Tension, aqueous

Underwetting is most significant in aqueous-organic systems, and tends to occur at the high-surface-tension (aqueous) end of the composition range. Liquid viscosity may also have an effect. 

Gortalova. Zhur. Fiz. Khim. 25, 1043-9 (1951). Surface tension aqueous ketones, pyridine, chloral. 

As an example of the application of the method, Neumann and Tanner [54] followed the variation with time of the surface tension of aqueous sodium dode-cyl sulfate solutions. Their results are shown in Fig. 11-15, and it is seen that a slow but considerable change occurred. 

We have considered the surface tension behavior of several types of systems, and now it is desirable to discuss in slightly more detail the very important case of aqueous mixtures. If the surface tensions of the separate pure liquids differ appreciably, as in the case of alcohol-water mixtures, then the addition of small amounts of the second component generally results in a marked decrease in surface tension from that of the pure water. The case of ethanol and water is shown in Fig. III-9c. As seen in Section III-5, this effect may be accounted for in terms of selective adsorption of the alcohol at the interface. Dilute aqueous solutions of organic substances can be treated with a semiempirical equation attributed to von Szyszkowski [89,90]... 

Fig. III-9. Representative plots of surface tension versus composition, (a) Isooctane-n-dodecane at 30°C 1 linear, 2 ideal, with a = 48.6. Isooctane-benzene at 30°C 3 ideal, with a = 35.4, 4 ideal-like with empirical a of 112, 5 unsymmetrical, with ai = 136 and U2 = 45. Isooctane-

Fig. Ill-IS. Surface tension data for aqueous alcohol illustration of the use of the Gibbs equation. (1) -butyl (2) -amyl (3) -hexyl (4) -heptyl (5) -octyl. (Data from Ref. 126).

It is not uncommon for this situation to apply, that is, for a Gibbs mono-layer to be in only slow equilibrium with bulk liquid—see, for example. Figs. 11-15 and 11-21. This situation also holds, of course, for spread monolayers of insoluble substances, discussed in Chapter IV. The experimental procedure is illustrated in Fig. Ill-19, which shows that a portion of the surface is bounded by bars or floats, an opposing pair of which can be moved in and out in an oscillatory manner. The concomitant change in surface tension is followed by means of a Wilhelmy slide. Thus for dilute aqueous solutions of a methylcellu-... 

A 1.5% by weight aqueous surfactant solution has a surface tension of 53.8 dyn/cm (or mN/m) at 20°C. (a) Calculate a, the area of surface containing one molecule. State any assumptions that must be made to make the calculation from the preceding data, (b) The additional information is now supplied that a 1.7% solution has a surface tension of 53.6 dyn/cm. If the surface-adsorbed film obeys the equation of state ir(o - 00) = kT, calculate from the combined data a value of 00, the actual area of a molecule. 

The surface tension of an aqueous solution varies with the concentration of solute according to the equation y = 72 - 350C (provided that C is less than 0.05Af). Calculate the value of the constant k for the variation of surface excess of solute with concentration, where k is defined by the equation V = kC. The temperature is 25°C. 

In detergency, for separation of an oily soil O from a solid fabric S just to occur in an aqueous surfactant solution W, the desired condition is 730 = 7wo+7sw. Use simple empirical surface tension relationships to infer whether the above condition might be met if (a) 73 = 7w. (6) 70 = 7W, or (c) 73 = 70. 

Assume that an aqueous solute adsorbs at the mercury-water interface according to the Langmuir equation x/xm = bc/( + be), where Xm is the maximum possible amount and x/x = 0.5 at C = 0.3Af. Neglecting activity coefficient effects, estimate the value of the mercury-solution interfacial tension when C is Q.IM. The limiting molecular area of the solute is 20 A per molecule. The temperature is 25°C. 

IHP) (the Helmholtz condenser formula is used in connection with it), located at the surface of the layer of Stem adsorbed ions, and an outer Helmholtz plane (OHP), located on the plane of centers of the next layer of ions marking the beginning of the diffuse layer. These planes, marked IHP and OHP in Fig. V-3 are merely planes of average electrical property the actual local potentials, if they could be measured, must vary wildly between locations where there is an adsorbed ion and places where only water resides on the surface. For liquid surfaces, discussed in Section V-7C, the interface will not be smooth due to thermal waves (Section IV-3). Sweeney and co-workers applied gradient theory (see Chapter III) to model the electric double layer and interfacial tension of a hydrocarbon-aqueous electrolyte interface [27]. 

