Chapter 2 Adsorption of Surfactants at Interface.ppt

§1. The surface excess concentration and the Gibbs adsorption equation About adsorption The interfaces of adsorption G-L surface adsorption – foam L-L interface adsorption – emulsion S-L interface adsorption – wetting, dispersing (2) Surface active and adsorption Surface active ? Adsorption on surface (3) Tow type in surface adsorption Orientation adsorption of hydrophobic groups; (b) Orientation adsorption of hydrophilic groups. 2. Surface excess concentration Interface phase (or layer) two phases inter-dissolved ?、? Thickness of interface phase a couple of molecules ~ 0.5nm in dilute solution (2) Surface excess concentration If total mole number of i component : ni0 (b) The concentration of ?、? phase Ci? Ci? and Ci? Ci? (c) The boundary surface ss total volume of ?、? phase : V?, V? ni = Ci? V? + Ci? V? (d) Surface excess ni? = ni0- ni=ni0- (Ci? V? + Ci? V?) (e) Surface excess concentration ?i= ni?/A A – area of ss-surface 意义：单位表面积上i 组分的摩尔数比本体相中相同数量溶剂所含i 组分摩尔数的超量。 对于表面活性剂：稀溶液区， Ci? Ci? ? 1, 即i 组分在吸附界面上，单位面积的摩尔数。 ?i= ni?/A = [ni0- ni]/A =[ni0- (Ci? V? + Ci? V?)]/A ? ni0 /A 2. Gibbs adsorption equation Thermodynamics Mono-component: U=TS-PV Multi-component: U=TS-PV +??ini In surface phase: U? =TS? -PV? +??ini? + ?A Total differential: dU? =TdS? + S? dT - PdV? - V?dP +??i dni? +?ni? d?I + ?dA + A d? ………………① Thermodynamic equation dU? =TdS? - PdV? +??i dni? + ?dA ………② ①-②, then S? dT - V?dP +?ni? d?i + A d? = 0 ( )TP ?ni? d?i + A d? = 0 or d? = -[?ni? /A]d?i d? = -??id?i d? = -??id?i Two-component :d? = -?1d?1 - ?2d?2 ss surface uncertain! So ?i – uncertain! (2) Gibbs method: If solvent i =1, then ?1 = 0 Gibbs eq. d? = - ?2(1)d?2 (1)-solvent 1 as frame of reference ?2= ?20 + RTlna2 Gibbs eq. d? = - ?2(1)d?2 = - RT?2(1)dlna2 (b) Gibbs equation ?2(1) = -(1/ RT) d?/dlna2 = -(a2/ RT) d?/da2 ? -(1/ RT) d?/dlnc2 = -(c2/ RT) d?/dc2 d?/dc2 0, c2?, ?