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FOAMS • Introduction – Types of foams – Structure of foams – Foamability measurements • Foam stability – – – – – – Film elasticity Factors affecting foam stability Foam drainage Diffusion of air across lamellae Thickness of electrical double layer Surface viscosity • Relationship between surfactants and foam • Foam Stabilizers • Antifoaming agents Applications: Governed by Bubble Size and Stability FIRE FIGHTING FROTH FLOTATION SHAVING CREAM, SHAMPOO DETERGENTS STRAWBERRY & CREAM Foams Agglomeration of gas bubbles separated from each other by thin liquid films. A. Types of foams: Based on the state of aggregation of the two phases. (1) Gases dispersed in liquids-Foams, gas emulsion (2) Liquids dispersed in gases-Fog, mist, aerosol (3) Gases dispersed in solids-Solid foams (4) Solids dispersed in gases-Smoke, fume Difference between foam and sponge Foam – Sponge – Disperse phase and a continuous phase. Both phases continuous e.g. bread – mainly a sponge and partly a solid foam. B. Structure of Foams (i) For three bubbles 1200 Septum Plateau’s border Or Gibb’s triangle Septa to meet at 1200 for mechanical stability (ii) Four bubbles A two dimensional foam consists of more or less uniform hexagonal type of network. In three dimensional foams - Three septums to meet at 1200 - Four septums to meet at the tetrahedral angle of 109028’ Foamability Measurements Foaming efficiency Measure of (ease of) production of foam Foaming effectiveness Measure of stability of the foam produced Ross-Miles Method: 200 ml solution in a pipette (2.9 mm ID) allowed to fill 90cm onto 50 ml of same solution in a cylindrical vessel at 600C. Stability determined by measuring the film height after certain intervals of time. Foam Stability In a foam, liquid from the lamellae region drains because of following factors. (i) Liquid pressure at B < liquid pressure at A Laplace equation B A Max curvature in the plateau border Greater pressure across the interface in these regions (ii) Hydrostatic pressure When lamella thickness reaches a critical thickness (50-100Å), the film collapses. A. Film Elasticity The ability to resist excessive LOCALIZED thinning of the lamellae. Film elasticity is a necessary condition for the production of foams. It is not a sufficient condition for formation of a stable foam. Theories of Film Elasticity Local increase in surface tension with extension of the film. g1 g1 g2 g2 > g1 Restoring force = g2-g1 Marangoni Effect Explains the increase in the restoring force on the basis of the instantaneous value of g. Gibbs Effect Explains it on the basis of equilibrium value of g. Marangoni Effect (i) Significant only in dilute solutions (ii) Applicable within a limited concentration range. • Amount of solute adsorbed at a new surface in the absence of agitation or an energy barrier is given by n = 2 (D/p)1/2 C t ½ N/1000 n = no. of molecules / cm2 D = bulk diffusion constant C = bulk concentration in moles/l t = time in seconds N = Avogadro number Marangoni Effect: EXample What is the bulk concentration of the solute required to produce a foam? • Time required to replace the solute at a new surface should be of the order of the time required to produce a foam (0.01 seconds) D/p for 12-18 carbon chain surfactant = 1 * 10-6 cm2/sec N = 2 * 1014 molecules/cm2 Therefore, C = (n * 1000) / [2 * (D/ p)1/2 t ½ * N] = 1.7 * 10-3 M • The optimum concentration for maximum foaming has therefore been verified experimentally. Gibb’s Effect According to Gibbs, a coefficient of surface elasticity, E, is given by E = Coefficient of surface elasticity G = Surface excess concentration of solute hb = Thickness of bulk solution in the lamellae C = Bulk concentration of solute in moles/cm3 Cs = Surface concentration of solute, moles/cm2 Cm = Surface concentration of solute, moles/cm2, at surface saturation Gibb’s Effect • In thin films, length along the surface of the film is much greater than the thickness. Therefore, equilibrium normal to the surface, may be established much more rapidly than along the surface. • Significant within a certain concentration range. If the concentration is too low or too high (above CMC), the change in surface tension with increase in film area, will be too low to prevent rupture. • This mechanism also postulates an optimum surfactant concentration for foaming. Gibb’s Effect For surfactant concentration > 1/3 CMC Cs  Cm, therefore, E  when hb or C  E  G2; if G = 0, E = 0 For surfactants, Г falls in the range of 1×10-10 to 4 × 10-10 moles/cm2 At 27 C (300 K), therefore, or E = (1 