a eo & Contents CHAPTER A: 0 Surface residual energy Surface phenomena 0 Capillary phenomena & Adsorption a Adsorption a é s 2 ts a relative measurement of Surface free energy the energy atthe surface. Surface phenomenaa a Surface tension oo Surface residual energy e Mote ga ane ace C Ses ot ory 0h ato a REPL orion uo Fe ROR oon ee Intermolecular interactions in aliquid lower the intemal energy Molecules at the surface of the liquid experience fewer tiractions from other liguid-phase moleeulcs compared wit ‘molecules inthe bulk liguid phase and so have a higher average fenergy than moleales inthe bulk liguid phase. it requires ‘work to increase the area ofthe liquid vapor interface. Surface energy (for one component system) — [=| {Surface energy 6, crlem* eraPas The surface tension of = Energy needed io generate |e. surface tension of 4 unit surtace area energy to | Nad. YF is dofined as increase the size of surface) | the enetty (in Joule) needed (SGeveribleg inter) to create I m® of new liquide ts interfacial area a Sia=0 + Adwron oases sfc at Spon oe + (tt 2) => <0 2 No surface tension between gas-gas cocaineA) Surface tension gastiquia ©% Ex: For air, 25°C: [dyn.crv'} \Water: 72.75 Benzene : 28.28 (CCl, : 26.80 Surface tension liquiddiquid von on Ex: at 20°C, benzene water: 35,00 dyn cm! Surface tension gas-solid em” a *%eo 2e 20 3 Surface tension liquid-solid& Factors affect surface tension (© Temperature 2 Nature of phases ov" = MT, -T 6.0) De Wit = STE 8 = o,0-T/T)"; sas Effect of phase nature ‘Surface tension of water with various compounds 32086 (ayrvem aie | fso-pentane | benzene | n-hexane na 8 ey Measurement of surface tension (read in textbook) Capillary msthod Du-Nouy method Winery method Liquid drop weighting methodWeiting phenomena ingle t,t laeienan of he Mody th Mtl vol Gg = Gy + Oi C080 Tata aergonan ops aa /'* | amano te wt sto ee, (coaster praetor 19 Wotingleonct ange © 2 Weting segs: cosd 1 Weting enemy: 10° - 105 eaten ‘The contact anple it an angle tht a liquid creaes with a solid surface or capilay walls of a porous mateial when both ‘trials come in centat together. = ~_2_ ating Nomneting = Aenon Fores (ne ngosi pln. Cohesive foes > ahesive {i)> Cohesive Foes (vem Phin” forces, cs ~The molecule ofthe igi end ‘The molecules ofthe guid tend 0 4a inter more with ach other Interact mote with slid molecules thn wit dhe sod maleeles thom guid molecules eres Contact angle 12. This angle i detrmined by both properties ofthe soli and the liquid and the interaction and repulsion fores between liquid and solid ad by the three phase interface properties (gas liquid fang soho), 12 Those intractons are described by cohesion _and adhesion forces which are intermolecular frees. The balance between the echesive forces of similar molecules sich a6 ‘bere the lig molccules (ie Mydrogen bond and Van doe ‘Waals frees) and the adbesive forees between dissimilar molecules suchas between the liquid and solid molecules (Le. ‘mechanical and eleetostatie fores) will dewrmine the contat angle erated in he solid an guid interface. Capillary phenomena: The phenomenon of rise or fall of liquids ina capillary tube ~H ea) joo yy sz] [ox Weng creates meniscus (liquid-ir interface): convexa Thompson — Kelvin equation oe ~ Convex merisis: (postive rear» 0) RT inky = 200 = Concave mena: fegate rel ¢=-7<0) RTIngy = 222 Tiquid molar volume ai + Ex: water ~ Convex menses: 10% emf ~ Concave ments 10m. ADSORPTION a é Adsorption: Concentrating substances on the ‘phases’ separating surface 12 Adsorbent: materials on which the adsorpton occur. 