It is quite clear, first of all, that since emulsions present a large interfacial area, any reduction in interfacial tension must reduce the driving force toward coalescence and should promote stability. We have here, then, a simple thermodynamic basis for the role of emulsifying agents. Harkins [17] mentions, as an example, the case of the system paraffin oil-water. With pure liquids, the inter-facial tension was 41 dyn/cm, and this was reduced to 31 dyn/cm on making the aqueous phase 0.00 IM in oleic acid, under which conditions a reasonably stable emulsion could be formed. On neutralization by 0.001 M sodium hydroxide, the interfacial tension fell to 7.2 dyn/cm, and if also made O.OOIM in sodium chloride, it became less than 0.01 dyn/cm. With olive oil in place of the paraffin oil, the final interfacial tension was 0.002 dyn/cm. These last systems emulsified spontaneously—that is, on combining the oil and water phases, no agitation was needed for emulsification to occur. 

A saturated aqueous solution in contact with an excess of a definite solid phase at a given temperature will maintain constant humidity in an enclosed space. Table 11.4 gives a number of salts suitable for this purpose. The aqueous tension (vapor pressure, in millimeters of Hg) of a solution at a given temperature is found by multiplying the decimal fraction of the humidity by the aqueous tension at 100 percent humidity for the specific temperature. For example, the aqueous tension of a saturated solution of NaCl at 20°C is 0.757 X 17.54 = 13.28 mmHg and at 80°C it is 0.764 X 355.1 = 271.3 mmHg. 

Percent humidity Aqueous tension, mmHg H2SO4 NaOH CaClj ... 

The choice of the solvent also has a profound influence on the observed sonochemistry. The effect of vapor pressure has already been mentioned. Other Hquid properties, such as surface tension and viscosity, wiU alter the threshold of cavitation, but this is generaUy a minor concern. The chemical reactivity of the solvent is often much more important. No solvent is inert under the high temperature conditions of cavitation (50). One may minimize this problem, however, by using robust solvents that have low vapor pressures so as to minimize their concentration in the vapor phase of the cavitation event. Alternatively, one may wish to take advantage of such secondary reactions, for example, by using halocarbons for sonochemical halogenations. With ultrasonic irradiations in water, the observed aqueous sonochemistry is dominated by secondary reactions of OH- and H- formed from the sonolysis of water vapor in the cavitation zone (51—53). 

The higher members of the series decrease the surface tension of aqueous solutions well below the point possible with any type of hydrocarbon surfactant, although in practice because of their strong acid character and solubiUty characteristics, more commonly salts and other derivatives are employed. A 0.1% solution of C F COOH has a surface tension of only 19 mN/m (dyn/cm) at 30°C (6). 

Emulsifiers. The chemical stmctures of emulsifiers, or surfactants (qv), enable these materials to reduce the surface tension at the interface of two immiscible surfaces, thus allowing the surfaces to mix and form an emulsion (33). An emulsifier consists of a polar group, which is attracted to aqueous substances, and a hydrocarbon chain, which is attracted to Hpids. 

P. Dunlop and co-workers, "Aqueous Surfactant Solutions Which Exhibit Ultra-Low Tensions at the Oil-Water Interface," Paper presented at the... 

Surface Tension. The surface tension of aqueous solutions of PVA varies with concentration (Fig. 10), temperature, degree of hydrolysis, and acetate distribution on the PVA backbone. Random distribution of acetyl groups in the polymer results in solutions having higher surface tension compared to those of polymers in which blocks of acetyl groups are present (74—77). Surface tension decreases slightly as the molecular weight is reduced (Fig. 11). 

Fig. 10. Surface tension of aqueous poly(vinyl alcohol) solutions at 20°C and DP of 1700, where A represents 98—99 mol % hydrolyzed B, 87—89 mol %...

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