on the right-hand side of Eqs. (4)-(6) are then small and the relative surface excesses are simply taken as the surface excesses, which, in turn, may be seen as the surface concentration. For example, dilaur-oylphosphatidylcholine forms a saturated monolayer in the liquid-expanded state at the nitrobenzene-water interface when its concentration in nitrobenzene is 10 moldm [30]. Then the experimentally obtained value, 1.76 x 10 °molcm, can be considered to be the surface concentration. 

Charge transfer reactions at ITIES include both ET reactions and ion transfer (IT) reactions. One question that may be addressed by nonlinear optics is the problem of the surface excess concentration during the IT reaction. Preliminary experiments have been reported for the IT reaction of sodium assisted by the crown ether ligand 4-nitro-benzo-15-crown-5 [104]. In the absence of sodium, the adsorption from the organic phase and the reorientation of the neutral crown ether at the interface has been observed. In the presence of the sodium ion, the problem is complicated by the complex formation between the crown ether and sodium. The SH response observed as a function of the applied potential clearly exhibited features related to the different steps in the mechanisms of the assisted ion transfer reaction although a clear relationship is difficult to establish as the ion transfer itself may be convoluted with monolayer rearrangements like reorientation. 

Girault and Schiffrin [4] proposed an alternative model, which questioned the concept of the ion-free inner layer at the ITIES. They suggested that the interfacial region is not molecularly sharp, but consist of a mixed solvent region with a continuous change in the solvent properties [Fig. 1(b)]. Interfacial solvent mixing should lead to the mixed solvation of ions at the ITIES, which influences the surface excess of water [4]. Existence of the mixed solvent layer has been supported by theoretical calculations for the lattice-gas model of the liquid-liquid interface [23], which suggest that the thickness of this layer depends on the miscibility of the two solvents [23]. However, for solvents of experimental interest, the interfacial thickness approaches the sum of solvent radii, which is comparable with the inner-layer thickness in the MVN model. 

Provided that Ag

P2 are constant, and Tjjx is proportional to (c "). The observed nonlinearity at higher electrolyte concentrations [2] is probably due to a change in the inner-layer potential difference A"y>, with the surface excess charge density. The inner-layer potential difference (< 50 mV) was evaluated from the linear part of the Tjj vs. plot, and was found to depend on the nature of the... 

Kakiuchi and Senda [36] measured the electrocapillary curves of the ideally polarized water nitrobenzene interface by the drop time method using the electrolyte dropping electrode [37] at various concentrations of the aqueous (LiCl) and the organic solvent (tetrabutylammonium tetraphenylborate) electrolytes. An example of the electrocapillary curve for this system is shown in Fig. 2. The surface excess charge density Q, and the relative surface excess concentrations T " and rppg of the Li cation and the tetraphenylborate anion respectively, were evaluated from the surface tension data by using Eq. (21). The relative surface excess concentrations and of the d anion and the... 

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