§8.2 Surface phenomenon of liquid Out-class reading: Levine p. 387-390 13.2 Curved interfaces §8.2 Surface phenomenon of liquid 8.2.2 Curved surface and additional pressure Convex surface Concave surface pex pex pin pex p pin pex p p additional pressure For convex surface: p>0 For concave surface: p < 0 §8.2 Surface phenomenon of liquid 8.2.2 Curved surface and additional pressure For curved surface: 1 1 p r1 r2 Laplace-Young equation r is the radius of curvature. 2 p r For convex surface, r > 0, p > 0, point to the interior of liquid; For concave surface, r<0, p < 0, point to the gaseous phase; For plane surface, r , p 0, pex = pin, §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Δ r Vm dp Vm Δp For liquid with plain surface: RT ln p* For liquid in droplet: r RT ln pr The droplets gradually disappear and the water level in the beaker increases. For droplet or bubble pr M 2 Δ RT ln * Vm Δp r p pr 2M ln * RT r p Kelvin equation §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface (1) supersaturated vapor / supercooling If a vapor is cooled or compressed to a pressure equal to the vapor pressure of the bulk liquid, condensation should occur. The difficulty is that the first few molecules condensing can only form a minute drop and the vapor pressure of such a drop will be much higher than the regular vapor pressure. pr = 2.95p* p = p* §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Relative humidity: 30 oC, 100%, 4.242 kPa 70%, 2.969 kP (45~65 %) For condensation: 30 oC (23 oC) For forming 1 nm droplet, vapor pressure should be as low as 1.438 kPa, (1.006 kPa) corresponding to ca. 12 oC (7 oC ) Plain liquid surface vs. droplet §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Artificial rainfall 1) Depress temperature using dry ice ln p vap H m RT k 2) Increase the initial radius of the embryo: dust, AgCl particles Adsorption; larger liquid diameter 干天的雨难下! §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Droplet can not form from the pure saturated vapor spontaneously. Therefore, in clean systems, large degrees of supersaturation or super-cooling are possible. Is embryo of a new phase possible? fluctuation Microscopic fluctuation plays important role in formation of new phase. §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface fluctuation §8.2 Surface phenomenon of liquid pex 8.2.3 Vapor pressure under curved surface 2) superheated liquid: pl pin p pin pex pl Δp r 0,Δp §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Boiling of a superheated water drop in sunflower oil。 The temperature of the system is 190 oC at ambient pressure Once the bubble of relative large diameter formed, the evaporation would proceed in an explosion manner—explosive boiling. §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Superheating: When temperature is over boiling point, liquid does not boil. 2 1 1 R ln 1 T T0 H vap rp0 The smaller the bubble, the higher the boiling temperature. For water with air bubble with diameter of 10-6 meter as seed, it boils at 123 oC. §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface Unsaturated, Saturated or Supersaturated? Video provided by Prof. Guo §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface 3) condensation in capillary: When liquid forms concave surface in capillary, r < 0 pr 2M ln * RT r p pr < p*, it is easy for vapor to condense in capillary. vapor Constant-temperature evaporation liquid Porous materials §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface 沐雾甲虫(Onymacris unguicularis), §8.2 Surface phenomenon of liquid 8.2.3 Vapor pressure under curved surface 3) supersaturated solution and ageing of crystal By simple modification of the above analysis, the same equations apply to the supercooling / supersaturated liquid or solution. Decrease in diameter of S r 2M solid will increase surface ln area and thus specific S RTr surface energy of the system and lower melting point, increase solubility of the solid. ageing of crystal The melting point of ultrafine powder may be only 2/3 of its normal one. Thermal plating §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading Superhydrophobic, superhydrobicity §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (1) Adhesion g-l + g-s s-l G = s-l – (g-l + g-s) = -Wa S Work of Adhesion g l Wa = g-l + g-s – s-l Wa > 0 The solid can be wetted by the liquid. §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (2) Immersion g-s s-l G = s-l - g-s = -Wi Work of immersion Wi = g-s - s-l > 0 §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (3) Spreading g-s s-l + l-g G = s-l + l-g - s-g = -S spreading coefficient S = s-g - s-l - l-g > 0 The liquid spreads over the solid spontaneously. §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading The contact angle () is the angle (4) Contact angle () measured through the liquid, where a liquid/vapor interface meets a solid surface Hydrophobicity of conversion layer on Mg alloy goniometer §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (4) Contact angle () g-l g-s s-l s g l s cos g l The direction of surface tension Under equilibrium: g-l cos + s-l = g-s Young equation When :g-s - s-l = g-l , cos =1, = 0 o, Complete wettable. When :g-s-s-l< g-l , 0<cos <1, <90 o, wettable. When :g-s < s-l , cos < 0, > 90 o, nonwettable. §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (5) Lyophobic and lyophilic solids g-l g-s g-s – g-l – s-l > 0 g-s > g-l + s-l s-l g-s > g-l The greater the specific energy, the easier the spreading of liquid over solid. §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (5) Lyophobic and lyophilic solids g-s > 100 mN m-1, high-energy surface: Metals, oxides, chlorides, inorganic salts. g-s 500 ~ 5000 mN m-1 g-s < 100 mN m-1, low-energy surface: organic solids, polymers. PTFE: g-s 18 mN m-1 Nonstick cooker §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (5) Lyophobic and lyophilic solids How can we judge the cleanness of the glass surface? §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (6) Spreading over liquid SO/W = - G = W - O - W/O SO/W > 0, oil can spread over water SO/W < 0, oil floats in shape of lens. Liquids Iso-C5H12O C6H6 C6H12 CS2 CH2I2 SO/W 44.0 8.8 3.4 -8.2 -26.5 §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (6) Spreading over liquid Clapham Common (2000 m2) 1774 Benjamin Franklin (2.4 nm) The film formed over water is of one molecule thick. (proved by Pockels and Rayleigh): Unimolecular film, monolayer, Insolvable film §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (6) Spreading over liquid Floating oil drop on chicken soup (lense) Floating oil on sea surface §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (6) Spreading over liquid wreck of a tanker Spreading of oil over seawater A environmental disaster §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading (6) Spreading over liquid 2010年5月5日,美国墨西哥湾原油泄漏事件 §8.2 Surface phenomenon of liquid 8.2.5 Interaction between two phases--Wetting and spreading §8.2 Surface phenomenon of liquid 8.2.4 Capillarity Capillary rise / depression §8.2 Surface phenomenon of liquid 8.2.4 Capillarity p pl 2 r h h( 1 2 ) g 2 ( 1 2 ) gr r cos R 2 cos h ( 1 2 ) gR Discussion §8.2 Surface phenomenon of liquid 8.2.4 Capillarity §8.2 Surface phenomenon of liquid 8.2.4 Capillarity §8.2 Surface phenomenon of liquid 8.2.4 Capillarity 2 cos h ( 1 2 ) gR Measurement of porosity distribution: p This relation can be used to determine the surface tension of liquids – capillary rise method Mercury method §8.2 Surface phenomenon of liquid Why cloud is white? And why does it turn dark before storm?
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