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gibbs adsorptiom

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Gibb’s Adsorption Isotherm: 

Gibb’s Adsorption Isotherm

SURFACE EXCESS: 

x 0 Δ A P Area left of x 0 : represents underestimated value of P i Area right of x 0 : represents overestimated value of P i SURFACE EXCESS A Property, P, of system vary across the interface (of thickness S) from that of phase ‘ A ’ and ‘B’ If P i is the value of the Property P at the ideal border of the interface, then: A B x 0 x P A P B Δ B S x A B x 0 x P P B P A Interface P i

SURFACE EXCESS (Cont.): 

SURFACE EXCESS (Cont.) X 0 - may be selected such that two shaded areas are equal -may divide the profiles of other properties differently Property which is least convenient to handle mathematically can be eliminated by selecting its surface excess to be zero. Note - dividing surface only a Reference Level rather than a physical boundary. - Surface excess can be positive or negative.

THE GIBBS ADSORBION EQUATION: 

THE GIBBS ADSORBION EQUATION Amount of surfactant adsorbed per unit area can be calculated from surface or interfacial tension measurements Where, d  = change in surface tension  i = surface excess concentration of ‘i’ d m i = change in chemical potential of ‘i’ At equilibrium where a i = activity of ‘i’ in bulk phase = mole fraction x activity coefficient

THE GIBBS ADSORBION EQUATION: 

THE GIBBS ADSORBION EQUATION Therefore For dilute solutions containing one non-dissociating surfactant Where C = molar concentration of surfactant in bulk At constant temperature Surface excess given by slope of plot of g versus log C Knowing  , area per molecule at the interface can be calculated.

AREA PER MOLECULE AT THE INTERFACE: 

Important in assessing Degree of packing Orientation of adsorbed molecules a = area per molecule (in Å 2 ) at interface, given by Where N = Avogadro number  = Surface excess in moles/m 2 AREA PER MOLECULE AT THE INTERFACE 1 x 10 20 N  a =

APPLICATION OF GIBBS ADSORPTION: 

APPLICATION OF GIBBS ADSORPTION Surface tension of aqueous solution of the nonionic surfactant CH 3 (CH 2 ) 9 (OCH 2 CH 2 ) 5 OH at 25 0 C is as given: C (x10 -1 ) mol/m 2 0.1 0.3 1.0 2.0 5.0 8.0 10.0 20.0 30.0 g( mN/m) 63.9 56.2 47.2 41.6 34.0 30.3 29.8 29.6 29.5

APPLICATION OF GIBBS ADSORPTION: 

CMC Surface excess is given by: Average area occupied by each molecule, APPLICATION OF GIBBS ADSORPTION