to 16) × 10-9 / (hb × C) For E to be 10 dynes or more, hb must be 10-3 to 10-4 cm at C = 1 × 10-3 M, hb = 10-4 to 10-5 cm, at C = 1 × 10-2 M Factors Determining the Foam Stability (i) Drainage of liquid in the lamellae Drainage by gravity (thick lamellae) Bulk viscosity is a major factor. It can be increased by, (a) adding thickness (b) orienting surface molecules Drainage by Surface tension (thin lamellae)  P = g (1/RA + 1/RB) Greater the difference between RA & RB (bubble size) and the greater the surface tension g, greater the pressure difference causing drainage. B A Factors Determining the Foam Stability (ii) Diffusion of gas through the Lamellae The rate of diffusion q, of a gas, between two bubbles of radii R1 and R2 is given by, q = - J A P J = permeability of diffusion path A = effective area through which diffusion occurs P = difference in gas pressure of the two bubbles  P = g (1/RA + 1/RB), and P  2 g / R Larger bubbles tend to grow. As curvature  , drainage . Factors Determining the Foam Stability Transfer of gas between bubbles takes place through aqueous pores between the surfactant molecules in the surface films of the lamellae. Closer packing should reduce gas diffusion. Resistance to gas diffusion , when -CH2-  or molecular mass of the polar head . Addition of Lauryl sulfate and Lauryl Alcohol makes the permeability of surface films reduce sharply. (Condensation of lauryl sulfate film by the lauryl alcohol). Factors Determining the Foam Stability Thickness of the Electrical Double Layer A film of liquid composed of two charged monolayers may resist further thinning by: (a) repulsion between the approaching charged surfaces (b) high osmotic pressure (due to counter ion concentration) - - - - - - - - - - - + +++ + ++ ++ + + +++ - - - - - - - - - - - - 30 A 3/ 3/ 30 A ha - final total thickness = 6/ + 2 x (monolayer thickness), For 10-3 M Sodium Oleate solution NaCl (M) 0 10-3 Film thickness, Å Estimated 600+60 430+60 Experimental 700 420 10-2 10-1 180+60 60+60 280 120 Surface viscosity High surface and bulk viscosity can (a) Reduce the drainage rate. (b) Provide cushion against mechanical, thermal or chemical shocks. (c) Slow down self healing by surface transport mechanism. No definite correlation between surface viscosity and foam stability has been established. Solution drained, ml Surface viscosity Octanoic acid: Octanol molar ratio Surface viscosity Solution drained, ml Decanoic acid: Decanol molar ratio Relationship of Surfactant Structure to Foaming Foamability of a surfactant depends on (i) Its effectiveness in reducing the surface tension, and (ii) On the magnitude of its intermolecular cohesive forces Ionic surfactants more effective than nonionics in aqueous media. (due to larger surface area/molecule and the absence of highly charged surface in the nonionics.) Relationship of Surfactant Structure to Foaming In ionic surfactants effectiveness decreases with increased size of the counter ion e.g. in the dodecyl sulfate series NH4+ > (CH3)4N+ > (C2H5)4N+ > (C4H9)4N+ - Foamability also depends on the hydrocarbon chain length (goes through a maximum with increase in carbon chain) - Optimum chain length increases with increase in temperature C12 – C14 at 250C in distilled water C16 at 600C C18 at 1000C - Optimum chain length decreases in hard waters (Ca++) 300 ppm CaCO3 C12-C14 sulfates at 600C. Foam Stabilizers • • Additives that decrease the rate of attainment of surface tension equilibrium (e.g. by lowering the CMC) Additives that produce a closer-packed, more coherent film of high surface viscosity Examples: long chain, often water insoluble, polar compounds with straight chain hydrocarbon groups of about the same length as that of the surfactant. (i) Lauryl alcohol with sodium dodecyl sulfate (ii) Lauryl acid with potassium laurate (iii) N,N-bis(hydroxyethyl) lauramide with dodecyl benzene sulphonate Antifoaming Agents Foam Breakers- destroy existing foam by: (i) Reducing the surface tension locally (e.g. ethyl ether γ =17 mN/m) (ii) Promoting drainage of the liquid from foam (tributyl phosphate reduces surface viscosity) Foam Inhibitors- prevent the formation of foam by eliminating surface elasticity (i) By swamping the surface with non foaming rapidly diffusing, non cohesive, and only moderately surface active molecules (ethylene oxide-propylene oxide block copolymer) Antifoaming Agents Foam Inhibitors (contd.) (ii) By replacing the elastic surface film with a brittle, close-packed surface film. (calcium stearate or palmitate with the foam of sodium dodecyl benzene-sulphonate or sodium lauryl sulfate.