12 Adsorbate: substances which i attract on the adsorbents surface (the phases’ separating sutace) 15 Reason: tne ron- equirum interacton forces ot surtace’s $e Adsorption: Concentrating substances on the phases’ separating surface [Roe nda Uptake Adsorbent‘Types of adsorption Physisorption (NI Ad meron ie) (Chemiserption Chemisorption vs. Physisorption fy i emma bio Adsorption capacity: P or x (mol/g or ml/g) Cienianrin Paytaapton & adsorption isotherms a Te. lista eT 100K C01 1 Factors affect adsorption [200K = Cone. r swpeenenpy| <2-¥hisImt | 50k ow enbaey ‘Temp. wes a cial ny ior bia) Bi — = roi | Soocepanes | Meenas ce i = Sono lner aoe oe =| Seeciny Tigh non-selecivty strngeinteracon [7 y— 1hAl Gas/solid adsorption "a Langmuir isotherm tor nondiesoiaton modeh a Assumptions Uniform surface = Menelayer aéeorption = No interacion between adsorbed species and no ‘movement ofthe adsorbed species Langmuir isotherm a _ P Linear form: = o-SP_ Skerenagenne sone \V, Vig; Volume/ maximum volume of THKP stems adsorbed gas on the adsorbent (ml/g). a é Langmuirisotherm Langmuirisotherm ie pa ke _, KP VeNn TKR XO FKP 5 IF Fis low (KP <1) > v, care arecty proportonal to F IF Pishigh (KP >> 1) + v,x> max,A) Example a peepee ste ees sconces el ‘Sirscamvennare acne crane (ys nensane Vous eh ‘Shecdio tava ib Pa) Ancol rca eg Langmuir model ' y= 0.00018 + 1.196 RP 09984 Freundlich isotherm = b-P'"| inv=ind+ 2 adsorption capasity; : pressure of gas on the adsorbent at equirum; bonveanstant Freundlich isotherm a Application: - For gas'solid adsorption: tin 1 = 0.5 - For liquid/solid adsorption: (replace P by C) 1in=02-1 12 Adsorbed species iret only th the below and above species, not the besidea Determination of specific surface area: [m?/a] v,N-A Vim a a) oe Adsorbents 12 Solid adsorbents: selective adsorption, heterogeneous Catalysis, cataysts supports, Gas-chrematography, water treatmentpuriation i vine ees ss Non-porous Porous lon-exchange Sear eeeeeeiertes) © v adsorbents adsorbents ‘adsorbents eee tre ca [ie Pip.) TO=PIR) VC Val | a os Molecule adsorption Liquid/ solid adsorption (adsorption of non-lectrolytes) © Basic nes: © Simitar gasisolid adsorpticn, except the competition of the solven: during the adsorption which lead to complexity of the liquid/solid adsorption. @ Freundlich, Langmuir. BET car be applied for liquid/solid adsorption (replace > by C) Rule of molecule weight: adsorption capacity increase {as increasing the C-chain length. However, adsorption ‘capacity decrease rapily at certain U-chain length for porous adsorbents due tothe space constrain, + Basic ies: Repinala'srute: Oireccion of adsorpion is equtlorate the polarity 3 the phases, The greater polarization aferenceresuls inthe stronger adsorption.a oe Adsorption of electrolytes Rules: 4. For simiar valence ions, large ion rats are adsorbed ai fst due to tin hydration layer and lange polarization: a. LieNa‘ anion exchange). callont (containing ‘cabox}i, sul» cation exchange) 10 Characteristics: high selectivity because this Is a Chemical adsortion. reversible process is possi the rate is slow, especially the inner pad of the ‘adsorbents. The pH of the solution may change due to the rolease of H* Adsorption for water treatment Adsorption on liquid-gas interface urfactant Sal hy “7 Aderpan onthe merfise>0) 1 Spotncs 8 Ce eee egatneadoon (TO) "Ronayne ares (Cat Pur)Adsorption at liquid gas interfaces Gibbs adsorption equation ldo RT’ d\nC Gibs surface excess. T= TT the surface excess concentration (the Gibbs suface excess, mol/n?) ) a eee eee reese 2 for: ionic sractans inthe abn of add lets eter oeed aura tron univer gs consant ‘absolute temperature